Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Lubricants
Handbook:
Technology,
Properties,
Performance,
and Testing
George E. Totten, Editor
Section Editors
Steven R. Westbrook
Rajesh J. Shah
ASTM International
100 Barr Harbor Drive
PO
Box C700
#
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Foreword
This publication, Fuels and Lubricants Handbook: Technology, Properties, Performance,
and Testing, was sponsored by ASTM Committee D02 on Petroleum Fuels and Lubricants and edited by George E. Totten, G. E. Totten & Associates, LLC, Seattle, Washington. The section editors were Steven R. Westbrook, Southwest Research Institute,
San Antonio, Texas; and Rajesh J. Shah, Koehler Instrument Company, Bohemia, New
York. This publication is Manual 37 of ASTM's manual series.
Contents
PrefaceGeorge E. Totten, Steven R. Westbropk, and Rajesh J. Shah
ix
31
61
89
115
145
169
185
199
249
267
Remmelmann
297
vi
CONTENTS
Chapter 13Hydraulic Fliiids
Willie A. Givens and Paul W. Michael
353
383
413
431
465
497
525
557
573
587
635
649
Chapter 25Volatility
Rey G. Montemayor
675
707
717
729
757
CONTENTS
Chapter 30Oxidation of Lubricants and Fuels
Gerald J. Cochrac and Syed Q. A. Rizvi
787
Chapter 31Corrosion
Maureen E. Hunter and Robert F. Baker
825
833
879
Hoover
885
909
963
1017
1043
Index
1061
vii
Preface
There are many books on various aspects of fuels and lubricant chemistry, applications,
and testing. However, few focus on testing and none provide extensive, in-depth coverage on fluid properties and testing methodologies together. And while there are numerous national and international standards that deal with specific testing procedures
appropriate for fuels and lubricants, it is generally beyond the scope of these procedures to provide an extensive discussion of the principles behind the tests and their relationship to the properties themselves. Therefore, there is a strong need to address
these informational shortcomings in the Fuels and Lubricants industry, which is one of
the most significant tasks undertaken in this work.
The ASTM Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing is an extensive, in-depth, well-referenced handbook that provides
a detailed overview of various testing methodologies and also provides a thorough
overview of the applications-related properties being tested. Since this manual provides
an overview of all of the ASTM and important non-ASTM test procedures relating to the
application areas addressed, it is an excellent companion text to the Annual Book of
ASTM Book of Standards, or it is an invaluable reference manual on its own.
The organization of the ASTM Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing is based approximately on the committee structure
of the ASTM D.02 Petroleum Fuels and Lubricants Committee and the standards for
which each committee is responsible. The information in this text is subdivided into
four sections: I-Petroleum Refining Processes for Fuels and Lubricant Basestocks;
II-Fuels; Ill-Hydrocarbons and Synthetic Lubricants; and IV-Performance/Property
Testing Procedures.
This manual contains thirty-eight chapters covering the following topics:
An overview of petroleum oil refining processes
Liquified petroleum gas (LPG)
Aviation, automotive diesel, non-aviation gas turbine, and marine fuels
Gasoline and oxygenated fuel blends
Petroleum hydrocarbon base oil chemistry
Synthetic hydrocarbons
Environmentally friendly fluids including those formulated from vegetable oil and
synthetic ester basestocks
Lubricating oils for turbines, compressors (industrial and refrigeration), gears, and
automotive applications
Metalworking fluids
Petroleum waxes
Lubricating greases
Oils used in non-lubricating applications: heat transfer fluids and metal quenchants
Detailed discussion on: static petroleum measurement, volatility, elemental analysis,
fuel combustion characteristics, oxidation, corrosion and viscosity
Properties of coke, petroleum pitch, and carbon materials
Hydrocarbon structural analysis procedures
An extensive discussion of lubrication and wear
Environmental and toxicity testing
Statistical quality assurance testing procedures
Essentially, all of the numerous important applications and test methods involved
in the Fuels and Lubricants industry are discussed and referenced here. We strongly
believe that this book will be an invaluable resource for anyone working in this
industry, especially since this information is not available in any other single source.
ix
PREFACE
The preparation of a text of this scope was an enormous task involving many people.
The editors are deeply indebted to the authors for their h a r d work and incredible patience. Specicd thanks go to Monica Siperko and Kathy Demoga at ASTM for their continued support and encouragement throughout the development of this text. The editors are especially indebted to their families for many evenings and weekends lost to
this project. We Eilso acknowledge the vital support of Southwest Research Institute and
the Koehler Instrument Corporation.
George E. Totten
General Editor
G.E. Totten & Associates, LLC.
Seattle, WA, USA
Steven R. Westbrook
Section Editor-Fuels
Southwest Research Institute
San Antonio, TX, USA
Rajesh J. Shah
Section Editor-Lubricants
Koehler Instrument Company
Bohemia, NY, USA
MNL37-EB/Jun. 2003
Copyright'
2003 by A S I M International
www.astm.org
HANDBOOK
C, + C,
GASES
REF. FUEL
PROPANE
LPG
ALKYLATE
-MTBE
GASOLINE
LPG
BUTANES
CRUDE
LSR
A
T
M
D
I
S
T
ATM V
ISOMERIZATION
-GASOLINE
NAPH
HYDROTREATING
KERO
HYDROTREATING
GAS OIL
CAT
REFORMING
JET FUEL
HYDROTREATING
GASES
RESID
No. 2 FO/DIESEL
MTBE
ALKYLATION
L
V
A
C
D
I
GASOLINE
GASOLINE
GASOLINE
FLUID
LVGO
LCO
No. 2 FO
CATALYTIC
HCO
CRACKING
HVGO
DO
No. 6 FO
CARBON BLACK
H, PLANT
HYDROCRACKING
No. 6 FO
ASPHALT
VAC RESID
REFORMER FEED
JET FUEL
VISBREAKING
DEASPHALTING
COKING
HYDROCRACKING
Vacuum Gas Oils (LVGO and HVGO)i:\iese cuts are usually processed in the FCCU. They can be processed in a hydrocracking unit (HCU) wherein they can be converted
into catalytic reformer feed, jet and diesel fuel, and for production of lubricating oil base stocks.
Vacuum ResidThe residuum portion of crude oil is the
non-distillable cut, boiling above, say, 575C. It cannot be
distilled without causing substantial thermEd destruction
of its hydrocarbons. This cut is sold to the asphalt and
heavy fuel oil markets, or processed by the options shown
in Fig. 1.
CHAPTER 1: PETROLEUM
TABLE 1Crude section cuts.
Carbon
Number
Name/Other Names
Gases
Light straight run gasohne
light n a p h t h a
LSR
gas condensate
Heavy straight run naphtha
Heavy naphtha
Naphtha
Reformer feed
Kerosine or kerosine
jet
Light atmospheric gas oil
furnace oil
diesel
Heavy atmospheric gas oil
AGO
gas oil
Light and heavy vacuum gas oils
LVGO and HVGO
Vacuum resid"
vacuum bottoms
short resid
vacuum reduced crude
asphalt
C1-C4
C5-C6
Approximate
Boiling Range, "C
-160-0
25-90
C6-C10
85-190
C9-C15
160-275
C13-C18
250-340
C16-C25
315^10
C22-C45
370-575
C40+
500+-565 +
OIL REFINING
Chain/Ring
Saturated/Unsaturated
Example
Chain
Chain
Ring
Ring
Saturated
Unsaturated
Saturated
Unsaturated
Hexane
Hexene
Cyclohexane
Benzene
The four types are listed in the order shown after chemical analysis, and are usually referred to by the term PONA
analysis (ASTM Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption, D 1319-98). In chain hydrocarbons, all carbon atoms
can be linked in a straight row; these are the "normal" versions, such as the example of a six-carbon hydrocarbon,
normal hexane (n-hexane). "Isomers" of n-hexane exist as
branched-chain versions; as a group, these are labeled
isoparaffins, for example i-hexanes. They are commonly
connotated as nC6 and iC6s. When a hydrocarbon type
analysis is made that includes a normal/isoparaffin split, the
normals keep the letter P, the isos take the letter I, and the
olefin/aromatic order is reversed, resulting in the acronym
PIANO. This same split is not attempted for the normal and
branched-chain olefins because of the greater number of
potential olefin structures and the lesser impact on refinery
process options.
HYDROCARBON TERMINOLOGY
There cire four basic tjrpes of hydrocarbon chemical structures. Their differences relate to the bonding between carbon
atoms and whether the carbon bonds create a chain- or ringshaped molecule. The number of electrons in the outer shell
of a carbon atom requires each atom to have four bonds to be
stable. This four-bond requirement can be peirtially met by a
carbon atom forming single or multiple bonds with adjacent
carbon atoms. Nearly all hydrocarbon molecules encountered in refining chemistry consist of all singly bonded carbons, or contain pairs of doubly bonded adjacent carbons;
the remaining bonds cu-e satisfied with hydrogen. When eill
carbon-carbon bonds in a molecule are single, it is called saturated, because it contains the maximum possible amount of
bonded hydrogen. When there cire double bonds present, the
hydrocarbon is labeled unsaturated, since it holds less than
Region
Asia/Pacific
Western Europe
Eastern Europe/FSU
Middle East
Africa
North America
So. America/Caribbean
Chemical
Name
CI
C2
Methane
Ethane
Ethylene
Propane
Propylene
C3
C4
End Uses
n-Butane
i-Butane
Butylenes
1020
740
540
300
160
1010
340
23
36
35
34
15
46
43
4110
Source: Oil & Gas Journal Worldwide Refining Report for January, 2001.
13
15
8
5
6
33
19
9
13
12
9
11
19
5
41
58
38
37
25
68
29
Coke
0.4
0.5
0.8
0.3
0.2
4.5
1.8
MANUAL
HANDBOOK
By chemical naming convention, all saturated hydrocarbons, the paraffins and naphthenes, end in the letters "ane,"
while all unsaturated hydrocEirbons, the olefins and aromatics, end in the letters "ene." Each of the four species has different properties and reactivity, and this plays a major role in
refinery unit selection and operation. The amount of the various heteroatoms and the m a n n e r in which they are bound to
carbon also is critical to refinery operation. These factors will
be apparent throughout the remainder of this chapter as well
as in other parts of this manual.
C R U D E OIL
Hydrocarbon Composition
Crude oil is composed of aromatic, paraffin and naphthene
hydrocarbons. Minor amounts of olefins may be present. Average aromatics content is about 50%; however, it can range
from as low as 2 5 % in light paraffinic crudes to as m u c h as
75% in heavy oils, such as those recovered from Canadian tar
sands. The paraffin/naphthene ratio is widely ranging and is
qualitatively identified via the labeling of many crudes as
"paraffinic" or "naphthenic." Hydrocarbon composition affects many considerations in selecting processing options, or
meeting product specifications, as shown by the following examples:
Aromatics
Because of their inherent molecular stability, they are the
bane of refining. Aromatics are the most difficult compounds
to thermally crack, hydrogenate, and desulfurize. They are
increasingly "unwanted" species in fuel products because
they are the hardest to completely combust, thus contributing more to pollution and equipment maintenance. As product aromatics content is regulated to lower levels, refinery
process severity and costs will increase. Aromatics do have
value in the refinery flow plan as a high-octane gasoline
blending component from the catalytic reforming unit and in
the recovery of chemical grade aromatic feedstocks for the
petrochemical industry.
Paraffins
and
Naphthenes
Nitrogen
Generally, nitrogen content is about 5-20% of sulfur content
in most crudes. This is a helpful circumstance because nitrogen removal requires greater process severity than sulfur removal since nitrogen is mostly bound in ring form while a
greater percent of sulfur is bound in chain form. Heteroatom
removal from rings is more difficult than from chains. Many
California crude oils are high in nitrogen content, often
equaling sulfur content, and thus require greater process
severity than other crudes of equal sulfur content.
Metals
Organometallic compounds are predomineintly found in the
vacuum resid. Important metals are nickel, vanadium, copper and iron, with nickel (Ni) and vanadium (V) usually in
highest concentration. Ni + V levels in resid range from a few
p p m to as m u c h as 1000 ppm. The metals, particularly Ni,
have an adverse effect on catalyst performance and have
specified maximum limits in products such as heavy fuel oil
and petroleum coke. This can affect crude selection options
for many refinery process configurations and product slates,
as well as in process selection for future refinery revamp/expansion projects.
Oxygen
Acids, particularly naphthenic acids, and phenols constitute
the main organic oxygen compounds in crude oil. A substantial portion are in the naphtha, kerosine, and gas oil boiling
ranges. These compounds are readily eliminated via hydrogenation, and will pose less concern as more hydrotreating is
CHAPTER
added to the flow plan to achieve greater sulfur removal. If
these streams are not hydrotreated, the acids are usucJly removed by many variations of caustic treating.
PRODUCTS
The main refinery products, except for the gas streams shown
in Table 3, are automotive gasoline, kerosine/jet fuel. No. 2
and No. 6 fuel oils, and No. 2 diesel fuel. Changes to the refinery flow plan have mainly been driven by changes in crude
oil quality, and in specifications and demand for these products. It should be noted that all industry fuels and lubricants
are presented in this manual including a complete presentation and discussion of test methodology and properties.
Gasoline
The first meaningful specifications evolved in the 1920s.
From this beginning until 1990, the two key control properties have been "octane number" and "volatility." Octcine number, the measure of the engine to resist the rapid "pinging"
noise, called "knock," due to improper combustion, steadily
increased as engines became larger and more powerful, peaking in the eeirly 1970s. The refinery met the required octane
appetite of the car population by instcJling processes that
produce high octane streams, such as the FCCU, CRU, and
alkylation and isomerization. In addition, organolead compounds, mainly tetraethyllead (TEL), were used to add about
eight octane numbers to the gasoline pool.
Two laboratory octane n u m b e r test methods are used to
measure and control this gasoline quality parameter, the Research Octane N u m b e r (RON) and Motor Octane N u m b e r
(MON), per ASTM Test Methods for Research Octane Numb e r a n d Motor Octane N u m b e r of Spark-Ignition Engine
Fuel, D 2699-97a and 2700-97, respectively. Their different
operating conditions, detailed in this manual, act to delineate
and bracket the potential for knock in the automobile population. In most of the world, RON is the value the consumer
sees at the "pump," while in the United States and Canada,
the average of both the RON and MON is the guiding specification.
The first significant response to pollution from vehicular
emissions came with the passage of the U.S. Clean Air Act in
1973. This legislation stipulated that the m a i n pollutants
emitted from the automobile tailpipe; namely, u n b u m e d hydrocarbons, carbon monoxide and nitrogen oxides, had to be
reduced by 90%. The automotive industry chose to use a catalyst to comply with this regulation. This "catalytic converter" requires platinum, or other noble metal such as palladium, to effect the desired emissions reduction chemistry.
Platinum's activity, however, is adversely affected by lead. As
a result the oil industry had to remove lead from gasoline and
would have lost the eight octane numbers from the addition
of TEL. The Act also required an increase in fuel economy
from 12.5 mpg (5.35km/l) to 27.5 mpg (11.77km/l). This led
to a reduction in vehicle weight and power, which in turn reduced octane appetite by about four numbers. Thus, the net
effect on the U.S. oil industry from 1974 through the mideighties was to add about four octane numbers to the base
gasoline pool. This was achieved mainly by the addition of
1: PETROLEUM
OIL REFINING
process technology such as catalytic reforming and alkylation. However, the industry also introduced organic oxygenates to gasoline blends, initially alcohols and then ethers,
since such compounds have high octane quality (Table 4).
Of the three utilized alcohols, the only surviving member is
ethanol, which is used in the U.S. through the help of government price subsidy. Concern for water solubility, corrosion, and emissions problems from the alcohols, verified or
not, drove the U.S. refining industry to the ethers. The first,
a n d still dominant, ether was methyl tertiarybutyl ether
(MTBE), which was initially provided by ARCO Chemical
converting tertiarybutyl alcohol, a by-product from their
propylene oxide process, to the isobutylene feed needed to
make the ether.
Volatility requirements can be described as the control of
the boiling range of the gasoline to assure that the automobile operates properly during startup, warm-up, and hot operation. Gasoline specifications assure that there is a proper
balance among the C5 through C l l hydrocarbons that constitute the gasoline boiling reuige, and that the final boiling
point is limited. Volatility control also includes the need to
add liquefied n-butane to provide sufficient vapor pressure
(ASTM Test Method for Vapor Pressure of Petroleum Products (Reid Method), D 323-99a) to ensure cold engine startup.
This results in "seasonal" volatility grades wherein butane
content and boiling range Eire varied to match expected ambient temperature.
As industry used the oxygenates to meet octane number requirements, data showed oxygenates can reduce pollutants
such as carbon monoxide (CO) and nitrogen oxides (NO^).
And, as analysis of the effect of various gasoline constituents
on tailpipe emissions became better defined, it became apparent that other compositional changes would be beneficial.
This was addressed by passage of the U.S. Clean Air Act
Amendments in 1990. This legislation, and subsequent regulations such as those enacted in Ccdifomia, has substantively
changed the entire composition of gasoline (Table 5), per
ASTM Specification for Automotive Spark-Ignition Engine
Fuel, D 4814-99. As a result, the refinery has undergone continuous change to meet the cleaner fuel product requirements. These changes, initiated in the U.S., are being adopted
throughout most of the world; in some instances, legislation
in other locales is resulting in even more severe specifications
(Table 6).
Source
Name
Alcohols
Methanol
Natural Gas
Ethanol
Crops
t-butyl alcohol Propylene Oxide By-Product
Alcohol
Ethers
MTBE
TAME
ETBE
TAEE
DIPE
133
130
109
99
96
93
54
27
17
6
118
111
118
100
98
102
Olefin
Methanol
Isobutylene
Methanol
Isoamylene
Ethanol
Isobutylene
Ethanol
Isoamylene
(Propylene + Water)
32
16
12
104"
94
86
0.8
100
90
0.9
62-103
0
1992-1994
1974-1991
Remove Pb,
Increase Fuel
Economy
91
83
0.1
"
98
88
0.1
1995+
91
83
0
98
88
0
50-90
2.0-2.7*
0.8-1.0
165-180
20-35
4-10
30-150
2.7*
0.3-1.0"
185-190
30-45
8-15
300-500
United States
1998-2000
2004
Locale Year
Oxygen, %w
MTBE, %w
Benzene, %w
Sulfur, p p m w
Aromatics, %v
Olefins, %v
2.0-2.7
11.0-14.8
0.95-1.0
150-350
25-32
6-12
0.0-2.7
Unknown
0.8-1.0
30-150
20-30
4-9
Europe
1996
2000
2005
2.0
11.0"
0.8-1.0
30
25
4-6
2.7
14.8
1.0
150
35
14
2.7
14.8
1.0
10-30
30-35
12-14
Today's military and commercial aircraft use jet fuels that are
produced almost exclusively from the kerosine fraction of
crude oil or similar boiling range cuts from certain refineiy
processes (Table 7). Key requirements focus on sulfur and
aromatics contents, clean burning characteristics, and storage stability (ASTM Specification for Aviation Turbine Fuels,
D 1655-99). Increasingly, refineries use hydrotreating technology, as well as crude slate selection, to meet specifications
and aircraft power demand. Legislative reduction in sulfur
and aromatics is not currently anticipated.
F u e l Oil
The various fuel oil grades are shown in Table 8 (ASTM
Specification for Fuel Oils, D 396-98). The major products
are No. 2 and No. 6 fuel oils. No. 2 fuel oil, commonly called
furnace oil or home heating oil, is the fuel used for residential and small commercial oil heating systems. No. 6 fuel oil
is commonly called industrial or heavy industrial fuel oil
when used by utilities for electricity and steam generation.
It is called Bunker, or Bunker C, fuel when used by the marine industry for those ships powered by "furnaces." Nos. 1,
4, and 5 are specialty products. For example, No. 1, also
known as stove oil, is a kerosine-type blend for small stovelike non-atomizing b u r n e r s a n d some farm equipment,
while Nos. 4 and 5 are lower viscosity industrial fuel oils for
smaller commercial furnaces such as those used by schools
and hospitcds.
Sulfur content is an important quality parameter. While
most No. 2 fuel oil is specified at 0.5%, maximum, (ASTM
Test Methods for Sulfur in Petroleum Products, D 129-95,
D 1266-98, and D 2622-98, for example) m u c h product has
considerably lower sulfur because of the n e w low sulfur
diesel requirement. Many refiners have found that the added
cost to desulfurize No. 2 fuel oil to match diesel specifications may be offset by reducing the n u m b e r of separate products, providing increased product blending options and reducing storage and distribution costs. No. 6 fuel oil sulfur
ranges from 0.25-3.5% depending on end use and locale. It is
anticipated that average "six-oil" sulfur content will decrease
over time.
No. 1
Stove
and Farm
No. 2
Home
Heating
850
288
38
-18
0.3-0.5
876
338
38-55
-6
0.3-0.5
1.3
2.1
1.9
3.4
No. 4
No. 5
No. 6
Light
Industrial
Medium
Industrial
Heavy Ind'l
& Marine
55
-6
55
60
0.25-3.5
5.5
24.0
5-9
9-15
15
50
CHAPTER
TABLE 9Diesel fuel specifications.
No. 1
No. 2
No. 4
Uses
Farm,
City Bus
Automobile
Truck,
Railroad
Railroad,
Marine,
Stationary Engine
288
10-5000
40-55
38-55
10-35
338
10-5000
40-55
52-55
10-35
20 000
30
55
Grades
Diesel Fuel
Key diesel fuel specifications and major uses eire shown in
Table 9 (ASTM Specification for Diesel Fuel Oils, D975-98b).
The U.S. Clean Air Act Amendments also required the reduction of sulfur to 0.05% (500 ppmw), maximum, for over-theroad usage; namely, buses, trucks, and automobiles. The legislation did not require lower sulfur for other use such as the
railroad and marine industry. Again, as with the fuel oils,
m u c h No. 1 and 2 diesel is made "low sulfur" for all markets
to minimize product distribution costs. Driven initially by
European and California legislation, diesel fuel sulfur is being further reduced toward 10-50 ppmw, requiring more severe hydrotreating.
While the U.S. law did not substantially constrain aromatics content, California law did, requiring reduction of aromatics to as low as 10%. Worldwide adoption of this level of
dearomatization will be difficult to achieve near-term, but a
trend toward lower aromatic content diesel is occurring. This
is being affected in part by requiring higher Cetane N u m b e r
diesel fuel (ASTM Test Method for Cetzuie Number of Diesel
Fuel Oils, D613-95). Aromatics decrease "cetane rating."
P o u r point (ASTM Test Method for Pour Point of
Petroleum Products, D97-96a) and cloud point (ASTM Test
Method for Cloud Point of Petroleum Products, D5771-95)
are importctnt parameters to assure proper flow of fuel oils
and diesel fuels under all anticipated ambient temperatures.
Pour point must be low enough to prevent solidification of
the entire fuel while cloud point must be low enough to assure that normal paraffins will not solidify and block fuel
flow in piping or through nozzles.
1: PETROLEUM
OIL REFINING
HANDBOOK
Condenser
0iS^SI I
Atmospheric
Distillation
*'Wet Gas
*LPG
Reflux
Light
"B-' Water
r'stabifeation'l Straight Run
-*
and.
^
L.SpJtttinjtJ_*
xr
~ ) P Stripper
Naphth:
Kerosene
Crude
Stripper
Steam
-Water
* Diesel
Preheat
Desaiteri
"Gas Oil
Steam
Brim
Preheat L f i j J
Preflash
Drum
Vacuum
Distillation
Furnace^i=J
-Topped Crude
Steam
Non-condensat)les
and steam
PreCondenser
High Pressure
Steam
NonC.W. condensables
O
Naphtha
Sour Water
Topped
Crude
Q Ejectors
Coil
Steam
Stripping
> Vacuum Resid
Steam
FIG. 2Atmospheric and vacuum distillation units.
coke "lays down on" the fluidized catcJyst particles, diminishing their activity. The "coked-up" catalyst is continuously
removed from the reactor section and transported with air to
the regenerator wherein controlled combustion converts the
coke into a "flue gas" consisting mainly of carbon monoxide
(CO), carbon dioxide (CO2), water (H2O), and sulfur and nitrogen oxides (SOx and NOx) resulting from the presence of
sulfur and nitrogen in the feed. This combustion raises the
catalyst temperature to 680-760C which, in turn, supplies
most or all of the heat to raise fresh feed to its reactor temperature as the "hot" regenerated catalyst is continuously removed from the regenerator and re-mixed with fresh feed. In
fact, many FCC units operate in heat balance, meaning that
all heat to raise the feed to reactor temperature is supplied by
the regenerated catalyst.
CHAPTER
nozzles, and taking advantage of favorable FCCU process
economics. Factors favoring economics include the ability to
produce high yields of high-value gas and gasoline from low
value feed, substantial yield flexibility resulting from catalyst
selection and variable operating parameters, operation at essentially atmospheric pressure, and no addition of hydrogen
as is required in the hydrcracking process.
The cyclone systems in both the reactor and regenerator are
mechanical devices to collect the catalyst carried out of the
dense phase fluidized beds by the respective cracked product
and flue gas vapors. Although thousands of tons of catalyst
circulate each day, cyclone efficiency is so close to 100% that
losses are kept in the 1-10 ton-per-day range. The losses from
the reactor are returned via the downstream product recovery
train. Losses from the regenerator are collected and then disposed, thus creating the need for daily catalyst replacement.
Early catalysts were silica-alumina "clays" incapable of
processing resid and limited in activity. Today's catalysts
contain various highly active zeolites, combined with appropriate silica-alumina bases, which permit the processing of
heavier, dirtier feed, as well as provide increased yields of
Reactor Vapor
Reactor
Reactor Riso'
Regenerator
/
Spent-Catalyst
Stripper
Combustor
Riser
Catalyst
Cooler
(Future)
Combustor
Spent-Catalyst
Standpipe
RecirculatedCatalyst
Standpipe
RegeneratedCatalyst
Standpipe
CooledCataiyst
Standpipe
(Future)
Chargestock
t
Combustion Air
UitGas
FIG. 3Fluid catalytic cracking unit.
1: PETROLEUM
OIL REFINING
11
Gasoline
Gas
Distillate
Reactor Products, %w
C1-C2
C3s
C4s
Gasoline
Light Cycle Oil
Heavy Cycle Oil
Coke on Catalyst
3
6
11-12
46-52
15-19
7-8
6
6
22
20
27
12
5
8
2
4
8
38
35
9
4
12
MANUAL
HANDBOOK
case, the sensitivity of the catalysts to coke, and to deactivation from heteroatoms such as sulfur and nitrogen, requires
that the naphthas first be hydrotreated.
Fresh hydrotreated naphtha feed plus recycle hydrogen is
heated to reactor temperature of about 500-530C in a furnace and fed to the first reactor. The over-riding chemistry is
endothermic dehydrogenation of naphthenes to aromatics.
Thus, as the feed progresses down through the catalyst, as
m u c h as 60C cooling occurs from top to bottom in the first
reactor, reducing activity and hence aromatics yield. The net
effect is that octane n u m b e r gcdn in one reactor is not enough
to make the process attractive. Therefore, the reactor effluent
is reheated in a second furnace, or in a second coil within the
same furnace, back to 500-530C and fed to a second reactor,
and so on, until desired octane product is attained. Cat reformers usually consist of three reactors although as many as
five are utilized.
Typical yields at two product RON levels are shown in
Table 11. The net hydrogen produced from aromatics formation is the m a i n source of hydrogen in the refinery for its
desulfurization and related needs. Refineries are in "hydrogen balance" if all such hydrogen can be provided by the reformers. If not, refiners purchase hydrogen or build their
own hydrogen plants.
Figure 5 depicts the main process parameters of catalytic
reforming; namely, the "yield-octane" relationship. Higher
octane n u m b e r d e m a n d requires higher reactor temperature
and/or longer residence time. Both will cause more of the
naphtha feed to crack into gas and thus reduce gasoline 3rield.
"Reformer severity" is uniquely defined as the unleaded RON
of the C5 + liquid product, the second major gasoline blending component. In fact, the gasoline streams from the fluid
cat cracker emd cat reformer make u p about two-thirds of the
world's gasoline.
Significant changes in feed composition to the reformer
a n d in downstream utilization of the reformate are occurring, related to the move toward cleEmer fuels. The major
source of benzene in gasoline is catal3^ic reformate. The
trend is to reduce benzene to a m a x i m u m of 1%, with the potential for even lower limits being legislated in parts of the
world. When the p u s h for lower benzene content began,
worldwide benzene levels ranged from as low as 1.6% in the
U.S. to as high as 5% in pEirts of Europe and Asia. Refiners
can reduce benzene concentration as follows:
1. Remove benzene precursors from the feed. This is accomplished by increasing the initial boiling point of the heavy
naphtha feed, or, in essence, raising the cut point between
light and heavy straight run naphtha. This results in less
feed available to the reformer and lower octane quality in
the resultant higher boiling range light straight r u n
stream.
2. Leave the benzene precursors in the feed. In this case, refiners can then distill the C6 cut from the reformate. Benzene can be extracted from this cut for chemical sale, or the
benzene can be reacted with olefins to produce alkylbenzenes. The C6 cut can also be hydrotreated to convert benzene to cyclohexEine with a resultant loss in octane number.
Clcciner gasoline also mcindates lower final boiling point
and lower total aromatics. This requires the refiner to eliminate a substantial portion of high boiling fraction from the
naphtha feed and, in some cases, to r u n the reformer at lower
Recycle hydrogen
Off Gas
^^-^c^O
Heavy
Naphtha
C3s&C4s
Separator
Reformate
Continuous Catalytic
Reforming Unit
Spent Catalysi
Product
'Separatiofi
Naphtha &
Recycle Gas
13
HANDBOOK
102
94
Yield, %w
Hydrogen
CI + C2
C3
iC4
nC4
C5+ Reformate
3.0
3.7
3.5
1.8
2.5
85.5
1.7
1.0
1.8
1.4
2.1
92.0
96
2
g>
76
94
96
98
100
RON without Pb
FIG. 5CRU yield/octane relationship.
102
104
CHAPTER
1: PETROLEUM
OIL REFINING
15
'^Raffinue
Bxtfictio
^Tnadngind
Fnctiamtioii
Feed
LSGBflD
EEXTRACTOR
S'STRlPfCR
RC - RECOVERY COLUMN
SR - SOLVB^TREOENERATOR
FIG. 6Solvent extraction unit for btx recovery.
Alkylation
The reaction of an olefin with an aromatic or isoparaffin is labeled alkylation. Benzene is alkylated with ethylene to eventually produce styrene, and with propylene to eventually produce phenol. These "petrochemical" technologies are found
in some refineries. But the "alky" process that is part of the
typical refinery flow plan (Fig. 1) is the reaction of C3-C5
olefins with the paraffin isobutane.
The process requires that the paraffin be branched to provide a reactive tertiary carbon atom, bonded to only one hydrogen. Normal paraffins, having only primary or secondary
carbon atoms, are not sufficiently reactive. Isopentane could
be used, but it is already a clean, high-octane liquid contained in the C5 part of the gasoline pool. Thus, the gas isobutane becomes the obvious choice since it is reactive, not part
of the gasoline pool, and reasonably available in the refinery
as a crude oil component, as well as in the C4 product from
processes s u c h as the FCCU, CRU, a n d hydroprocessing
units.
The chemistry can be accomplished with any olefin. Ethylene is not used because it is expensive to recover, operating
pressure would have to be considerable since the process is
carried out in the liquid phase, and the resulting alkylate octane quality is poor compared to processing higher molecular weight olefins. Propylene is a n "alky" feed in many units,
but its use competes against its value as a petrochemical feed
for polypropylene, propylene oxide, and linear alpha olefins.
The butylenes are the predominant alky feed because of their
availability, cost t o separate into chemical grade components, and high octane quality of the alkylate. However, as
the light olefin content of gasoline diminishes due to evolving
legislation, refiners may also find it economically attractive
to use amylenes as alky feed, instead of converting them to
lower octane pentanes in a hydrotreater.
In many refineries, there is insufficient isobutane to match
the availability of olefins from the FCCU and cokers. The
missing iC4 can be produced by isomerizing available nC4,
by purchase from the natural gas condensate pool, or from
nearby refineries lacking an alky plant.
The catalysts that are commercially employed are 98-99%
sulfuric acid (H2SO4), or concentrated hydrofluoric acid
(HF) because the chemistry requires a very strong acid. Commercialization of solid-type catalyst is in progress. The process in concept is simple: pressurize the system to liquefy the
hydrocarbon feeds, mix them with the strong liquid acid, and
separate the alkylate from the catalyst. The process in reality
is complex because of acid carryover into the alkylate; formation of acid-hydrocarbon molecules; significant exothermic heat of reaction; the need for substantial excess isobutane to suppress olefin polymerization; high catalyst
consumption and utility cost in the case of H2SO4; and safety
considerations, especially with hydrofluoric acid.
Sulfuric acid alkylation m u s t r u n at low temperature,
namely, about 5-10C, in order to minimize olefin polymerization, acid consumption, and by-product yield. This requires refrigeration of the catalyst and feed, and substantial
4Mafenp
Hydiogra
[ ^
ri
c:^
X
.J^
iall:^^
OM
sr
LEGEMD
D-DRYER
R-REACrOR
ST STABILIZER
C5-C
booMnli
FIG. 7Isomerization unit.
alkylate, cooling of recycle acid, recovery and recycle of isobutane, cleanup of alkylate, and separation of products. Typical
product yields, quality, and disposition are shown in Table 12.
MTBE
Oxygenates were introduced into the gasoline pool in the
1970s to help replace the lost octanes from lead additives.
Their use has now been mandated in many parts of the world
based on data showing their ability to reduce harmful vehicle
emissions. The majority of worldwide use of MTBE is by
commodity chemical p u r c h a s e . However, a substantial
a m o u n t is made within the refinery gate, in particular in the
United States. Typically, the MTBE unit is installed in front
of a n alkylation unit. The C4 cut from the FCCU is first fed to
the MTBE unit where the isobutylene is reacted with purchased methanol. The effluent C4 paraffin and olefin stream,
minus isobutylene, is then sent to the alky plant.
MTBE has helped the refiner meet gasoline d e m a n d and
octane, and is being adapted for blending worldwide. In fact,
during the 1980s and much of the 1990s, it was the fastest
REACTION
SECTION
BOSIRIFFER
DEFKOPANIZER
17
HFSnUFPER
Mixed
Batane*
OUfin
Feed
"j
DiyingAnd
Diokfin
Saianlioa
C3 + C4
C4
Yields, %w
4-10
Propane
n-Butane
2-5
3-6
80-93
Alkylate
76-90
Alky Bottoms"
3-8
3-8
1
Alky Tar*
1
Alkylate Dist, C
Initial BP
40
40
75
10%
70
100
30%
90
105
100
50%
110
70%
105
125
90%
120
195
Final BP
190
96
RON, without Lead
93
MON, without Lead
92
94
^Too high boiling for gasoline. Usually blended to diesel and fuel
oil.
' A "waste" stream of high molecular weight. May be processed in
cracking units, burned as fuel, or disposed.
18
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
"0"
As little as possible
Hydrocracking (HC)
Additional Terminology
HDS
HDT
HDN
HDA
25 +
NHT
DDS
MHC
ARDS
VRDS
Objectives
Cleanup without conversion
Cleanup of higher boiling streams
with minimum conversion
Cleanup + Conversion
Hydrodesulfurization
Hydrotreating
Hydrodenitrogenation
Hydrodearomatization
Naphtha Hydrotreater
Distillate Desulfurizer
Mild Hydrocracking
Atmospheric Resid Desulfurization
Vacuum Resid Desulfurization
tions for this technology are also listed in Table 13. The refinery streams that can/must undergo hydroprocessing, and the
reasons for the process selection are summarized in Table 14.
An example of a simplified process flow diagram is shown
in Fig. 9. Fresh feed, with hydrogen recycle and make-up hydrogen for the a m o u n t c o n s u m e d by the hydrogenation
chemistry, are heated to reaction temperature in a furnace
and then fed downflow through one or more fixed catalyst
bed reactors in series. After the desired reactions have occurred, the remainder of the process involves the recovery of
a high purity hydrogen recycle stream, separation of any
cracked hydrocarbon gases from the desulfurized liquid
product, as well as distillation of the liquid into appropriate
cuts. Start-of-run r e a c t o r t e m p e r a t u r e ranges from 2 8 5 400C a n d pressure from 900-20 000 kPa; generally, the
higher the boiling range axid "dirtiness" of the feed and the
greater the desired cracking severity and dearomatization,
the greater is the required temperature, pressure and n u m b e r
of reactors, as well as chemical hydrogen consumption. Excess hydrogen via the recycle is needed to minimize coke formation and laydown on the catalyst; this recycle is about 3-5
times the expected hydrogen consumption.
The catalysts comprise the widest selection among all the refinery processes because this technology is used to "clean" all
refinery streams from light straight r u n gasoline through vacu u m resid. The two most common formulations consist of
combinations of cobalt and molybdenum or nickel and molybd e n u m promoters on an alumina base. The "cobalt-moly" catalyst, as it is typically called, is preferred for sulfur removal
while the "nickel-moly" combination is active for nitrogen removal and some aromatics saturation. Some catalysts also utilize nickel-tungsten. Noble metal catalysts such as platinum as
well as zeolites are now employed, in particular for deep
deciromatization. Cobalt-moly and nickel-moly catalysts contain in the range of 3-25% promoter metals depending on feed
properties and planned hydroprocessing severity.
Hydroprocessing is exothermic and increases with hydrogenation severity. Reactor outlet temperature in a fixed bed
reactor can be as m u c h as 35C greater than inlet temperature when processing vacuum gas oils and resid. Further, as
the run proceeds, slow b u t inevitable loss of catalyst activity
due to coke and metals laydown occurs and is compensated
by raising furnace outlet temperature. Hydrogenation reaction rate increases with temperature and at about 470C, can
result in a "runaway" reaction. Since there is always an ex-
At the end of a run, burning the coke off can regenerate the
"coked up" catalyst. This also is accomplished in-situ or exsitu. Ex-situ removal more efficiently removes the coke, but
at increased cost. If performed in-situ, the catalyst will usually remain in the reactor for 2-4 runs, after which refiners
will d u m p the spent catalyst and replace it with fresh material. Spent catalyst is usually then taken to hazardous waste
disposal. If the catalyst has been used to process resid, it may
be sent for nickel and vanadium recovery or to a process that
can remove enough of the feed metals to reactivate the catalyst and allow its reuse.
Hydrogen consumption and throughput rate, often called
"space velocity," are two of the key process and economic
variables. As the boiling range of the feed, and thus its heteroatom and aromatics content, increases, it can be expected
that hydrogen consumption will increase a n d throughput
will need to decrease to increase residence time. A similar response occurs for a given feed as conversion increases. Examples of yield, hydrogen consumption and residence time
for different feeds are shown in Table 15.
Hydroprocessing will continue to play a n ever-increasing
role in worldwide refining. The factors driving this conclusion are:
19
B.P.
Sulfur
Diolef.
Acids
X
X
FCCU GasoHne
Catalytic Reformate
Kerosine/Jet
Lt Attn Gas Oil
Atm Gas Oil
Coker Gas Oil
Resid
End Use
Isomerization Unit Feed
Cat Reformer Feed
Gasoline Blending, Cat
Reformer Feed
Low Sulfur Gasoline
Low Benzene Gasoline
Jet Fuel, Low Sulfur Diesel
Low Sulfur Diesel
Gasoline Blending, Cat
Reformer Feed, Jet Fuel,
Diesel Fuel
FCCU Feed
Gasoline Blending, Cat
Reformer Feed, Jet Fuel,
Diesel Fuel, Lube Oil
Base Stocks
Cat Reformer Feed,
Jet Fuel, Diesel Fuel,
FCCU Feed, Coker Feed,
No. 6 Fuel Oil
STABIUZER HlACnONATOR
LightEmli
3. The aromatics content of fuel products has been decreasing and this trend should continue and expand worldwide.
The technology and catalysts to achieve these results are
available; the only missing ingredient is money. If gasoline,
jet fuel, and diesel fuel continue as the major sources of
transportation fuels, then the industry will be forced to uti-
FCCU LCO +
Coker Gas Oil
FCCU
LCO
Crude
VGO
940
22 400
940
220
275
375
935
28 000
1 000
365
470
575
980
8600
24
730
<1
<1
27
770
<1
35
810
<20
1
68
865
<20
94"
900
500
120
215
280
385
38
825
<20
<2
1.4
2.8
3.1
"Includes AGO
Temperature, "C
465^85
435^55
1-2
4-8
The original driving force for the sociker drum process was
to minimize coking in the furnace coil and thus increase run
length. However, improvements in furnace design have narrowed the differences in process severity so that either process may be selected.
TABLE 16Resid process capacity.
Capacity, Million mt/year
Process
Worldwide
North
America
Western
Europe
AsiaPacific
Visbreaking
Delayed Coking
Fluid Coking
Fixed and Fluid Bed
Hydrocracking
159
155
24
11
96
8
62
13
1
21
16
3
110
35
10
48
CHAPTER 1: PETROLEUM
FRACTIONATION
TOWER
HEATER
START
^>-4vvv1-
ftd
I i
QUENCH
f
RESID
FRACTIONATION
TOWER
X-
SOAKER
HEATER
START
TT
()--^^-^
QUENCH
RESID
345
970
4.1
720
Resid
Product
345
78
990
4.3
250
Feed
540
Resid
Product
1015
540
72
1035
100 000
45 000
Typical product yields are shown in Table 17. The thermally cracked gases contain olefins, but less than FCCU
gases, and provide an added source of petrochemiccd and
alkylation unit feeds. Visbroken light naphtha can be blended
into gasoline after removal of diolefins and mercaptan sulfur,
and the heavy naphtha can be sent to the cat reformer hydrotreater (often called the naphtha hydrotreater) for olefin
saturation and sulfur/nitrogen removal, followed by octane
number upgrading in the reformer. The visbroken gas oils
will usually be blended to the fuel oil pool, but can be hydrocracked for diesel and jet fuel blending, or hydrotreated to
yield additional FCCU feed.
Solvent Deasphalting
This is the only process of the six in which no chemical
changes to the molecules occur. The process is based on the
low solubility of asphaltene-type residuum oil molecules in
low molecular weight paraffins. Asphaltenes are highly aromatic, difficult to crack, and contain the majority of the sulfur, nitrogen, and metals heteroatoms that are found in resid.
In the deasphalting process, feedstock, usually vacuum resid,
is mixed with a paraffin solvent, either propane, butane or
OIL REFINING
21
Percent DAO
C3
C4
C5
25-40
50-65
80-95
Delayed Coking
This is the dominant resid upgrading process in the U.S. and
is showing growth in Europe and, in particular. South America. Like visbreaking, this is also a thermal cracking process.
Unlike visbreaking, this process runs at essentially 100% conversion; all of the resid feed is converted into other products;
namely, cracked gases, coker naphthas and gas oils, and
coke. While the cracked gases and liquids are assumed to
have higher market value than the resid feed, it is the market
utilization and pricing of some of the coke that further helps
to drive favorable economics.
A schematic of the process is shown in Fig. 12. The cracking chemistry takes place in pairs of "drums." Cracked gases
and liquids leave the top of each drum, while the product
100
80
o
<
60
40
/y
o
20
^C
f. I
i^^^A
C^C^^ ,
^'^^""
40
20
60
80
100
Quench
XZ
^r^^ (nh
L5^
I
Coke Drums
Fumace Steam
'Gasoline
Stripper
Steam
* Light Gas Oil
Heavy Gas Oil
Rc
\
'Gas
Fresh Feed
Main
Column
^^ ~ ^''^^'^ recycle
CHAPTER
coke r e m a i n s in the d r u m s . At start-up, both d r u m s are
empty. The resid is fed to one d r u m for u p to a day while the
other drum remains idle. On the second day, feed is cracked
in the other d r u m while the coke that has filled the first d r u m
is removed (decoked). This back and forth coke removal creates the continuous process. Drums have t3rpically been sized
to hold 24 h of coke make, since it required that amount of
time to decoke early units. Improvements to the decoking operation have enabled many units to r u n in 12-18 h cycles.
This has led to increased capacity revamps in existing units
or the opportunity to build smaller drums in new plants.
In a typical design, the resid fresh feed enters the bottom
section of the coker product m a i n fractionator. This provides
for heat balance in the distillation column bottom, the picku p of coke fines carried from the drums with the cracked
products, and the removal of a heavy coker gas oil product
for recycle to improve lighter product yield. Some fractionator designs also recover a lower boiling gas oil recycle. The
feed/recycle is then heated to cracking temperature, about
490-510C, in the coker furnace. Steam is usually added to
the feed to increase furnace coil velocity and thus minimize
coke laydown on the furnace tubes as the feed reaches cracking conditions. The purpose is to delay coking as much as
possible until the feed enters the bottom of the drum, hence
the process name.
The time-temperature parameters in the drum cause complete conversion of the resid. As coke is produced, steirting at
the bottom, the feed, which is part vapor-part liquid, continues to crack. As coke forms, it provides surface-induced
cracking as the feed passes through it. This operation succeeds because most of the coke that is produced is amorphous and spongy and is actually named sponge coke; thus,
the fresh feed is able to pass through.
The cracked p r o d u c t s are recovered and separated in
equipment similar to other processes. An example of 5rields
and quality is shown in Table 18. Unlike the FCCU, changes
in operating parameters, in this case temperature, pressure
and recycle ratio, have only a minor effect on product yields,
to the point that yields can be approximated based solely on
resid feed properties, in particular aromatics content, by using either carbon residue (ASTM Test Method for Conradson
Carbon Residue of Petroleum Products, D189-97) or API
gravity as the predictor. Coker n a p h t h a has lower octane
quality compared to cat gasoline. In addition, it must be selectively hydrogenated because non-catalytic cracked naphtha has a m u c h higher diolefin content, making it thermally
Resid Feed
Products
H2S
C1-C4
Naphtha
Atm Gas Oil
Vac Gas Oil
Coke
1025
Sulfur,
%w
Nitrogen,
ppmw
2.9
3000
0.5
0.95
1.9
3.7
70
600
2200
Carbon
Residue,
%w
22
Ni + V ,
ppmw
250
Yield,
%w
1.1
11.1
10.4
32.4
12.0
33.0
740
850
960
2.5
2
750
1: PETROLEUM
OIL REFINING
23
24
MANUAL
HANDBOOK
Fluid Coking/Flexicoking
These technologies also convert all of the resid feed into
cracked products and coke. The chemistry takes place, however, in a reactor containing vapor phase fluidized coke particles. The heated feed is sprayed onto the coke through feed
nozzles around the reactor circumference. The product coke
deposits on the fluidized coke, which is continuously removed from the reactor. In the fluid coking process, sufficient coke is burned in a separate "burner" vessel to raise its
temperature so that this hot coke will maintain heat balance
upon its recirculation to the reactor. In the Flexicoking process, essentially all of the coke is converted to a low heat content gas in a third "gasifier" vessel, the hot gas then reheats
the circulating coke via heat transfer in what was the fluid
coker burner vessel. As an example, if the chemistry yields
30% coke in the reactor, net coke from the fluid coker will be
a b o u t 20-24%, b u t will only be a b o u t 0.5%, as a p u r g e
stream, from the Flexicoker.
The net coke from the fluid coker is in the form of shot coke
and can only be used as fuel. Because the delayed coking process yields a higher average value of coke, it accounts for
about 85% of worldwide coking capacity. The Flexicoking
process provides the refiner the option of generating a fuel
gas that can be scrubbed of H2S, instead of coke laden with
sulfur, nitrogen and metals. Because the gasifier operates on
steam and air, rather than steam and oxygen, the resulting
gas heat content is in the range of 3000 to 4500 kJ/m^.
Cracked gas and liquids yields from the fluid coking process are similar to yields from the delayed coking process. A
washing section is installed above the reactor to prevent carryover of coke fines to the coker main fractionator, produce
a coker gas oil recycle and, as a result, control coker gas oil
final boiling point.
an equilibrium catalyst activity can be maintained. This eliminates the need to raise feed inlet temperature as run length
progresses, as required in fixed bed units. In addition, the
a m o u n t of recirculating liquid product required for proper
catalyst bed operation is usually sufficient to provide a complete heat sink for the exothermic heat of reaction; thus, the
reactor essentially operates isothermally. This permits startof-run temperature as high as 435C, which is not technically
or economically feasible in fixed bed reactors. This temperature, in turn, provides enough thermal energy to substantially
crack vacuum resid, and, from the presence of hydrogen at
high pressure, typically 15000-18000 kPa, enough hydrogenation reactivity to yield substantially desulfurized lower
boiling products.
LGO
175-345
8.8
865
300
200
HGO
345-550
52.7
910
1300
400
10
Vac
Resid
550-134.i
980
11000
2800
2700
Recycle Oil
25
Feed
Naph
LGO
HGO
Vac Res
Naph
LGO
HGO
Vac Res
565 +
C5-175
9
710
300
85
175-345
18
860
800
480
345-565
32
920
2500
1900
565 +
34
1010
12 400
5200
C5-175
12
710
900
175-345
23
860
2700
630
345-565
38
930
11800
2500
565 +
20
1060
27 800
7000
1037
54 000
4000
Conversion levels of 50-90% have been commercially attained. And, the unit can process any quality feed, recognizing that heavier, dirtier feeds will require lower throughput
rate (space velocity), and increased hydrogen consumption
and catalyst replacement rate. Examples of yields and quality
for a representative resid feed are shown in Table 20.
use of the n-paraffins as wax product. The two largest markets for this wax are the maJcing of candles and the coating of
cardboard cartons for the preservation of fruits and vegetables from farm to table. Separation of the solid paraffin crystals from the mother liquor is aided by solvents such as
methyl ethyl ketone and urea.
The refiner usually supplies some 4 to 9 lube base oils, that
vary mainly in viscosity, to lube plants that blend, package,
and ship finished product. The largest single market for lube
oil base stocks is for the production of motor oils. Hundreds
of other products, including greases, are also prepared for a
myriad of industrial needs. Overall, this is still a specialty
area of refining, accounting for only 1% of crude oil capacity.
Partial Oxidation
CO + H2O = CO2 + H2
This exothermic reaction takes place at about 350C over a
fixed bed of iron oxide catalyst. Some plants employ a lower
temperature second catalytic shift using a copper-zinc catalyst to convert any remaining CO. The product gas is then
treated for CO2 removed; the carbon dioxide is then vented or
recovered.
Unfortunately, the hydrogen product gas may still contain
u p to 1-3% CO/CO2 which will adversely affect catalyst in a
hydrotreater. Thus, a third reaction, called methanation, may
be employed to reduce impurities to acceptable levels. This
step is carried out in a fixed bed using a nickel catalyst and
uses a small amount of the product hydrogen, per the following chemistry:
Sulfur Recovery
Hydrogen sulfide is removed from refinery gas and liquid
streams via contact with liquid or solid absorbents and adsorbents. Among the dozen or so choices, the ones most
widely used in refineries are the ethanolamine liquid absorbents. As a result, this step on the sulfur recovery flowsheet is commonly ccilled "amine treating." After the H2S has
been separated from the hydrocarbons, it is converted into elemental sulfur in the sulfur recovery unit (SRU) by the Claus
process and its m3rriad variations. Recovery of sulfur from refineries and from natural gas production now accounts for
the majority of sulfur supply to its end users.
The most commonly used amine treating absorbents, or
solvents as they are normally called, are the primary amine,
monoethanolamine (MEA); the secondary amine, diethanolamine (DEA), and the tertiary amine, methyldiethanolamine
(MDEA). Selection is based on concentration of H2S in the
hydrocarbon gas stream, a m o u n t of other acid gas components such as carbonyl sulfide and carbon dioxide, and the
relative solvent activity compared with useable concentration of amine in water.
The hydrocarbon feed stream is contacted countercurrent
to a "lean" solvent, free of H2S, in absorbers (Fig 14). The sol-
Sweet Gas
Lean
Amine
-^MQ-J'
(POX)
^Ll
Mal<eup
-Water
Amine
Stripper
Sour Gas
Amine
Contactor
Flash
tank
Rich Amine
CKl
Lean Amine
FIG. 14^Amine treating unit.
Acid
'Gas
27
AIR
COMPRESSOR
THERMAL
REACTOR
SULFUR
SULFUR
CONVERTER CONDENSER REHEATERS
AeUQu
Fran Ajidiit
RMNnnlioQ
AddOM
From Sour Water Stripper
Com.
FIG. 15Claus unit.
28
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
COGENERATION
Refineries continue to add "cogen" plants to the flow sheet.
They offer the opportunity to convert various low value fuels
or blend components into electricity. The electricity, in turn,
can be used to supply part or all of the refinery's needs, or the
plant can be large enough to permit the refiner to sell electricity to nearby utilities. With the advent of utility supply
and price deregulation, this option can take on added attractiveness. Cogen feeds range from gases to heavy fuel oils to
delayed and Quid coke.
PRODUCT BLENDING
Blending equations have been developed over the decades to
allow the refiner to optimally blend the fuel products with a
high degree of accuracy. The equations may be relatively simple for properties such as viscosity, or relatively complex for
predicting blended gasoline octane number. These equations
have been built into the refinery computer models with the
goal that each batch of product will be blended correctly and
will meet specifications at m i n i m u m cost. While the computer models and test methods continue to improve, most
product is still blended by mixing the computer-indicated
components in a product storage tank, sampling the tank,
and then waiting for appropriate laboratory data to certify
that the blend meets specifications. Some refineries do online product blending, meaning that components are mixed
directly into a product pipeline, for example, with key tests
being performed using on-line instrumental analysis. On-line
octane analyzers are being used for gasoline blending, and
newer test methods such as near and mid-infrared are beginning to replace m o r e complex or time-consuming older
methods.
CHAPTER
the refinery's crude slate and overall fuel product demand
balance. It is also euiticipated that some of the new sulfur
removal processes will gain substantial commercial acceptance, offering a n opportunity to meet future gasoline sulfur specifications with p e r h a p s less octane n u m b e r loss
and less hydrogen consumption.
OxygenatesAs worldwide legislation for cleaner fuels
spreads, every region or country appears to be requiring
the use of oxygenates for pollution abatement, with the
concomitant octane benefit. It is not possible to know if the
expected b a n on MTBE in California and the consideration
of a countrywide ban by the U.S. Congress will cause a similar worldwide response. Removal of MTBE will likely
place a b a n on TAME, increase interest in ethanol, require
an increase in cat reforming, cat cracking and edkylation
capacity, increase the need for isomerization of light
straight r u n gasoline and introduce the chemical conversion of isobutylene to isooctane.
The quality of No. 2 diesel fuel will mainly focus on sulfur
and aromatics. As the world likely adopts a m a x i m u m sulfur
specification in the 10-50 p p m w range and some reduction
in aromatics concentration, refiners will in turn install or revamp middle distillate hydrotreaters that have the flexibility
to achieve deeper aromatics saturation with perhaps only the
need for a catalyst changeout.
Future product demand may be virtually impossible to predict. For example, in the U.S., the rapid acceptance of the van
and sport utility vehicle in place of the standard car led to a
decrease in overEiU vehicle fuel economy because of lack of
regulation for such vehicle tjrpes. This is in the process of being corrected but, meanwhile, gasoline demand in the U.S. is
increasing at rates exceeding earlier estimates.
Alternative sources of vehicle power create a long-term
uncertainty for the refiner. Natural gas and LPG are available in varying degree in m a n y parts of the world; LPG is a
readily available automotive fuel in European countries, for
example. Ignoring availability, the main detriment to rapid
expansion of these fuels is the needed supply and distribution infrastructure. Electricity-driven vehicles, via the battery, are not likely to play any substantive role unless a major b r e a k t h r o u g h in energy efficiency is found. Vehicles
powered o n externally-supplied hydrogen have little hope of
p e n e t r a t i n g the marketplace because of high p r o d u c t i o n
cost, delivery infrastructure, and safety. However, hybrid
battery/gasoline powered vehicles will be available shortly.
The fuel cell may have an impact on future refineries. This
would be intriguing if it becomes technically and economically feasible t o produce a hydrogen/CO synthesis gas by
steam reforming of naphtha "under the hood," since this liquid can take the place of gasoline or diesel fuel without any
changes at the "pump." Should this occur, octane n u m b e r
becomes a non-issue, the value of catalj^ic reforming, fluid
catalytic cracking and, hence, alkylation would diminish,
and hydrotreating and hydrocracking to supply additional
"clean" n a p h t h a would increase, also requiring a major increase in refinery hydrogen.
Crude a n d product pricing has become a substantive unknown for the refiner. On the crude oil side, the difficulty
has been unexpected changes in price, as well as the inability to predict future prices or the price spread between
1: PETROLEUM
OIL REFINING
29
ASTM STANDARDS
Number
Title
D 86-99a
D 1160-95
BIBLIOGRAPHY
[1] Wauquier, J.-P., Crude Oil. Petroleum Products. Process Flowsheets, 1st edition. Editions Technip, Paris, 1995.
[2] Wauquier, J.-P., Separation Processes, 1st edition, Editions Technip, Paris, 2000.
[3] Leprince, P., Conversion Processes, 1st edition. Editions Technip, Paris, 2000.
[4] Gary, J. H. and Handwerk, G. E., Petroleum Refining Technology
and Economics, 4th Edition, Marcel Dekker, Inc., NY, 2001.
[5] Kaes, G. L., Refinery Process Modeling, 1st edition, The Athens
Printing Co., Athens, GA, 2000.
[6] Meyers, R. A., Ed., Handbook of Petroleum Refining Processes,
1st and 2nd editions, McGraw-Hill Book Co., NY, 1986 and 1997,
respectively.
Pretreating Methods to Remove Sulfur," Hydrocarbon Processing, Vol. 78, No. 11, November 1999, pp. 43-51.
[12] Swaty, T. E., Nocca, J. L., and Ross, J., "What are the Options to
Meet Tier 11 Sulfur Requirements?," Hydrocarbon
Processing,
Vol. 80, No. 2, February 2001, pp. 62-70.
[13] Law, D. v . , "Hydrocracking: Past, Present and Future,"
Petroleum Technology Quarterly, Vol. 5, No. 4, Winter 2000/2001,
pp. 55-63.
[14] Chang, T., "Worldwide Catalyst Report," Oil & Gas Journal, Vol.
97, No. 39, September 1999, pp. 45-68.
MNL37-EB/Jun. 2003
HISTORY
The LPG industry did not start until about 1904, more than
40 years after the start of North American crude oil and natural gas production a r o u n d 1860. Natural gas (methane)
cooking and lighting appliances were commonplace by 1900,
but it was difficult to make the gaseous fuel portable. It was
not feasible to transport and store compressed natural gas
(CNG) in the bulky pressure vessels of the day.
LPG is the ideal fuel for mobile and remote gas applications. It is a high BTU content liquid at typical ambient temperatures and modest (<250 psig) pressures, that is practical
for storage and transportation. It can be used like natural gas
once vaporized, in natural gas appliances adapted to gaseous
LPG mixtures with small adjustment for air/fuel ratio.
The early years of the industry were cheiracterized by the
need to solve the immediate problems of the day, without any
standardization or regulatory controls. LPG was one of the
first c o n s u m e r goods transported and sold in pressure
vessels. There were many economic and technical challenges
to produce, transport, and t h e n sell it to the public. The
industry was at the forefront of many areas of research and
development, ranging from processes, equipment and
appliances for m a n u f a c t u r e and use, to analytical test
methods for composition a n d properties. The results (in
retrospect) were predicable, a n d excesses abounded. However, in a short n u m b e r of years, the emerging industry was
compelled by marketing a n d regulatory forces to develop
31
Copyright'
2003 by A S I M International
www.astm.org
32
MANUAL
HANDBOOK
10.000.0
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FIG. 1High temperature vapor pressures for light hydrocarbons. Reprinted with permission from the Gas Processors
Association.
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33
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FIG. 3n-Butane P-H diagram. Reprinted with permission from the Gas Processors Association.
100
10000
200
300
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Rstorence Slates:
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FIG. 4Propan P-H diagram. Reprinted with permission from the Gas Processors Association.
34
GAS
35
36
MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
gas daily. Stoves leaked too [12]. Even so, the industry was
modestly successful. Some "Blaugas" plants remained in operation into the 1920s b u t were all gradually displaced by
LPG recovered from crude/natural gas production a n d
refining. Small regional businesses were built up around individual supply sources and different gas mixtures and gas
sets. While the sets were relatively successful, they did experience problems from residues and ice causing regulators to
malfunction. Gasoline and heavier hydrocarbons collected in
the gas bottle, and had to be periodically drained out. Success
depended more on the ability of the equipment to tolerate the
mixture than anything else. There were no specifications to
control dryness, icing, residues, or composition.
The first commercial use of LPG produced from crude oil
or natural gas was in 1912, indirectly as result of a burgeoning demand for gasoline due to mass production of automobiles after 1908. Condensable liquids were reported as early
as 1893 in natural gas (methane) cryogenic drying processes
for natural gas distribution. There are indications of a lowpressure condensate from crude oil p r o d u c t i o n being
distributed in wooden barrels in the 1900-04 era, but it was
the automobile that changed everything. Automotive gasoline had to be liquid in atmospherically vented tanks, but
volatile enough to evaporate when mixed with air in a carburetor. The automobile created an i m m e d i a t e d e m a n d for
naphtha from crude oil as well as condensate from natural
gas or crude p r o d u c t i o n . Customers w h o b o u g h t a quart
of l a m p oil now w a n t e d gallons of gasoline. The liquid
condensate from gas production, called "casinghead gasoline," became a preferred product for sale to early refiners for
blending into gasoline, and a new industry was b o m . LPG
was displaced in importance by the frantic scramble to produce casinghead gasoline, which was m o r e profitable, at
least in the wintertime, when there was a strong demand. Initicdly, a high-pressure condensate was allowed to "weather"
in standing tanks, until enough boiled off that it was "acceptable" for use in gasoline. The limits of acceptability were only
loosely defined at the time, but these fundamental requirements eventually led to the "weathering test" and "vapor
tension" specification requirements many years later.
Propane a n d b u t a n e continued to be problematic byproducts from both crude and gas production. Propane was
too volatile to be a significant portion of gasoline, and not
volatile enough for even moderately pressurized natural gas
distribution networks pipelines. It was essentially worthless,
so there was a large economic incentive for producers to include as m u c h of the volatile propane/butane as possible into
casinghead gasoline. While m a n y of the blends provided
good fuels for the engines of the day, "a frantic scramble to
meet demands, coupled with not a little ignorance, began to
create significant problems" [13]. Many serious incidents occurred due to excessive volatility and evaporative losses that
sometimes exceeded 40%, and from boiling and over pressuring rail cEirs. In 1915, a rail car explosion killed 47 persons, injured more than 500, and virtually destroyed the town
of Ardmore, Oklahoma. Casinghead gasoline was almost universally condemned, and developed such a poor reputation
that one major refiner stopped using it in gasoline a n d
advertised it as a consumer benefit. By 1919, the last major
refiner announced that it was n o longer in the market for casinghead gasoline, and declared, "specifications were urgently
needed" [14]. As late as 1921, there were more than 100 different specifications for casinghead gasoline, most of them
meaningless and many based on what a producer may have
been producing on a particular day [15].
In April 1921, representatives from 31 companies formed
the Association of Natural Gasoline Manufacturers (ANGM),
following upon two previous efforts to organize gas processors. This Association later became the Natural Gasoline Association of America (NGAA), and now the Gas Processors
Association (GPA). Its purpose was to impose both business
a n d technical controls on the unruly new industry. They
created a new, m o r e acceptable product, called "natural
gasoline" to replace "casinghead gasoline." The ANGM
moved quickly to develop technical standards and related tariff agreements, a n d to improve operations. Within three
months, the first specifications were written for seven grades
of natural gasoline A-G, and four grades of blended natural
gasoline m o t o r fuel. The Natural Gasoline specifications
were based on density (API gravity) and percent recovered
(by evaporation). The lower gravity grades were preferred for
gasoline blending a n d c o m m a n d e d a higher price. The
blended gasoline grades were defined by a wider set of specifications, including gravity, end point, initial boiling point,
vapor tension, color, and an important new concept, percent
recovery in a standard distillation test. Boiling point criteria
and the distillation test marked significant advances in the
development of m o d e r n specifications [16]. The blended
gasoline specifications were intended to eliminate practices
such as "dumbbell" blending of kerosene with "wild" casinghead gas to give a blend with a naphtha range gravity that did
not work well in automobiles. The blended gasoline specifications were eliminated two years later, deferring to specifications developed elsewhere by the refining industry. The
natural gasoline specifications were modified several times
both for definition for the grades and for test methods as they
were developed, and are still published today by the GPA.
In 1910, a Pittsburgh motorcar owner walked into U.S. Bureau of Mines chemist Dr. Walter Snelling's office, complaining that the gallon of gasoline he had purchased was only half
a gallon by the time he got home. He thought the government
should look into why consumers were being cheated because
the gasoline was evaporating at a rapid and costly rate. Dr.
Snelling took u p the challenge and discovered that the evaporating gases were propane, butane, and other hydrocarbons.
Using coils from an old hot water heater and other miscellaneous pieces of laboratory equipment. Dr. Snelling built a
still that could separate natural gasoline into its liquid and
gaseous components [17]. This resulted in a 1913 patent for
a continuous process "to obtain the most volatile ingredient
or mixture in the form of a liquid gas under pressure" by fractional condensation of compressed heated vapors of natural
gasoline [18,19]. This virtually eliminated b o t h excessive
pressure and residue problems, and became the keystone of
the m o d e m LPG industry. The first m o d e m LP business venture, American Gasol Co., was founded by Snelling, and three
prominant "gas men" of the time, Frank Peterson and two
cousins, C. L. a n d A. N. Kerr. The products were called
"Gasol" (propane) a n d "Gasolite" (butane). The company
failed for lack of markets and the burden of cylinder and distribution costs, and was sold two years later. Snelling went
back to the U.S. Bureau of Mines explosives research, and the
CHAPTER
three "gas men" went into the casinghead gasohne business,
which was more profitable at the time.
The three "gas men" returned to the LPG business after
WWI. A. N. Kerr became president of the Casinghead Gasohne Association about 1915, one of the failed predecessors of
the ANGM (GPA). The Kerrs founded the Rockgas Products
Co. in Pittsburgh, and in 1925 the Imperial Gas Company in
Los Angeles. They tried to develop other markets for the light
ends, such as LP-gas/air town gas distribution plants and for
cutting steel. In 1932, the Kerrs authored the first chapter of
the Handbook of Butane Propane Gases on "A Chronology of
Liquid Gas Development"[20].
In 1912, F r a n k Peterson of the Bessemer Gas Engine
Company p u r c h a s e d rights to a 1909 patent to inject
naphtha gasoline into hot compressed natural gas to absorb
casinghead gasoline. He later patented a multistage compression/liquefaction process in 1912 [21]. These "hot blending" and "compression" processes were licensed to customers
using Bessemer compressors and gas engines. In 1914 he
patented "a liquefied fraction of n a t u r a l gas containing
ethane, propane and butane, substantially free of heavier hydrocarbons and from methane"[22]. He also developed one of
the first tests to estimate the "wetness" of a gas sample based
on absorbing/desorbing the sample in a mineral seal oil. Details of the test were held closely by the Bessemer Company,
which ran the test for $5 per sample. The fee was returned to
any prospective producer who purchased Bessemer equipment [23]. The close association of the liquids producers and
equipment suppliers has endured and evolved into today's
GPA and GPSA (Gas Processor Suppliers Association).
The LPG industry grew very slowly prior to 1932. In the
early years, it was inhibited by a shortage of tanks and materials due to WWI, by the wide variety of LPG mixtures and
equipment, and by competition from the casinghead and natural gasoline business. The entire infrastructure for LPG was
new, and there were many technical problems (and costs) associated with production, transportation, equipment, and
appliances. E q u i p m e n t a n d transportation costs were of
p a r a m o u n t importance, since the cost of the fuel itself was so
low. During this period there was litigation on several patents
associated with the production (and therefore the use) of
LPGs of various compositions. Most notable were the Saybolt
patent for absorbtion, held by Standard Oil, and the "stabilization" patent, held by the Carbon and Carbide Company
(now Union Carbide). Both patents were eventually held to be
invalid. In addition, the first significant regulations on tanks,
rail cars, equipment, tariffs, production limits, etc., were
p u t in place, t h r o u g h Government agencies such as the
B u r e a u of Explosives, Interstate Transport Commission,
Texas Railroad Commission, National Fire Protection
Association, and others.
Many now-familiar company and brand names appeared,
including Blaugas, Phillips (Philgas), Rockgas, Carbide (Pyrofax), Skelly (Skelgas), Shell (Shellane), and S t a n d a r d
(Flamo). Phillips and Carbide were two of the founding members of the ANGM (NGAA, GPA), and are generally credited
with developing the m o d e m LPG business. Frank Phillips,
founder of Phillips Petroleum, purchased the Snelling patent
rights, and marketed "Philgas" in the mid 1920s. Phillips
established an active research department, and did much of
the early laboratory research on liquefied gas. George G.
2: LIQUEFIED
PETROLEUM
GAS
37
HANDBOOK
LPG S P E C I F I C A T I O N S
History of ASTM LPG Standards
Virtually all of the technical developments relating to ASTM
standards were done through GPA/GPSA member companies, and Government/Industry sponsored Research at organizations such as the USBM, Institute of Gas Technology
(IGT) and Gas Research Institute (GRI). The GPA research
reports and standards and the GPSA Engineering Data Book
have been a primeiry source of technical information for the
industry. These are available on a commercial basis, both to
GPA members and non-members [39].
The GPA maintained the LPG and NGL standards from
first publications in 1921-32 until 1960. By this time, LPG
had become an important consumer fuel, widely available
and with an ever increasing diversity of applications. National Standards were needed to ensure universal acceptance
throughout the downstream industry, and to address
potential regulatory and liability issues inherent to producer
only-specifications. In 1961, ASTM published D1835 specifications for commercial propane and butane that were technically identical to the GPA specifications, including GPA test
methods. In 1964, ASTM published D2154 Special Duty
Propane, which was similar to GPA HD-5, but later incorporated this grade into D1835 in 1975, adding butane-propane
mixtures. The GPA 2140 specifications are still maintained
by the GPA, and remain technically equivalent to ASTM
D1835. ASTM test methods adapted from the original GPA
methods are now used in both standards.
Specifications and many test methods for LPG/NGL products not covered in D1835 are still maintained by the GPA.
This includes GPA 3132, which is the current version of the
original 1932 Natural Gasoline specification, and a variety of
other NGL products, chemical feedstocks, sampling methods, and test methods. The GPA 2140 LPG specification is
widely used for contractual purposes within the upstream
gas and fractionation segments of the industry. The products
covered under ASTM D1835 and GPA 2140 specifications are
often referred to as "spec" products. All of the others tend to
be called NGL's, such as C2+ ("see-two plus," meaning
ethane and heavier), fC4 (field butane), etc. For example,
"spec butane" means that it conforms to one of the consumer
products in D1835 or GPA 2140, or another industry specification or purchase/sale contract. The composition of "NGL
Mix," or "C2-I-" or "condensate "can vary over wide ranges,
and are not manufactured to strict composition limits.
39
40
MANUAL
HANDBOOK
flame. These are not normally present in "spec" products, except at very low p p m levels t h a t are not significant for
intended use (see Composition below).
Propylene has a low pure component octane value, and requires individual control (5% max) because it can be varied
widely in commercial grade. Traces of the other olefins are
effectively controlled by the m a x i m u m vapor pressure
(ethylene) a n d m a x i m u m C4-t- content (butanes, butylenes
and heavier).
The defining specification for ASTM D1835 "Special Duty"
propane (GPA 2140 HD5) is the m a x i m u m 5 vol% propylene
content, intended to control the m i n i m u m octane n u m b e r for
severe service engine applications (HD5 is "Heavy Duty, 5%
maximum propylene"). Propane meeting the special grade
(HD5) specification would have a n octane rating of 95 or
greater by the D 2623 LP-method (if it were run). Commercial
grade with higher propylene content can still be used for
lower severity engine applications. The true HD5 (propane
optimized engines) market has yet to materialize.
This has resulted in decades of debate for the need for actual octane n u m b e r determination versus a linear sum calculation. Gasoline and LPG blending is known to be non-linear,
but the LPG calculation method has prevailed This is probably more because the composition limits of "HD5" propane
are restrictive enough that non-linear blending effects are too
small to be significant. The same cannot be expected for
blends of significantly broader composition [47], or for optimized engine applications that are more optimized for the
fuel. In addition, there are some discrepancies in the pure
component octane values used in ASTM D 2598, EN 589 and
the original ASTM Motor LP Knock Test Method Development as documented in SAE 670055. These differences are
relatively small, generally within 1 octane number. However,
it may be necessary in the future to optimize either the calculation or the engine determined octane number, or as more
recently suggested, by methane number.
The methane n u m b e r of a gaseous fuel is a knock engine test
using conditions similar to D2699 MON, but using methane
and hydrogen as the primary reference fuels. The method has
not been standardized to date. The advantage of the methane
n u m b e r is that the test can be extended to include all gaseous
fuels, including hydrogen, natural gas, LPGs cuid their mixtures, inert diluent gases such as N2 and CO2, and potentially
other combustible gases such as CO and HH3. In principle, it
is possible to relate methane n u m b e r to octane number, but
there are several difficulties in practice. The octane scale, with
iso-octane having a value of 100, is extended to 120 with the
addition of about 6 mL/usg tetraethyl lead. This tends to make
the test increasingly insensitive to non-linear fuel effects in
the high range, and the use of TEL even in the lab is problematic. Similarly, the methane n u m b e r does not respond well to
fuel effects at the low end of its range. Even so, a reasonably
good correlation has been found to exist [48,49].
ASTM D 2623, Test Method for Knock Characteristics of Liquefied Petroleum (LP) Gases by the Motor (LP) Method was
originally used to rate octane n u m b e r of LPG mixtures. This
used a standard CRC knock engine fitted with an LP-gas carburetor. It was withdrawn because the octane n u m b e r of
these simple mixtures could be accurately estimated by linear
blending of component octanes based o n GC analysis per D
2598.
Olefins
CHAPTER
in a similzir m a n n e r to gasoline [50,51]. However, there are
some significant differences, and there is no consensus at this
time. Propane tanks are not atmospherically vented, so there
is no oxidative stability concerns for propane, as there is for
gasoline and other fuels. LPG carburetor vaporizer deposits
are associated with non-volatile residues, and not oxidative
gums from fuel olefins, thiophenes and other trace reactive
c o m p o n e n t s of gasoline. However, developers of m o d e r n
LPG electronic fuel injection (EFI) systems have experienced
significant difficulties with both inorganic and organic deposits that interfere with the proper operation of injectors.
Propane derived from crude oil and natural gas contains essentially n o olefins. Propane from refinery cracking processes
contain olefins, which may can either processed further (alkylation, polygas), separated for propylene sales, or blended into
propane u p to specification or contractual limits. Refinery
propane usucJly requires removal of propylene to meet the
ASTM "Special Duty" or GPA HD5 specification.
A recent study and review sponsored by the California Air
Resources Board (CARB) r e c o m m e n d e d relaxation of the
propylene a n d volatile residue specifications for a u t o
propane, citing that a 10% propylene/5% butane fuel gave the
best equivalent emissions performance [52]. The Board also
recommended a new limit of 0.5% m a x i m u m butenes, pentanes, and heavier. These changes were proposed to preserve
and enhance the current supply of auto propane fuel in California, while maintaining adequate emissions performance.
About half the propane produced in California is a byproduct
of refining processes [53].
This is a possible area of future research and standardization
Vapor Pressure
Historically, vapor pressure was the most critical LPG specification, being responsible for most of the serious problems
in the early days of the industry (see History of LPG). Vapor
pressure is invEiriably tied to pressure vessel and safety valve
certification and transportation regulations, so it is generally
viewed to be critical for regulatory compliance. However,
m o d e m pressure vessel standards as well as LPG production
e q u i p m e n t a n d analyzers have all b u t eliminated vapor
pressure as a significant operational problem.
Certification standards vary by jurisdiction, but typically, a
large safety margin is built into the system. For example, a
typical consumer cylinder pressure rated for 250 psig "working pressure" would be pressure tested after manufacture to
twice this (500 psig) and equipped with a "pressure relief
valve" (pressure safety valve or vent) 250-500 psig, 50-100%
of the test pressure. Propane, at the maximum specification
pressure, would have to be heated to over 140F to even reach
the opening ("cracking") pressure of the safety relief valve. In
addition, the actual burst pressure is controlled to typically at
least three times the working pressure (manufacturers are required to pressure test 1 cylinder out of each lot to destruction as a quality control procedure for the quality of steel and
welds). It is common practice for the manufacturer to "overbuild" cylinders to eliminate any uncertainty in the costly
certification process. For example, sample cylinders rated for
1800 psig working pressure are often tested at about 5000
psig, a n d have burst pressures far in excess of m i n i m u m
2: LIQUEFIED
PETROLEUM
GAS
41
three times the working pressure, often in the 12-15 000 psig
range. Finally, all consumer cylinders, storage vessels, trucks,
and rail cars require periodic inspection and recertification.
These considerations have essentially eliminated LPG vapor
pressure (VP), per se, as a significant problem.
The LPG VP specifications indirectly control the maximum
concentration of light ends, principally ethane in propane
and propane in butane. The manual "Reid" VP test method
was developed in a competition in the 1920s to improve upon
the original U.S. Bureau of Mines "vapor tension" method
(essentially a pressure gage on a length of 2 in. pipe). The
competition was won by Dr. Reid (D323 Reid method), and
an adaptation of this is used in D 1267 for higher VP (>26
psi) LPGs. The test has changed little over the years. Many
laboratories are no longer equipped to r u n the LPG Reid
Method. It is now much more common to calculate VP from
composition by D 2163 using calculations in D 2598 than it is
to run a manned D 1267 Reid VP. However, D 2598 method
has no component VP data for m e t h a n e (if it is present),
which may force the use of the manual method in some circumstances. In addition, D 2598 VP calculation is known to
be biased high (e.g., conservative) at high ethane contents,
due to use of a component VP extrapolated from above the
critical point of ethane.
By historical convention, the VP of LPG is reported in
"gage" or "gauge" pressure in pounds per square inch relative
to atmospheric pressure (psig). The pressure gauge used in
the D 1267 LPG Reid method reads zero at the start of the
test, but unlike D 323 or D 4953 the apparatus starts out liquid filled, and no air is introduced into the test apparatus
during the test. The test result is essentially the partial pressure of the LPG relative to atmosphere, a n d the absolute
pressure is higher by the barometric pressure at the time of
the test. This has caused significant confusion over the years
when using pressure transducers calibrated in psia units, or
when reporting in metric units (kPa), which by definition
would be interpreted as being an absolute pressure. As a result, the specifications require reporting in kPa (gage), which
is not a true SI unit. Also, this difference is sometimes confused with the high bias at high ethane contents when using
D 2598 calculation.
ASTM is currently developing a s t a n d a r d test m e t h o d
based on newer instrumentation similar to D 5191 and D
6378 for gasoline. This method uses an absolute pressure
transducer, so this requires that atmospheric pressure be
subtracted from the result to report a VP (gage) final result.
There is no universally accepted criteria for setting the maximum VP specification for propane, and this is an area for future research and international standardization. The first
GPA VP specification was 225 psig at 105F set to meet the insulated rail tank car requirements of Interstate Commerce
Commission (ICC). In 1955, the specification was revised to
215 psig at 100F, mainly to use a single water bath for both
natural gasoline and propane. Still later in 1955, the VP was
lowered to 210 psig at 100F to meet United States DOT safety
standards for rail tank cars [54]. A variety of other regulatory
limits also exist. This includes DOT 173.301 (f) (2), which limits VP in cyhnders to 300 psig at 1 SOT, Section 170.314 (c) 225
psig at 105F, and Section 173.315 (c) (1) cargo and portable
tanks at 250 psig at 115F [55]. Other regulatory requirements
would be expected in different jurisdictions. The origined HD5
42
HANDBOOK
CHAPTER
2: LIQUEFIED
PETROLEUM
GAS
43
4176 "Clear and Bright," or "visually free of undissolved water" that is used for butane (and other fuels). It takes about
20-40 p p m of free water in a fuel to visually detect a haze
with the unaided eye. In essence, visual ratings only require
t h a t the fuel does not contain a n excessive a m o u n t of
undissolved ("free") water.
The butane test relies on visual detection of water collected
in the bottom of the sample cylinder, and not a haze rating.
The less stringent criteria is because auto-refrigeration of butane does not cause temperatures low enough to cause ice/hyd r a t e formation. As a result the same criteria applies to
b u t a n e as for other fuels.
Simple tank draining, which leaves the remaining propane
saturated with water, is not nearly enough to meet the LPG
"dryness" criteria. The presence of free water at any time in a
propane system is sufficient to put the product severely off
spec and unusable without dehydration or the addition of
methanol (see cautions below). This is critical for proper operation of LPG handling equipment and appliances. Ice accumulation can block vapor or liquid fuel lines, Eind disrupt
proper operation of mechanical equipment, such as pumps,
meters, filters, VEJVCS (fuel lock-offs), and especially regulators (vaporizor/regulators). Icing can occur very quickly, and
can be difficult to diagnose.
"Wet" propane is anything that does not pass the "dryness"
criteria, including the approximately 30-100% saturation
range, even when there is no free water. For example, a storage tank of LPG that is deemed to be "wet" may or may not
have any free water at the bottom of the tank. Water saturated LPG (but n o free water) fails all of the dryness criteria
by a wide margin. The presence of any free water amounts to
"gross" contamination.
"Wet" propane that does not contain free water responds
extremely well to low levels of methanol. Unlike ethanol, IPA,
and higher moleculetr weight alcohols, methanol does not increase the solubility of water in propane (or any other fuel).
It is a popular misconception that methanol is an effective
de-icer because it increases the solubility of water in the fuel.
Methanol decreases the solubility of water in fuels, and causes
phase separation when it is injected into water-saturated fuel.
The phase-separated liquid is non-freezing, so it will not cause
ice/hydrate blockage. When the LPG is sub-saturated with
water, the methanol remains dissolved in the propane along
with the soluble water. It phase separates along with the water whenever the temperature gets cold enough, and prevents
the separated water/methanol mixture from freezing. If the
m e t h a n o l concentration is high enough in the separated
phase, it wiU not freeze at temperatures down to the normal
boiling point of propane of 43C (i.e., nominal 50/50 vol%
methanol/water mixtures Eire commonly used as windshield
de-icing fluid good down to 40C).
of Dissolved
Water in
Propane
44
MANUAL
HANDBOOK
contain more water. This section assumes no hydrate formation, similar to other fuels. Hydrates will be considered
immediately following.
The formation of "free" or undissolved water from a drop
in temperature is similar to other fuels, except that it occurs
at a lower concentration level due to lower solubility. The solubility of water in fuels increases with the temperature and
aromatics content of the fuel, ranging from about 100 p p m w
in low aromatics parafinic fuels to over 500 weight p p m in
high aromatics content gasoline or diesel fuels at 70F [59], A
drop in temperature of water-saturated fuel causes the phase
separation of a bulk (undissolved or "free") water phase to
form as a "haze" of small water droplets. These tend to coalesce into larger droplets and gravity settles them to the bottom of the storage tank. Pure water ice (not hydrate) will only
freeze if the temperature is below freezing. Since the solubility of water in propane is already low, there is m u c h less
water available to phase separate with a drop in temperature.
As a result, classical "fuel line freezing" is not very prevalent
in liquid propane systems, and most problems are associated
with smaller, m o r e easily plugged orifices in valves a n d
regulators than in m u c h larger diameter fuel lines.
If free w a t e r is present (e.g., grossly c o n t a m i n a t e d
propane), dispersed droplets can "super-cool" below freezing
in cold gases or liquids, including propane. This can result in
rapid ice accumulation that tends to be most severe in the - 4
to 10C range, very similar to automotive carburetor icing
and aircraft wing or propeller icing ("rime" icing). As each super-cooled droplet impinges on a surface, a portion of the water spontaneously freezes, adding to the surface ice deposit at
the impingement point. The remaining liquid water droplet is
heated to 0C by the heat of fusion, but is rapidly cooled again
by the surrounding cold fuel. This causes the remaining water to either freeze, or to form another smaller super-cooled
liquid droplet, which can repeat the process to extinction.
Flow patterns can create a small impingement point, and filter/screen surface area that is already plugged diverts flow to
unobstructed areas. This can result in a very fast and efficient
plugging mechanism. Ice accumulation in pipe elbows, meters, filters and screens is often associated with "snap" cooling to just below freezing, a condition that favors formation
of super-cooled water hazes and "rime icing." Ice accumulated under these conditions often looks like a translucent
"milky white" thick coating t h a t appears to have been
"painted" on. These conditions are more commonly found in
production facilities, prior to final drying, but can occur during downstream distribution if water has gotten into the system. Methanol is very effective at eliminating rime icing,
since only a very small concentration of methanol in the separated phase is required to reduce the freezing point to less
than about -10C.
Propane fuel systems are sealed under pressure, and not
vented to the atmosphere. Tanks in the distribution system
are never allowed to be totally liquid filled for safety reasons.
An equilibrium vapor phase is therefore always present in
downstream distribution (but not necessarily in production
facilities). Most end use applications draw equilibrium vapor
from the top of the tank, and large tanks always have a Pressure Relief Valve (Pressure Safety Valve or vent in other jurisdictions). These are safety devices that vent vapor in the
event of an overpressure situation. As a result, the water con-
Hydrates
CHAPTER
ing equipment, pipelines, and even under deep-sea conditions
due to gas seepage into cold ocean water (with the potential of
becoming a significant "new" energy resource) [62,63]. Hydrate blockages in pipes can be very hazardous. Depressurizing one side of the line can result in the hydrate blockage becoming a ballistic projectile, with the capability of causing
considerable damage. The propane-water and methane-water
systems have been studied in great detail due to their commercial importance. Several GPA and other research reports
are available detailing the phase behavior of hydrates [64].
The c o m m o n industry "rule of t h u m b " is that hydrate formation requires free water to be present, and that it cannot
occur with sub-saturated, on-spec propane. Technically, this
is not true, but it is good enough for most applications, with
some caveats to cover high dissolved water contents and high
pressures. Technically, free water does not have to be present
for propane hydrate to form, but in such cases, there is so little soluble water available for hydrate formation that it is
rarely a problem, or at least is not a more severe problem
t h a n if only water ice were formed. The presence of free
w a t e r in the hydrate formation t e m p e r a t u r e range can
cause severe problems because m u c h larger quantities of
hydrate can form. Below freezing, there is no practical reason
to differentiate between hydrates and water ice in most
applications.
Propane hydrates are stable above the freezing point of
water. The higher the pressure, the higher the temperatures
at which they are stable. They can form at any temperature
below about 5.5C (42F) in propane at its saturated VP. No
externally applied pressure (for example, a pump) is required
for propane hydrates to form. Externally, the symptoms of
having ice or hydrates in LPG systems are virtually identical.
They both form only when it's cold, they both accumulate
and plug lines and orifices, and they both are "melted" by
methanol, leaving the same a m o u n t of liquid methanol/water
mixture at the bottom of the tank. The problems are the
same, the fix is the same, and the result is the same. Most of
t h e time, it doesn't matter, a n d there is n o need to
differentiate between water ice and propane hydrate.
Gas hydrates are the "phantoms" of the LPG world, and are
notoriously difficult to "diagnose" when they do occur. They
decompose (sublime) to water and hydrocarbon gas at ambient pressures very quickly, since they are essentially solids
with a VP of about 80 psi. The sublimation rate can be high
enough to support a burning flame [65]. Often they are gone
by the time the e q u i p m e n t is depressurized and opened
for inspection.
It is always uncertain whether hydrate, pure water ice, or
both are involved when icing occurs in LPG systems. The
biggest difference is that "icing" can occur between 0 and
about 4.5C in LPG systems, due to hydrate formation. It is
r a r e for the t e m p e r a t u r e to be stable in this range long
enough during a n icing episode to make it obvious that hydrate and not water ice is the cause. The day/night temperature difference is generally m u c h larger than this. However,
even w h e n this occurs, people will generally first tend to
think that the thermometer is off by a couple of degrees, or
that there is some auto-refrigeration somewhere, rather than
a hydrate event occurring above 0C.
Hydrates can form both in the liquid and vapor phases, but
there are some differences in behaviors that can be important
2: LIQUEFIED
PETROLEUM
GAS
45
in some situations. Firstly, hydrates tend to form at free-water surfaces. This is because propane type II hydrate has a
composition of a b o u t 17.1:1 mole ratio of waterrpropane,
which greatly exceeds the propane solubility in water. As a result, when a tank containing free water is cooled towards
zero, it will tend to form a thin layer of hydrate on the water
surface, like the first thin skin of ice on a pond, puddle, or ice
cube tray. The hydrate layer becomes a barrier for propane
diffusion, effectively limiting the rate of further hydrate formation. As the t e m p e r a t u r e drops further below 0C, the
underlying "metastable" water can freeze to water ice.
Thermodynamically, the hydrate and water ice should not
exist together; they are only there due to a kinetic rate limitation. Under thermodynamic equilibrium conditions, water
ice would not form until all of the propane is consumed first
forming hydrate, leaving water or water ice in equilibrium
with hydrate, and no propane liquid. As a result, mixing and
turbulence are invariably factors in hydrate formation from
propane liquid.
Secondly, hydrates can form very quickly on tank surfaces
exposed to the vapor space by deposition from the vapor (i.e.,
the opposite of sublimation). The equilibrium concentration
of water is always higher in the vapor phase, which favors hydrate formation from the vapor. This can be a very fast and
"efficient" process, as there is no kinetic barrier, and the water
vapor and propane are already mixed. Only the rate of diffusion and convection of the water vapor limit the rate of hydrate formation. Hydrate formation from saturated equilibrium vapor depletes water from the vapor phase, essentially
dehydrating it. Additional water will vaporize from the liquid,
and contribute to additional hydrate formation. If liquid water were in the tank bottom, and one waited long enough, all
of the water would eventually form hydrate at the tank bottom, or dissolve into the liquid propane, vaporize, and form
hydrate on the vessel walls that are exposed to the vapor. This
process would continue until all the free water was consumed,
leaving only hydrate on the tank bottom and vapor walls. The
liquid propane in equilibrium with the hydrate can still be "off
spec" near the high end of the hydrate formation range. The
real fun begins when the tank gets emptied out and re-filled
with dry or warmer propane, which immediately goes "offspec" for no apparent reason, or the temperature changes
rapidly, and slugs of water or chunks of "ice" show up.
This can result in some truly exasperating situations when
investigating water related problems in cold LPG systems.
You are never sure if free water is present, or if the liquid or
vapor is in equilibrium, or if any sample is representative.
The basic concept of obtaining representative samples is
s o m e w h a t uncertain. You generally don't have a b o t t o m
drain, and you can't see inside of the tank liquid or vapor
space. When you open it up, it's all gone. This, plus the inherent difficulties of sampling/measuring low p p m levels of
water and methanol in LPG makes reliable quantitative measurement of water virtually impossible in cool/cold weather,
without extraordinary attention to sampling and analytical
detail. Throw in a couple of different test methods with no
precision statements, no calibrants, no reference standards,
no QCs and uncertain correlation, and "exasperating" is an
understatement.
It is left to the reader's imagination the many hours of stimulating conversation possible between the lab, the process
46
MANUAL
HANDBOOK
of Methanol
in
Propane
CHAPTER
The use of methanol is mandated under certain codes and
standards to minimize free water from tanks prior to putting
t h e m into service or if water is reasonably expected to be
present [69].
Methanol works by creating either a second non-freezing
separated phase in the liquid, in the vapor (hydrate), or the vapor if re-condensed. Methanol/water mixtures will not freeze,
but will gravity settle, and tend to collect at tank bottoms,
where it can be difficult to remove. This can promote other
problems such as corrosion and resulting sediment and filter
plugging, which is undesirable in the downstream applications. As a result, there is a general consensus that propane
should be manufactured as dry as necessary for "normal" operations, and that methanol should be used as needed for new
tank commissioning, and cold weather operations in downstream (post refining) distribution and use.
Methanol is equally difficult to detect as water at low p p m
levels, especially in the field. As a result, the actual amounts
of water or methanol present are rarely measured directly. It
is also recognized that methanol interferes with some of the
c o m m o n "dryness" test methods once it has been added to
propeme. D2713 "valve freeze" test is quite explicit in stating
that the test does not apply to LPG containing antifreezing
agents (although it is commonly used for this purpose in
spite of this caveat). The CoBr test is believed to be relatively
i m m u n e to methanol, but this test is not widely used. The
chilled mirror dew point test is affected by methanol, since it
phase separates with water. Electronic hygrometers (dew
point meters) m a y or may not be affected by m e t h a n o l
depending upon the principle of operation.
In colder climates, it is common for methanol to be added
to bulk storage during distribution as a preventative measure. Long-term field experience indicates that this is a n effective strategy to minimize regulator freeze-up problems, so
long as addition is controlled to the m i n i m u m required. Different companies have applied mzmy different criteria, in the
absence of reliable field tests that can be used to monitor and
control water/methanol. This is an area of r e c o m m e n d e d
focus for future research and standcirdization
A 50 wt% methzmol/water mixture (common windshield
wiper Emti-freeze in cold climates) will not freeze down to
below 40C. Therefore, as long as any separated
methanol/water phase is at least this concentrated, no freezeu p is possible under typical conditions of LPG use. Methanol
is more soluble in propane than water, so more remains in
the propane phase in equilibrium with the methanol/water
separated phase. Limited low temperature solubility data indicates that the methanol solubility in propane in contact
with a 50 wt% methanol/water solution at -40C is about
400-800 p p m w [70]. This indicates that it would take about
400-800 p p m w methanol to prevent freezing down to about
40C at ambient pressures for w a t e r saturated p r o p a n e
(about 100 p p m w at 70F). This is smaller than the solubility
of methanol in propane at ambient temperature, so methanol
use tends to be "robust" so long as gross overdoses are
avoided (and a dry grade of methanol is used). Slightly lower
treat rates would be expected for lower water contents, or if
freezing protection was only required to a higher temperature. The lower limit to eliminate all solid formation at -40C
would be expected to correspond to the 400-800 p p m w solubility of methanol in propane u n d e r these conditions. The ab-
2: LIQUEFIED
PETROLEUM
GAS
47
of
Water
of Water in LPG
There has cJways been a desire in the LPG industry to have better test methods for "dryness," especially for production and
terminal bulk receipts, which are the two main control points
48
MANUAL
HANDBOOK
Green
Blue
Lavender
Pink
Very Dry
From nearly 0% to 30%
From 30% to 52%
From 52% to 100%
^ The humidity of the equilibrium vapor is dependent on temperature, since the wt. "K ratio varies from about 10 at 60F to about 15
at 32F. As a result, both the CoBr and Dew Point test methods are
more severe (conservative) at 32F than at 60F (or higher). This temperature dependence is not considered in the test methods, and the
same pass/fail criteria is applied regardless of the temperature of the
storage tank and equilibrium vapor.
CHAPTER
the scope. This is another area of recommended research and
stEmdardization.
R e s i d u a l Matter (Oil Stain & R e s i d u e )
Non-volatile materials that are soluble in liquid propane tend
to a c c u m u l a t e at the point of p r o p a n e vaporization as a
residue or gum that can interfer with the proper operation of
some equipment. The oil stain test attempts to concentrate
non volatile residues that can be visually detected by putting
it dropwise on a clean filter paper. This test is quite subjective a n d can be influenced by the grade of filter paper, or
color of the residue. Historically, the main purpose of the test
was to detect traces of compressor oils, a c o m m o n occurence
in the early days of the industry, but less c o m m o n today.
Other sources of heavy naaterials can be heat transfer fluids
from distillation processes, caustic, amine and glycols used
in some processes, greases and "pipe dope," sample cylinders, hose plasticizers, or cross contamination with other hydrocarbon fuels and lubricants if any c o m m o n equipment is
used in distribution.
Contaminants that form "oily residues" or "waxy solids"
with auto-refrigeration of vaporizing propane, especially in
association with fine particulates, can interfere with proper
operation of safety lock-offs, overpressure vents and regulators. Non volatile additives are generally not recommended
for use in propane intended for vaporizing service, and specific warnings are included in D130 copper corrosion test
pertaining to corrosion inhibitors ("masking agents"). Some
higher boiling or polymeric materials may interfere with catalytic heaters or automotive catalysts if present in the liquid
propane. ASTM specifications currently do not include limites for higher t e m p e r a t u r e evaporation limits. This is a
potential area of future research a n d standardization.
Propane is a very poor solvent for parafin wax (n-parafins
or near parafins) or for asphaltenes, and has been used in
commercial de-waxing and de-ashpalting processes. Contamination of LPG with "black" oils that contain asphaltenes
(IFO, HFO, Bunker, Pitch, Crude) or distillate fuels that contain wax (diesel, furnace oil, marine gas oils, kerosene, Jet)
can result in the precipitation and collection of waxy or asphaltene solids. This can cause m u c h more severe operational
problems than an oily liquid because of more severe impacts
on equipment. Care must be taken to prevent cross contamination of these materials. Sources for such contamination can
include leaking heat exchangers, pipeline "dead legs" or idle
p u m p loops, meter provers or other distribution equipment
that may be inadequately cleaned from a previous service.
Nonvolatile additives may be beneficial for certain applications, such as detergent/dispersant additives for autopropane,
similar to gasoline. However, this can introduce the need for
a segregated fuel, since they can still be detrimental to vaporizing services. Maintaining a single universal grade would
require additive injection at the point of dispensing. This is a
potential area of future research and standardization.
2: LIQUEFIED
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GAS
49
Contziminants
Magnetic
Residues
("Black Deposits")
and
Particulates
50
MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
[77]) as a result of widespread problems especially in automotive LPG fuel systems [78]. Iron particulates either from
heat treating "mill scale" or corrosion processes can adversely affect the operation of components that magnetically
attract and trap these materials in the working mechanisms
(e.g., magnetically coupled level gauges and electronic
solenoid valves). Collection of gross a m o u n t s of solid
residues (magnetic or otherwise) can adversely affect operation of filters, filter lock-offs, regulators, mixers, pressure release valves, etc., by mechancial blockage. Two to ten micron
(absolute. Beta 5000) filters have been found to be effective to
remove these materials with good filter life (granular well
behaved filter calie).
Ammonia
A m m o n i a is not used in the production process, a n d is
generally removed by gas stripping and distillation if it is
present. Anhydrous a m m o n i a is widely used in agriculture as
a fertilizer, and is transported in the same pressure rated
equipment as LPG. It is c o m m o n for rail and truck cargo vessels to transport "anhydrous" during the spring and s u m m e r
growing season. The s a m e rail or truck cargo tanks are
converted to LPG service for the fall and winter heating season. This is advantageous for optimal use of transportation
equipment, but offers increased chance of cross contamination without adequate cleaning in the change of service
procedure.
Anhydrous e q u i p m e n t a n d LPG p r o d u c t i o n e q u i p m e n t
generally use only carbon or stainless steel fittings. Brass
(copper alloy) veilves and fittings are commonly used in LPG
systems, particularly those at the dealer and consumer level.
Ammonia can cause stress crack corrosion in brass and copper fittings at concentrations above about 5-10 ppmv [79].
There is no firm specification or guideline on the maximum
allowable ammonia concentration of propane for either short
or long term exposures, Eind a level of < l p p m (detection by
field litmus paper test) is usually recommended.
Field tests based on color change of wet red litmus p H
paper are adequate to detect ammonia down to about 1 ppm,
and provide an effective go/no-go test after change of service
or at any time during distribution [80].
The time required for the color change due to the field test
can also be used to judge the severity of the contamination.
Very high (>20 ppm) concentrations cause a strong color
change in only a few seconds. Moderately high (5 ppm) will
cause a medium color change in about 10 s and low ( < l p p m )
will cause slight change in about 30 s.
The litmus test is very sensitive to any material with even a
slightly higher than 7.0 pH. This includes saliva (depending
on what was last eaten), high p H potable ("tap") water in
some regions, or soaps or detergents that may have been used
to wash the hands or equipment.
Controlled tests indicated that p r o p a n e with low concentrations of a m m o n i a would have n o effect on the
concentration of ethyl mercaptan odorant [81].
Halocarbons
(Refrigerants)
CHAPTER
Chapter W.l.l, Compressibility Factors for Hydrocarbons:
0.350-0.637 Relative Density (60F / 60"F) and -50F to
140 F Metering Temperature, and 11.2.2M, Compressibility
Factors for Hydrocarbons: 350637 kg/m^ Density
(ISV)
and 46C to 60C Metering Temperature, also give procedures to determine the VCFs due to pressure. These
procedures cover the lower densities indicative of most
LPG and NGL.
Until 1998, the VCFs due to temperature for the LPG and
NGL not covered by Chapter 11.1 were calculated from a variety of sources. The major source was a set of Petroleum
Measurement
Tables published in 1953 by ASTM International and the Institute of Petroleum (IP). New implementation procedures for liquids with relative densities (60760)
of 0.3500 to 0.6880 (272.8 to 74.2API) were p u b h s h e d
in 1998 as Technical Publication TP-25 Temperature Correction For The Volume Of Light Hydrocarbons. This is a GPA
publication, but GPA, API, and ASTM have jointly adopted it
[84]. These procedures are based on an experimental program sponsored by all three above organizations. Based on
this expanded database the TP-25 factors are different by as
much as 0.2-0.8% from the 1953 Table factors.
The underlying procedure in TP-25 is quite different from
the fairly empirical equation forms used in the other standards. The TP-25 factors are determined from the interpolation of the properties of reference fluids via a corresponding
states formulation. Corresponding states theory has a rich
history for the use of correlating various t h e r m o d y n a m i c
properties. This particular formulation is unique in that it
uses the relative density at 60F as the interpolating variable.
The calculation of the density at a temperature is based on a
comparison of the properties of the reference fluids at the
same reduced conditions. All the reference materials and critical properties required to do the calculations are available in
the standard.
The organization of the VCF standards in the API Manual
of Petroleum Measurement Standards is being changed. The
revised Chapter 11.1, Temperature and Pressure Volume Correction Factors for Generalized Crude Oils, Refined Products,
and Lubricating Oils, will combine the previous Chapter 11.1
and 11.2.1 temperature and pressure correction procedures
into a single unified procedure. The nominal API gravity
range will be 10 to 100, so it will still only cover the heaviest of LPG. Two important changes will be that the single set
of procedures will be valid for the customary and metric standard temperatures (60F, 15C, and 20C) and for measurem e n t temperatures and pressures in customary or metric
units. Chapter 11. Iwas approved for D 1250-2002 and will be
published in 2003.
The revised Chapter 11.2, Temperature and Pressure Volume Correction Factors for Light Hydrocarbons, will use the
TP-25 procedure as the basis for the temperature portion of
its VCF procedures. It will cover the range of relative densities (60/60) of 0.3500-0.6880 (272.8-74.2API), just like TP25. Like the revised Chapter 11.1, this will contain a single set
of procedures valid for the customary and metric standard
temperatures (60F, 15C, and 20C) and for measurement
temperatures and pressures in the customary or metric units.
Technical work is being done to incorporate pressure correction procedures. It is expected that this revised Chapter 11.2
will also be published in 2003.
2: LIQUEFIED
PETROLEUM
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51
The VCFs are always based on averages on a range of materials, or by interpolation between reference standards. Individual mixtures that have similar density but different
composition than either the average or reference may have
significantly different expansion coefficients. Use of the
standard VCFs will give a biased result on these mixtures.
Provisions are made in the standards for contracting parties
to determine and use VCFs based on density measurements
on the individual material or mixture. Alternatively, to minimize uncertainty, contracting parties may specify that the
density determination used for custody transfer be obtained
as close to the standard conditions as possible. This is easily
done for temperature, but is more complicated for pressure.
In the past, pressure correction was often omitted or ignored,
or based on measurements done at the time and temperature
a n d pressure of custody transfer. To accommodate existing
industry practices, the new standard TP-25 contains two sets
of tables, one for temperature correction alone, and the other
for combined temperature and pressure correction.
AUTO PROPANE
LPG has been used as a spark ignition motor fuel for over 40
years, especially in fleet and workplace applications. The primary advantages over gasoline in these markets are related to
availability, cost, and tailpipe emission levels. Fleet operations can operate from centrally located refueling sites,
avoiding the need for widespread availability at retail gasoline service stations. The lower operating cost for fuel may
offset the cost of conversion, with a net benefit for high
mileage applications such as taxi or delivery fleets. The
breakeven mileage generally varies between 5000 to 25 000
km/year, depending mostly upon the presence and level of
Government incentives for conversion cost, registration and
differential fuel taxation. The tailpipe and environmental
benefits depend mostly upon the technology and calibration
of the engine using the fuel and to a lesser extent on the properties of the fuel itself. However, with equivalent levels of
technology, LPG tends to have a significant advantage with
emissions and emissions toxicity.
Historically, both gasoline and propane employed similar
carburetor and intake manifold configurations. This allowed
widespread "aftermarket" conversion of engines from gasoline to LPG, using engine coolant driven vaporizer/regulators
and various gas injector devices. These could be plates that
could be "bolted on" above or below the existing liquid gasoline carburetors for dual fuel operation, or gas carburetors
for dedicated LPG use.
LPG carburetor engines generally have lower tailpipe hydrocarbon and carbon monoxide (HC,CO) emissions than the
equivalent technology gasoline engine, when no computer
feedback engine control strategies are used. This is primarily
due to reduction/elimination of fuel enrichment for idle, throttle transient and high power engine operation. This made
propane a preferred fuel for such indoor engine applications
as forklifts, where indoor CO emissions must be minimized.
The widespread introduction of tailpipe catalysts and electronic fuel injection systems to meet increasingly more stringent emission standards has made aftermarket conversions
increasingly challenging on recent model automobiles to
52
MANUAL
HANDBOOK
LPG could be an ideal fuel for emerging micro-turbine applications a n d high-temperature partial oxidation (POx) fuel
cells. LPG can be produced in high purity and low sulfur that
may be necessary for these applications.
LPGSAFETY AND HANDLING
LPG F l a m m a b i l i t y
Propane is flammable in the a t m o s p h e r e at ambient
conditions between about 2-9.5 vol%, the Lower and Upper
Explosive Limit (LEL a n d HEL), respectively. This corresponds to about 0.3 psia peirtial pressure for the LEL, and
about 1.4 psia partial pressure for the HEL. LPG is normally
handled at pressures m u c h higher than this. LPG must be refrigerated to less than 100C before the equilibrium vapor
pressure enters the explosive range. This is virtually unattainable in normal operations and would only be a concern in
some research or specialty applications. Thusly, physical
mixtures of gases, especicdly in air, is always more important
for LPG t h a n "flash point" considerations.
Flammability is not a fundamental or t h e r m o d y n a m i c
property of any material. It depends upon the circumstances
at the time, including gas mixture, temperature, pressure, ignition energy, turbulence, aerosol, catalyst and even the nature of the surface and shape of the containment vessel. The
lower explosive limit is less sensitive to these effects than the
higher explosive limits. For example, the LEL is almost totally insensitive to the a m o u n t of "diluent" gas added [90,91].
The HEL is the most impacted with dilution by inert gas, essentially decreasing almost linearly to near the LEL at about
40-50% dilution (10-13% oxygen vs. 2 1 % undiluted). The
flammable envelope terminates at the point that the HEL
meets the LEL.
The explosive envelope tends to enlarge at higher temperatures, but again more on the HEL side vs. the LEL side. The
change in LEL is in fact quite small, with only an 8% relative
change in LEL with a 100C increase in temperature from
ambient [92].
In general, it appears that any increase in temperature,
pressure, gas composition, ignition energy, or configuration
has a m u c h more profound effect on the HEL than the LEL.
Use of the LEL determined at ambient conditions can reasonably be expected to apply over a very wide range of conditions in typical LPG handling situations. This is not true for
the HEL, which varies widely with similar changes in gas
composition, temperature, and pressure.
LPG H a n d l i n g
Most jurisdictions require that persons involved with the
handling or transport of LPG or installing LPG equipment
be trained and licensed. This generally does not include final connection of portable cylinders to consumer appliances
using approved fittings, but usually does include filling
of the portable cylinders or automobiles at the point of retail sale.
LPG, like any fuel, is safe if properly handled. It has a relatively n a r t o w explosive range, so explosions are rare. However, spills and fires are similar to other volatile fuels and
solvents. Certain properties of propane should be understood
CHAPTER
to p r o m o t e safety in handling the fuel, and a p p r o p r i a t e
responses in the event of a spill or emergency response.
LPG vapor is about 50% heavier t h a n air (molecular weight
44 versus 29). Vapors will tend to settle in low points and cavities in the absence of a ventilating air flow. Propane/air mixtures have densities closer to air, and are more easily mixed
and dispersed from thermal or a m b i e n t air currents. For
example, a mixture of one volume of propane vapor (MW 44)
diluted 9:1 with air will only be 5% heavier than air (about
the same relative difference as sea water a n d fresh water). It
will still be above the explosive range, but will be prone to
dispersion from ambient air currents. The heavier than air
vapor density allows a potential and usually temporary pooling. Leaking gases tend to exit from high-pressure sources at
a sufficient velocity to stir the air mass and cause mixing.
They will only tend to accumulate in low spots only in very
quiescent conditions.
When propane or propane/air mixtures (above the HEL)
collect in low spots, there will cilways be an interface at the
top of the vapor pool that is in the flammable range. This will
b u m very similarly t o any other flammable liquid. A very
good safety demonstration is to fill a tall (high 1/d) nominal
500 m L beaker with pure LPG vapor, and leave it open in full
view for the duration of the training session. When asked after several hours, most attendees generally believe that the
"volatile gas" has escaped and is rapidly dispersing itself
through the cosmos. However, lowering a match slowly below the rim convinces everyone that not very much gas has
escaped, a n d for approximately the next 15 s, you can see the
flame level drop in the beaker, as the pool fire consumes the
propsme. This is a "worst case" demonstration, as ambient air
currents cannot penetrate and mix a tall vessel very far. However, it does serve to show that propane rich pockets of gas
can be stable for hours, days, and even weeks in the absence
of strong wind or air currents of a velocity sufficient to mix
the ambient atmosphere. It is important to vacate and properly ventilate an enclosed area that may have been subject of
a propane leak in the absence of ventilating airflow.
Small liquid leaks can turn large volumes of area into explosive mixtures under "ideal" circumstances. At room temperature, one liquid liter of propane expands to about 240
Liters of gas, which at 2% LEL is sufficient to create 12 000 L
of explosive atmosphere. It takes only a small liquid leak to
create a n explosive atmosphere in a confined area, if the
propane becomes well mixed. Since the entire system is under pressure, leaks can occur even when equipment is idle,
and collect over a long period of time.
Gas-Air mixtures may be brought below the flammable
limit by dilution with large volumes of non-flammable gasses
such as nitrogen, carbon dioxide, steam or air [93] (see
flammability above). Some precautions should be taken to
prevent ignition by static discharge with some CO2 fire extinguishers. A gas inerted area may still present an asphjrxiation
hazard. The rapid venting of gas and especially of gas/liquid
aerosols can create static chcirging situations. As a result, ignition of vented "vapors" can occur at any time, depending
u p o n circumstance.
Gas mixtures inside of the flammable region do not "bum"
like a pool fire. They forcefully explode, generating a shock
wave a n d a sharp "firecracker" type of sound. The largest energy release is when the mixture is at stoicheometric, and the
2: LIQUEFIED
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54
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
sphere at 70F, the hquid will cool down to the boiling point
(-42C) after about 40 wt% of the liquid has vaporized. High
appliance demand and rapid vapor withdrawal rates generally results in a large amount of condensation or frost accum u l a t i o n on the exterior of the c o n t a i n e r due to this
refrigeration effect.
LP-Gas vapor upstream of the regulator can condense to a
liquid if the lines external to the tank are at a lower temperature than the tank, and this requires special attention to detail, especially in cold climates. For example, during snap
cool situations, outside vapor lines cool down faster than the
bulk storage tank, due to the higher thermal mass of the tank.
The higher storage tank pressure causes condensation of liquid propane in the vapor lines. This can result in vapor lines
becoming filled with condensed liquid propane under snap
cool conditions.
Propane has a m u c h higher coefficient of thermal (and
pressure) expansion than other hydrocarbon fuels. Heating
an overfilled propane vessel can result in thermal expansion
of the liquid until the cylinder is fully liquid filled (the vapor condenses as the liquid expands). Very high pressures,
exceeding several thousand psi, can be generated with further heating and liquid expansion in a liquid filled ("hydraulically locked") cylinder. Pressure safety vents will generally prevent this, b u t the resulting leak of liquid can
become a fire hazard. All transportation codes require cylinders to be only partially filled for this reason, but it is not
commonly appreciated that this is relative to a reference
temperature (traditionally 80vol% fill at 60F). This protects
against hydraulic lock u p to over 140F for liquid fill at
60F. If the cylinder is filled at a temperature lower than
60F, it may be necessary to further reduce the fill density
for storage and transport. Consult the authority having jurisdiction for the applicable requirements.
LPG S a m p l e C y l i n d e r A p p r o v a l s
Consult the Authority having Jurisdiction for pressure vessel
certification r e q u i r e m e n t s for LPG sample cylinders (US
DOT in United States and Transport Canada in Canada). At
present there is no international approval process for pressure cylinders. Authorities in adjacent or other jurisdictions
m a y not approve cylinders approved in one jurisdiction.
Cylinders must be approved in all the jurisdictions in which
they are used for sample transport. Cylinders approved by the
Authority having Jurisdiction u n d e r "equivalent level of
safety" criteria are acceptable provided that they are used in
accordance with the applicable permits or exemptions. For
example, users may not subsequently alter valves or pressure
venting devices that are part of a permit or exemption. Periodic cylinder inspections may be required [94].
LPG E x p o s u r e
The health effects caused by exposure to LP Gases are much less
serious than its fire and explosion risk. LP gases at low concentrations are non-toxic, and liquids have limited ingestion routes
due to the physical properties of the materials. The Occupational Exposure Limits (GEL) are based mostly on the need to
avoid the explosive hazards by a wide margin. This is t5^ically
20% of the LEL or lower, which is a much lower level than
would be set for short or long term toxicity, or Eixphyxiants.
LP Gases at very high (explosive) concentrations are believed to be non-toxic, fast acting anaesthetic agents, as well
as being simple asphj^iants. The terminology "propane narcosis" is sometimes used, but this is not accurate. Narcotics
generally refer to drugs that act at opiate receptor sites,
which is not where general anaesthetic gases act. However,
the term "narcosis" is quite generic. The c o m m o n definition
is "to put to sleep, partially or totally" due to a general depression of the Central Nervous System (CNS), even though
sleep, anaesthesia and narcotics are distinctly different in
medical terms. There are some early references to LP gas
being tried or used as a medical anaesthetic, and one of the
LPG patent claims by F.P Peterson in 1914 was for use "in
surgery as an anesthetic" [95]. However, only cyclopropane,
nitrous oxide, ethers, and various halocarbons were used
clinically as anaesthetic gases, usually in combination with
other drugs.
Persons exposed to high levels of LPG gas and experiencing CNS depression effects are in a very dangerous
situation, since they are breathing explosive gas mixtures.
Any ignition source could produce a fire or explosion, resulting in injury or death. Individuals vary widely in their
susceptibility and tolerance to these effects. At high concentrations, the effects of narcosis and h3^oxia will be confounded, as they are outwardly similar in many respects,
and will occur simultaneously. There is a range of symptoms with increasing concentration from the onset of CNS
effects, hypoxia, and asphyxiation: disorientation, lightheadedness, dizziness, drowsiness, loss of physical coordination, impaired judgment, drunkenness, unconsciousness,
and death.
The CNS effect is believed to be dependent upon the concentration of the gas in the lipid bi-layer (cell wall m e m brane) of nerve cells. Different gases would be expected to
have a different potency, and require higher or lower exposures to obtain the same CNS effect. The relative solubility of
different gases in olive oil (surrogate for lipid), water (surrogate for blood), can be compared to a very wide range of
materials that have well known physiological responses. By
this method, the onset of einaesthetic effects is estimated to
be n e a r the lower explosive limit (2%) for butane, a n d
about twice the LEL (4%) for propane. Iso-butane causes
drowsiness in a short time in concentrations of 1%, with no
apparent injuries from i-C4 or n-C4 after 2-hour exposure at
concentrations u p to 5% [96].
The rapidity of both the onset and recovery of CNS effects
from gas exposure depends upon the speed at which the gas
is transported into and out of the body. This is dependent
upon the concentration of the gas in air, the breathing and
blood circulation rate, and the relative solubility of the material in lipid (oil) and blood (water). Gases with low water
(blood) solubility and high oil (lipid) solubility tend to be the
fastest acting. The large volume of blood/water in the body
tends to act as a "buffer" for water-soluble compounds, slowing accumulation and depletion from the nerve cells. The solubility properties of LPG lie close to cyclopropane, between
those of nitrogen and nitrous oxide/diethyl ether, where the
rates are well known. Cyclopropane anaesthetic, which is 4-5
times more soluble in water than propane, is not altered or
combined in the body; the major part is exhaled within 10
min, while full desaturation takes several hours [97]. LPG
exposure above the explosive limit would be expected to in-
CHAPTER
duce CNS effects quickly, certainly in less than 15 min, and
probably in less than 5 min.
Persons installing new equipment, flushing lines, repairing,
or re-lighting appliances, or investigating gas leaks are also
the most likely to be exposed to high LP-gas concentrations. A
Consumer Products Safety Commission (CPSC) study noted
that new LPG installations are more prone to accidents than
new natural gas installations and sponsored a n u m b e r of studies relating to LPG odorization [98]. While the lighter than air
density and higher LEL of methane are undoubtedly major
factors, the CNS effects may help explain the occasionally
bizarre circumstances of some LPG accidents.
The knowledge of possible impairment can be critical in
making decisions effective in reducing the accident rate. For
example, a person flushing a line might realize the need to
take a fresh air break instead of a "smoke" break, or ventilate
the area if it is u n d e r s t o o d t h a t the light-headed or tired
feeling may be due to explosive gas concentrations.
Anaesthetics also sensitize the myocardium to the effects
of epinephrine. Cardiac a r r h y t h m i a can occur when very
high concentrations of LP gases (above the HEL for propane)
are inhaled when the epinephrine level is elevated (e.g., anxiety, exertion) cind possibly during hypoxic conditions. Ccirdiac arrhythmia can have a sudden onset even with brief
exposures a n d may result in sudden death. This is an extreme
condition that is usually associated with substance abuse
(commonly called "huffing"). Similar problems have been reported in the nitrous oxide bottle gas industry. Additional
information is available on the web site of the Compressed
Gas Association [99].
LPG Odorization
LPG odorization requirements reside in different jurisdictions in different countries. The U.S. requirements are not in
the ASTM D1835 specifications, but in NFPA 58 and 19 CFR,
and State Regulations. Canadian requirements are in the
CGSB LPG product specifications that are referenced in various Provincial and Federal Regulations.
Historically, manufactured gas was odorized as a warning
aid due to the risk of carbon monoxide poisoning. Manufactured gas often contained high levels of CO, which was a
higher risk than flammability. Over time, a variety of matericils, including mercaptans, acetylene, and mixed refinery sulfides were used as odoureints. LPG production from sweet
natural gas wells had no olefins and a low sulfur content, so
had a n intrinsically low odor. Initially, there was no requirement to odorize gas distributed for fuel purposes, as it was
non-toxic relative to manufactured gases. However, a number of fires and explosions with non-odorized natured gas and
LPG highlighted the need to odorize as a warning aid to detect leaks. LPG odorization is now a regulated requirement in
all North American jurisdictions.
Natural Gas Euid LPG odorization has been the subject of
substantial product liability litigation, stretching over several
decades of work on the technical, political, and legcd issues
involved. These are summarized in a series of IGT sponsored
technical symposia [100], CPSC, GPA, NPGA, PGAC, and
BERC sponsored rescEirch, as well as transcripts of various
product liability cases. Current North American Odorization
practices are based on 1977 BERC smalysis [101] indicating
ethyl mercaptan (EtSH, or EM) to be a preferred odorant
2: LIQUEFIED
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55
56
MANUAL
HANDBOOK
USES OF LPG
Industrial
fork lifts, indoor carburetor engines (floor sweepers, washers, etc.)
oxy/propane cutters, heating/annealing, high pressure
welding
"plumber" torches, portable soldering irons, small torches
hand torches (pallet shrink wrap, localized heating/burning)
worksite heating/ventilating (lineman's tents, below grade
sites)
refrigeration (compressor cycle), evaporation, or specialty
(vap pipes)
pavement heating for grinding/recycling, roofing tar
heating
ground thawing, ice/snow melting, concrete heating, etc.
propellant for aerosol sprays, cosmetics, shaving cream,
perfumes, etc.
propellant for paint sprayers, paint airbrush (including PB
mix)
solvent for cleaning, reaction, diluent/chilling, precipitation
remote "smart" gen sets with remote start/stop, telemetry
integrated standalone packages (power generation, ventillate, heat/cool)
portable soil/trash reclamation, sterilization
jackhammers (construction road work)
Power
cyclopropane anesthetic
microturbine and distributed power systems
stationary generators
standby fuel for gas interruptible supply
Transportation
autopropane (conversions) and OEM
cargo heaters, engine coolant pre-heaters, ice removal
heavy duty truck alternate fuel (fumigation and OEM)
hydrocarbon fuel for reforming fuel cell applications
retrofit of small engines to tighter emission standards
utility right of way maintenance
micro-turbine hybrid vehicles
Agriculture
grain drying, bam/brooder heaters, orchard heaters, weed
control
general shop heat/power/oxy welders, etc.
Colorado Potato Bug eradication, potato guns
farm animal m a n u r e dehydration/sterilization (esp. swine/
chicken)
weed control as alternative to herbicides to control runoff
"scare crow" devices
irrigation water pumps
Utility
Gas
Acknowledgments
The author acknowledges review and significant technical input from Dr. H. ICing, ExxonMobil Research (hydrates), John
Jachura (VCF/density), Dr. D.Y. Peng (Peng-Robinson EOS),
Dr. H.J. Ng, DBRA Research Associates (Ng-Robinson EOS,
hydrates), Larry. R. Robertson, DaimlerChrysler (autopropane), Alex Spatura, Adept Group, (autopropane a n d
extensive review), Ian Drummond, lOL Industrial Hygiene
(exposure/CNS), Dr. Byrick, Uof Toronto (CNS), Dr. Roth,
University of Calgary (CNS), Nancy Bourque, lOL Research
Library (literature and patent searches), Tim Eaton, Superior
Propane Inc.(uses). Thanks to Mark Sutton and Ron Brunner
(GPA) for access to draft publication TP16 on history of LPG
specs (hopefully to continue to publication). Special thanks
to Ron Cannon (GPA, retired) for input, review, and liberal
reference to his excellent book "The Gas Processing IndustryOrigins and Evolution." This is highly recommended
reading for anyone in the industry, and a good book for both
libraries and reception areas.
The author acknowledges the support of Imperial Oil Ltd.
for the information/communications resources used in the
preparation of this chapter.
Residential
cooking, heating, clothes drying, hot water
catalytic/radiant/pipe radiant heaters, mantel lights
h o m e barbeques, refillable lighters, hair curlers, b b q
lighters
fixed installation mobile home heating/cooking
Recreation
mobile RVs/trailers cooking/heating, absorption cycle
refrigeration
REFERENCES
[1] Tiratsoo, E. N., Natural Gas, Scientific Press Ltd, London,
1967, p. 20.
[2] Redwood, B.,A Treatise on Petroleum, S'^ ed., Charles Griffon &
Company, Ltd., London, Lippincott, Philadelphia, 1926, pp. 82,
219.
[3] Tiratsoo, E. N., Natural Gas, Scientific Press Ltd, London,
1967, p. 20.
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]
[94]
[95]
[96]
[97]
[106]
[107]
[108]
[109]
[110]
[111]
MNL37-EB/Jun. 2003
Motor Gasoline
B. Hamilton^ and Robert J. Falkiner-^
nology levels, and have produced the "World Wide Fuel Charter" (WWFC) on this basis. The WWFC receives serious
consideration when nations and economic regions are revising fuel specifications, even though it is not an accredited
consensus standard, and is the subject of ongoing technical
debate. ASTM Standard Practices, Test Methods and Specifications continue to be key to domestic and International
Specifications and Regulations, and are used globally
through affiliated ISO Standard Writing Organizations.
Specifications for n e w generations of engines (electric/
hydraulic hybrids, gasoline direct injection, fuel cells, microturbines) and catalysts (lean b u r n , heated, selective reduction, HC absorption, particulate trap) have yet to be
developed. The trend continues to be more restrictive in composition and variation than in previous gasolines.
HISTORY OF GASOLINE
L e a d e d Gasoline ("Pre-control")
In the late 19th century, fuels, for the automobile were coal
tar distillates and the lighter fractions from the distillation of
crude oil. It's believed that a gasoline fraction was separated
by Joshua Merrill in Boston, and was used for lighting. It was
also used in Nicolaus Otto's first four-stroke cycle engine in
1876. By the late 1800s the early refiners were producing
volatile gasoline by batch distillation from crude oil. Natural
gas producers were making volatile naphtha from the hydrocarbon condensed from compressed natural gas (condensate,
casinghead, or "natural" gasoline). There were no standard
test methods or national specifications, or definition of quality. Some of the earliest standard test methods were not developed until the 1920s, allowing development of the first
widely accepted gasoline specifications. Some test methods
developed in the 1920s are still in use today, such as the Reid
Vapor Pressure (originally developed for casinghead gasoline) and Distillation (the oldest currently used ASTM gasoline test method, first published in 1930). The D86 was based
on tests developed for casinghead or "natural gasoline" by the
predecessor organization of the Gas Processors Association
(GPA). The data triggered a n intensive discussion of the relationship between gasoline distillation profile (volatility) and
engine performance, such as vapor lock, oil dilution, knock,
and "sooting."
Automotive engines were rapidly being improved and required a more consistent and suitable fuel. New test methods,
specifications, and refining processes were developed to better separate and increase the octane of components. Com61
Copyright'
2003 by A S I M International
www.astm.org
62
MANUAL
HANDBOOK
H i s t o r y o f Alkyl L e a d i n G a s o l i n e
During the 1910s, laws prohibited the storage of gasoline on
residential properties, so Charles F. Kettering modified a
Spark Ignition (SI) engine to r u n on kerosene. However the
kerosene-fueled engine would "knock" and crack the cylinder
head and pistons. He assigned Thomas Midgley, Jr. to confirm that the cause was the kerosene droplets vaporizing on
combustion, as he presumed. Midgley demonstrated that the
knock was caused by a rapid rise in pressure after ignition,
not during pre-ignition as believed. The combination of TML
and TEL along with alkyl bromide and chloride alkyl lead
scavengers were widely used stEirting shortly after discovery
by teams led by Thomas Midgley Jr. in 1922 [4-6]. Several
CHAPTER
3: MOTOR
GASOLINE
63
Melting Point, C
-90.7
-107.45
alkyl leads. Parafins have the best alkyl lead response, followed by napthenes, olefins, and aromatics, while the response of alcohols is negative. The RON of the gasoline could
be increased from 60 to 75, and the "highest useful compression ratio" increased from 5.3 to 6.8, increasing the constantspeed fuel economy by about 30%.
The Motor Octane N u m b e r (MON) was developed in 1932,
using conditions that better matched actual vehicle knock
performance climbing the long constant grade hill at Uniontown, Pennsylvania. This method is similar to the operating
conditions of the current Motor Octane procedure [9,10]. The
MON test was a tentative method from 1933 to 1939, when it
was adopted as a n ASTM standard. During the late 1940s
through the middle 1960s, the Research method became the
m o r e i m p o r t a n t rating because milder conditions m o r e
closely represented the octane requirements of the vehicle
current engines and driving conditions. Most retail fuels were
marketed according to their research octane rating.
1 9 6 3 C l e a n Air A c t , V e h i c l e E m i s s i o n S t a n d a r d s
a n d Alkyl l e a d P h a s e d o w n
During the late 1950s and 1960s, ambient air quality deteriorated, especially in densely populated urban areas. ReseEirch
quickly identified the "primary pollutants" in raw exhaust
(HC, CO, and NOx) and sunlight driven photochemical reaction to be a major source of SMOG (SMoke + fOG). Ground
level ozone and other "secondary poUutcints" are formed by
photochemical reactions driven by sunlight. The concentrations of pollutants followed a daily pattern determined by
driving cycles ("rush hours"), daytime sunlight intensity, and
local geography and wind patterns, with the most severe area
in the U.S. being southern California. The original Clean Air
Act was passed in 1963 "to protect and enhance the quality of
the Nation's air resources." The first vehicle emissions standards were imposed in California in 1966 a n d Federally in
1968. The early attempts to reduce HC and CO with carburetor calibrations and thermal reactor ("thermactor," air +
time delay) type exhaust systems were only about 60% effective for HC. However, this was still a larger drop (est. 10.6
g/mile to 4.1 g/mile HC) than all of the emission reductions
since, due to the high emission rates at the time. A n u m b e r of
attempts were made to develop "lead-tolerant catalysts" and
"alkyl lead traps" that would allow continued use of leaded
gasoline. However, several new potential problems with continued widespread use of leaded gasoline were found, and
R&D to develop viable exhaust oxidation catalysts went into
high gear.
Alkyl lead is a toxin by itself, and there was a drive to reduce exposure levels from m a n y sources, ranging from alkyl
lead solder in pipes, food cans, toothpaste tubes, alkyl lead
pigment in paints, and edkyl leads in gasoline. In addition, the
alkyl lead scavengers ethyene dibromide and ethylene dichloride could react with u n b u m e d hydrocarbons in the exhaust
Density, g/ml
0.684
0.6919
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MANUAL
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placing the octane boost from alkyl lead was a big problem
for the fuel manufacturers, as there was n o readily available
replacement. This required significant changes to both fuel
and engine design.
Gasoline manufacturers found that it was possible to produce, on average, a nonleaded regular gasoline with an 87
AKI and about 91 RON in the United States, and a premium
95 RON in Europe and elsewhere. United States automakers
built engines with EGR and reduced compression ratios initially around 8:1 for use on 87 AKI non-leaded gasoline to reduce engine-out NOx to regulated levels. Air injection reduced HC and CO by oxidation over a COC. Efficiency and
fuel economy were reduced because of the compression ratio
reduction. However, this was more t h a n offset by Corporate
Average Fuel Economy (CAFE) regulations in 1975 that required average LDV fuel economy determined in standard
tests to increase over a period of years u p to 27.5 mpg. This
was accomplished with a variety of technologies. Vehicle
size, weight, and rolling/wind resistance were dramatically
reduced ("downsizing"). The majority of the fleet converted
to front wheel drive, using more efficient transverse L4 and
V6 engines and transmissions, both using lower viscosity and
friction modified lubricants.
1 9 7 0 U S E P A C l e a n Air A c t a n d 1 9 7 7 A m e n d m e n t
The 1970 U.S. Clean Air Act (CAA) established the Environmental Protection Agency and required a 90% reduction in
automotive emissions by 1975 (HC/CO) and 1976 (NO^). This
resulted in the widespread introduction of conventional oxidation catcilysts and nonleaded gasoline in 1975 in response
to the HC and CO standards. These regulations were "technology forcing" especially for NO^, and the U.S. Congress put
an interim NOx standard in place until 1978. The 1977 Clean
Air Act Amendments required reduction in HC in 1980 and
CO and NOx in 1981. This resulted in the widespread introduction of sophisticated "three-way catalysts" computer controlled closed loop air-fuel ratio control with exhaust oxygen
sensors in most 1981 model year cars. The 1977 CAA amendments contained the first provisions that controlled the properties of "future" gasoline. It had a general requirement that
gasoline be "substantially similar" to fuel or fuel additives
used to certify 1975 or subsequent years vehicles [13]. The
intent was that future gasoline would not render the new catalysts or emission controls ineffective over time. The EPA
subsequently promulgated the "substantially similar" ruling,
which had a more detailed definition of the meaning. It eilso
provided that additives containing only C, H, O, N, S (which
combust to the regulated emissions) did not require a waiver
at concentrations below 0.25 vol%.
Vapor Controls
CHAPTER
ern carbon canister systems can reduce evaporative emissions by more than 95% from uncontrolled levels. On-board
canister systems tend to make Stage 2 balancing redundant
as the on-road population equipped with enhanced canister
systems increases.
1 9 9 0 CAA A m e n d m e n t s ( R e f o r m u l a t e d a n d
Conventional Gasoline)
A more complete technical discussion on Reformulated Gasoline (RFG) is contained in ASTM Research Report D02:1347
[15], and in numerous other Government and Industry Publications [16]. Officially published sources of information should
always be used for regulatory compliance purposes. A summary
of the United States EPA gasoline, additive, and related regulations is available at http://www. epa.gov/otag/gasoline.htm.
A chronology of EPA emissions control regulations is available at http://www.epa.gov/ otag/12-miles.htm.
The 1990 Clean Air Act (CAA) amendments and California
Air Resources Board (CARB) Phase 2 (1996) specifications
required further reductions in tailpipe emissions, more stringent test procedures and vehicle on-board monitoring technology, and new "clean fuels" programs. These established
emission limits for reformulated gasoline, compared with
typical 1990 "baseline" gasoline. The first stage, the "Simple
Model" was an interim stage between 1 Jan. 1995 to 31 Dec.
1997. The second stage, the "Complex Model" h a d two
phases: Phase I (1995-1998) and Phase II (2000+).
Metropolitan regions with severe ozone air quality problems were required to use reformulated gasoline containing
at least 2.0 wt% oxygen to reduce 1990 volatile organic carbon compounds by 15% (1994), and reduce specified toxic
emissions by 15% (1995) and 2 5 % (2000). Because of a lack
of data, the EPA was unable to define the required parameters for the CAA, so an advisory committee containing representatives of regulatory, petroleum industry, environmental,
and consumer interests recommended a two-stage system for
implementation ("reg-neg"). The EPA also gave the refining
industry a choice of standard, based on either "per gallon,"
(Never To Exceed, NTE, or "cap" limit), or "averaged," based
on volumetric averages over an annual or seasonal production period (Yearly Pool Average, YPA, or summer/winter). In
some jurisdictions, regulations include requirements around
sampling, test methods, and validation/demonstration of test
proficiency, as well as certified third party testing, auditing,
and field "attest" monitoring.
Areas in attainment with air quality objectives continued to
use "conventional gasoline." The "anti-dumping" provisions
of the regulation ensured that the quality of conventional
gasoline was not degraded to facilitate production of RFG.
Conventional gasoline must be blended to provide equivalent
emissions of the national baseline gasoline (default for domestic or import), or individual refiner's baseline based on
prior production. The intent of these "anti-dumping" restrictions was to ensure emission improvements and non-attainment did not result in emission increases in areas currently
in attainment with the National Ambient Air Quality Standards (NAAQS). Emission improvements had to be made by
increased refinery processing for the manufacture of RFG.
The Auto-Oil Air Quality Improvement Research Program
(AQUIRP, "Auto-Oil") provided the basis for the "simple" and
3: MOTOR
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65
"complex" models used in EPA and most other North American gasoline regulations. Measured emissions were correlated to gasoline properties in a wide variety of vehicle emission system types. These spreadsheet type correlation models
predict emissions from all sources associated with using
gasoline in vehicles. They tcike into account the time of year
(winter/summer), gasoline composition as measured by eight
parameters (called the model parameters), and an assumed
on-road vehicle fleet with a mixture of various generations of
emission control tjrpes. A copy of the complex model spreadsheet ("Final.exe") can be downloaded from the EPA web
site. California Phase 2 RFG allows a "Predictive Model,"
similar to the EPA complex model, as an alternative to the
original Phase 2 composition based requirements.
For Phase I, for example, the CAA specifies no increase in
NOx emissions, reductions in VOC by 15% during the ozone
season, and specified toxins by 15% all year. These criteria
indirectly established vapor pressure and composition limits
that refiners had to meet. The percent reductions are calculated with the complex model, which predicts volatile organic
compounds (VOC), specified toxic air pollutants (TOx), and
nitrogen oxides (NOx) as a function of eight composition related model inputs. Sulfur, benzene, vapor pressure, %oxygen and aromatics have the largest impact on predicted emissions. D86 evaporation volumes E200 and E300, and olefin
content have lesser, but still significant impact. Federal regulations reduced vapor pressure and benzene directly, however, aromatics or other parameters could be limited to meet
emissions criteria [17]. For example, a fuel with the maxim u m permitted 1.0% benzene requires total aromatics to be
limited to about 27% to meet the emissions reduction
requirements.
Federal (EPA) RFG and California Phase 2 RFG composition limits require the use of oxygenate. The California Phase
2 RFG requires the hydrocarbon composition of the RFG to
be significantly more modified than the existing oxygenated
gasoline to reduce unsaturated hydrocarbons, volatility, benzene, sulfur, and the reactivity of emissions. California Phase
2 does not require the use of oxygenates in the summertime
if using the "Predictive Model" except for federal ozone noncompliance areas of the state where the EPA RFG limits apply as well.
Oxygenates were first added to gasoline as a high percentage level blend component (as opposed to a p p m level deicer) to extend gasoline supply supported by some State and
Provincial Governments with a reduced gasoline tax rate. In
1992, 2 wt% oxygen gasoline was mandated in cold, high altitude areas starting in 1994, as a means to "lean" the mixture, and reduce unburned HC and CO by over 10% in carb u r e t e d vehicles. However, some oxygenates such as
methanol, ethanol, and light ethers increase the vapor pressure of the gasoline, causing increased evaporative emissions
that reduced or reversed the benefit. Newer Tier 0 and later
technology cars have very fast adaptive feedback loops to
control the oxygen content in the exhaust to near stoichiometric using the oxygen sensor [18]. These vehicles are much
less sensitive to fuel effects, so the net benefit of oxygenates
decreases with time, as the older predominately carbureted
engines are retired from service. Other researchers have observed similar reductions when oxygenates are added to reformulated gasoline on older and newer vehicles, but have
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also shown that NOx levels may increase, as also may some
regulated toxics [19-21].
By 2000, MTBE was the preferred oxygenate in RFG, but
concerns about toxicity and water pollution were mounting.
MTBE has a m u c h higher (4.3 wt%) solubility in water t h a n
hydrocarbons, a relatively low bio-degradability, and very
low o d o r threshold. This makes MTBE objectionable in
potable water at trace concentrations, and a concern for water contamination from spills, leaks and marine engines using gasoline-containing MTBE. In 1999, California applied to
the Federal government for a waiver from the Federal RFG
requirement concerning oxygen content to eliminate MTBE.
However, that application was declined in J u n e 2001. In
March 2000, the EPA provided advance notice of its intent to
initiate rulemaking pursuant to section 6 of the Toxic Substances Control Act (TSCA) to eliminate or limit the use of
MTBE as a fuel blend component. Several U.S. FederEil and
individual state bills have proposed elimination of MTBE
since t h e n including two U.S. Federal Energy bills. At the
time of this writing, use of MTBE is likely to be either banned
or significantly restricted.
Canadian refiners m u s t meet either a 1.0 wt% benzene
NTE, or optionally a 0.95 wt% YPA and 1.5 wt% NTE, effective July 1, 2000. In addition, a 72/91 summer/winter Benzene Emission N u m b e r (BEN) requirement is based on the
complex model, not including olefins. The BEN is the s u m of
exhaust a n d n o n e x h a u s t benzene, excluding calculation
terms of the complex model using olefins. There eire several
measurement and reporting differences between the U.S. and
Canadian RFG regulations. One Canadian province (BC) has
VOx and NOx requirements based on the full complex model,
but using a BC baseline gasoline for the calculation. Severed
other Canadian Provinces have standalone s u m m e r Vapor
Pressure regulations. Canadian vehicle emission standards
have tended to follow closely u p o n U.S. 49 state requirements, with some differences in phase in schedules.
GASOLINE PROPERTIES
Gasoline Composition
Hydrocarbons
Gasoline can contain over 500 different hydrocarbons with
between 4 and 14 carbon atoms per molecule. Detailed descriptions of structures can be found in any chemical or
petroleum text discussing gasoline [22]. The C3 and lighter
CHAPTER
hydrocarbons are too volatile to be used as a blending component of gasoline. Both methane and propane are widely
used as an SI engine fuel using pressurized fuel systems and
various designs of gaseous carburetors or fuel injectors. Hyd r o c a r b o n s larger t h a n about C14 are too heavy (nonvolatile), and tend to contribute inordinately to oil dilution
and incomplete combustion a n d "soot" related problems.
These functional limitations result in gasoline having a typical boiling range of about 25-225C at atmospheric pressure.
Vapor pressure, Driveability Index (DI) a n d model based
emission criteria all tend to narrow this boiling range by removing the highest and lowest volatility ranges.
The type and concentration of the various hydrocarbons in
any given gasoline blend can be determined by high resolution gas chromatography, typically using 50-100 meter capillary columns to obtain the high resolution required. The
n u m b e r of different hydrocarbons in any given blend depends upon the tj^e and severity of processing at any given
refinery. Composition surveys [23] on nonleaded gasoline
showed that gasoline blended with high percentages alkylate
or low severity reformate could contain less than 175 different hydrocarbon types. Gasoline blended with catalytically
cracked naphtha tended to contain more than 350 different
molecules.
U.S. regulations use a n ASTM external calibration GCMass Spec method for regulatory benzene and aromatic reporting. Current versions of the ASTM GC method peak
tables identify over 400 different hydrocarbons by formula,
and a n additional 50+ as "unknown." Most methods also
measure the c o m m o n oxygenates if present. Since the FID
detector is linear, the percentages of parafins, olefins,
napthenes, indanes, aromatics, and unknowns can be estimated by linear sum (commonly called a PONAU or PIANO
methods, which are acronyms of the first letter of the hydrocarbon t5rpes detected). With over 400 compounds identified,
3: MOTOR
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67
there is usually less than 2.5% "unknown" content in a typical RUL and less than 1% in a typical PUL. There are small
concentrations of additional isomers that are undoubtedly
present below the nominal 50 p p m w detection level of the
standard methods using Flame Ionization Detectors. These
tend to be highly branched CIO to C14 olefins, isoparafins,
and napthenes because of the large n u m b e r of isomers that
can be produced within each carbon n u m b e r in this range.
The magnitude of the "undetected" hydrocarbons can be inferred to be less than about 0.5% for a complex gasoline by
comparing results of high and low resolution methods.
The m u c h smaller number of isomers possible for aromatics makes the measurement of aromatics by FID detectors
more feasible since essentially all of the possible aromatics
up to about CI2 are identified. As a result, Canadian regulations use a Cap-GC/FID method for both benzene and total
aromatic reporting.
Saturated
Hydrocarbons
(Paraffins,
Alkanes)
Saturates are the most chemically stable species, and comprise 20-80% of gasoline, with 30-60% being typical. The octane ratings of these compounds depend on the branching
and n u m b e r of cEirbon atoms. The octane primary reference
fuels are both saturated hydrocarbons (0 = heptane, 100 =
224 trimethylpentane). Additional information is presented
in Table 1. The interested reader is directed to a standard organic chemistry text for further detail on these and the other
classes of hydrocarbons.
Unsaturated
Hydrocarbons
Dienes
Alkynes
Arenas
(Aromatics)
PNA (Polynuclear
Aromatics)
PAH (Polycyclic Aromatic
Hydrocarbon)
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Methanol
Ethanol
MTBE
ETBE
TAME
Gasoline
Oxygenates
Energy Content,
Net MJ/kg
Heat of Vaporization
MJ/kg
Oxygen Content
Wt%
19.95
26.68
35.18
36.29
36.28
42-44
1.154
0.913
0.322
0.310
0.323
0.297
49.9
34.7
18.2
15.7
15.7
0.0
(as Blend
Components)
See History of Gasoline (nonleaded and RFG). Table 3 provides properties of selected oygenates that are used as gasoline blend components.
Gasoline Additives
Additives are compounds added in trace a m o u n t s (<2500
p p m in the EPA "substantially similar" ruling), to enhance
some property of the fuel, or performance of the engine, vehicle, or emissions. Specifications and regulations allow for
additive use, and in some cases, require additive use, for example deposit control additives (DCA), which are beneficial
for in-use emissions.
Oxygenates
(De-icers,
Gas Line
Anti-Freeze)
Aliphatic alcohols and ethers added at 5-15 vol% are considered to be blending components and not "additives." However, at lower concentrations, low molecular weight alcohols,
especially methanol, ethanol, and iso-propanol, are effective
de-icing additives, commonly available as "gas line antifreeze." Alcohols are typically used in the 500-2500 ppmv
(0.05-0.25 vol%) range for this purpose, and function by preventing traces of water (typically from temperature drop and
condensation) from freezing in the vehicle fuel system. A
higher rate may be required for larger water contaminations,
or to prevent carburetor icing, which is accumulation of ice
in the carburetor throat and throttle plate. The cooling of
high humidity combustion air is caused by throttling (Joule
Thompson cooling) and fuel evaporation heat of vaporization
(auto-refrigeration). Gasoline with higher VP, Eind lower TIO
and T50 (high "front end" volatility) has a higher propensity
for producing carburetor icing
IPA is approved as aviation fuel system icing inhibitor
(FSII Type 2) at a treat rate of 1 vol% in aviation gasoline
(ASTM D 4171). Other alcohols and glycols have also been
used for carburetors or fuel line icing, including hexylene glycol, propylene glycol, dipropylene glycol, and various glycol
ethers. Methanol is the most commonly used for gasoline fuel
line freezing protection in fuel-injected vehicles in cold climates. De-icers are not commonly used in automotive fuels
in warm/cool climates, due to the low population of carbureted engines susceptible to carburetor icing. Some carbureted utility engines may require alcohols for operation in severe icing conditions ( > 8 5 % relative humidity, 0-10C).
Alkyl Lead
Compounds
Manganese
Tricarbonyl
(MMT)
As the toxicity of the alkyl lead and the halogenated scavengers became of concern, alternatives were considered. The
most notable of these is methylcyclopentadienyl manganese
tricarbonyl (MMT), an organo-manganese compound with
similar antiknock properties as TEL, but at m u c h lower concentrations to obtain about 1-2 octane n u m b e r increase. It
was used in the United States in nonleaded gasoline in the
mid 1970s, b u t a n application for an EPA waiver was declined in October 1978, effectively banning it in nonleaded
gasoline in the United States. In December 1995, the EPA was
forced to grant the waiver in U.S. conventional gasoline (not
RFG), and MMT can be used in conventional gasoline up to
1/32 g Mn/usg (8.3 mg/L) in all states except California, where
it is regulated separately [24]. In a separate case, the court
held that EPA's new rules that require pre-meirket testing of
new gasoline additives did not apply to MMT. The EPA has
stated it intends to monitor MMT use, but MMT was used in
only 0.02% of gasoline in 1998.
MMT has a high toxicity in concentrated form, but the
combination of relatively low volatility and its miscibility
with aromatic hydrocarbon solvents allows it to be stored
and handled with tj^ical equipment. MMT is light unstable
with a half life of about 30 s in strong sunlight, forming a
characteristic red "rust" colored precipitate (Mn02). This oxide is softer t h a n iron oxides, and is not considered to be
abrasive even at much higher concentrations than typically
used in gasoline.
MMT has been in continuous use in Canada since the first
introduction of nonleaded gasoline in 1972 to a maximum of
18 mg/L Mn, without major incidents. Most problems attributed to MMT are associated with excessive exhaust or catalyst temperatures. These cause the manganese oxide to "ceram" and form a gas impermeable glass that can coat and
effectively deactivate the catalyst [25] This is also associated
with front face catalyst plugging, due to the "sticky" nature of
the glass. Field experience indicates that this is not a serious
problem in tj^jical driving cycles, including Tier 0 and 1 vehicles equipped with OBDII emission control monitoring systems. Two provincial inspection a n d m a i n t e n a n c e (I&M)
programs using IM240 (d3mo driving cycle) and ASM2525
(25 m p h steady state dyno) test cycles have not found or identified any emissions related problems due to MMT on model
years 1982 to present.
Proponents claim benefits in NOx reduction, protecting the
catalyst from long term deactivation by sequestering catalyst
poisons (Zn, P, Pb) or coke, fuel cost benefits, emissions re-
CHAPTER
duction from reduced refining severity, and lack of adverse
health effects. Opponents cite high exhaust temperature catalyst plugging, exhaust gas sensor "rich shift" for the NOx effect, spark plug tracking, and the potential for adverse health
effects.
Dozens of controlled and noncontrolled tests and surveys
over 35 years have failed to conclusively resolve the debate
[26,27,28], probably because the test result depends upon the
specific automobile year and model being tested and how the
test is done.
Several countries are considering MMT as an alkyl lead replacement additive to facilitate alkyl lead phasedown.
Iron based
Organo-metallics
Additives
3: MOTOR
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69
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3 7: FUELS
AND LUBRICANTS
HANDBOOK
and
Contaminants
1. Free Water"haze" is considered to be a contaminant, associated with corrosion, filter plugging, and freezing problems. The large difference in density usually allows water
to settle out from traditional gasoline, and most additive
packages are checked for any propensity to stabilize a water haze and prevent water dropout. Gasoline components
are often dried at the refineries supplying gasoline into
very cold winter distribution systems, to prevent water to
phase separate due to condensation on cooling down.
Most specifications have a dryness, "clear and bright,"
(such as ASTM D 4176 for distillate fuels) or some similar
"suitable for use" criteria.
2. Sulfur, nitrogen, and oxygen are naturally occurring trace
constituents of crude oil, and are present in fuels at the
p p m level. These CEin be present as ashless, combustible,
additives. Nitrogen is typically not regulated in gasoline
formulation because the source of nitrogen in NOx emissions is from atmospheric N2, and not the fuel. The maxim u m sulfur specification prior to regulation was t3^ically
0.1-0.15 wt%. Current California a n d future U.S. a n d
Canadian regulations will reduce sulfur to a yearly pool average 30 p p m by 2005/6. Regulated changes to the baseline
gasoline used in any predictive model based regulation
equates to a change in the gasoline production required for
equivalence, including sulfur, which has a large impact on
the predicted emissions. This would restrict the use of any
sulfur containing additives in the future. (See Reformulated Gasoline for more detail.)
3. Gasoline may be contaminated by other partially soluble
or miscible liquids, such as kerosene, diesel, and oxygenates. Oxygenated fuel can have a higher solubility of
water-soluble contaminants, as well as allowing water-soluble c o m p o n e n t s to c o n t a m i n a t e any fresh water that
comes into contact with it.
4. "Adulterants" or "extenders" have occasionally been deliberately added to gasoline to increase the volume sold. Materials used have included new or used solvents, used lube
oil, formic/acetic acid, heJogenated solvents, refrigerants,
dry cleaning solvents, silicon oils/caulking/adhesives, and
even PCBs. Deliberate adulteration is usually involved
with a criminal activity for illegal waste disposal or fuel tax
fraud. Some jurisdictions now have "contaminated fuels
regulations" that prohibit these activities.
5. Particulate contaminants, such as dirt and corrosion products, can be readily removed by standard filtration procedures, and increasingly stringent cleanliness requirements
are resulting in a n increasing use of microfiltration at
truck loading and/or point of sale.
GASOLINE COMBUSTION
Spark Ignition
Engines
Spark ignition engines are ideally suited for light duty transportation uses. Their relatively lightweight (compared to
other internal combustion engines), wide REM range, broad
torque band, and high maximum RPM/power provide good
performance with a m i n i m u m number of transmission gears.
Vehicle spark ignition engines are air throttled to control
power, a n d have inherent limitations on peak cylinder temperatures and pressures due to engine "knock," so are thermally less efficient than compression ignition engines. As a
result, diesel engines d o m i n a t e the high torque, low r p m
heavy-duty truck, marine, locomotive, and stationary power
applications. Smaller high-speed diesel engines comprise
only a small percentage of the light duty vehicle market in
North America, but are more prevalent in Europe. This is
driven mainly by their significantly higher fuel efficiency,
which provides a significant market advantage, especially in
regions with high fuel prices.
Electronic fuel injection has replaced carburetors on essentially all Tier 0, Tier 1, and later model automobiles. This
facilitates "closed loop" computer control of air/fuel ratio, to
maintain exhaust composition within a n a r r o w range required for optimal operation of a "3-way" catalyst. The name
"3-way" is a reference to effectiveness for all three regulated
exhaust emissions: u n b u r n e d hydrocarbons (HC), carbon
monoxide (CO) by air oxidation, and oxides of nitrogen (NOx)
by chemical reduction with HC/CO. These systems require
the engine to operate in a narrow air-fuel ratio band on both
rich and lean side of stoichiometric, to maintain both the regulated emissions HC, CO, and NOx and O2 in the optimal
range where they react to extinction.
Hybrid gasoline-electric vehicles couple internal combustion engines with an electric motor for peak power and transient engine operations to obtain ultra-low "steady state"
emissions with no significant loss in performance. A smaller,
CHAPTER
generally m u c h higher voltage battery set stores enough
power for several minutes of high power electric motor operation for cold start or accelerations. This allows a n u m b e r of
very efficient and ultra low emission driving cycles, since the
majority of SI engine emissions are due to transient operations and cold start, before the catalyst heats up. The SI engine can shut down (zero emissions) during cold start or if
required for urban ZEV emissions. It can run at steady state
(for example on the highway) letting the electric motor handle variable power requirements (hills, wind load, comers,
etc.) that would otherwise cause increased emissions from
transient SI operation. It can be r u n at a higher steady state
power, using the electric motor as a generator to recharge the
batteries. Elimination of transients tends to provide highway
fuel efficiency in urban driving cycles, and ultra low emissions (lower t h a n the Super Ultra Low Emission Vehicle
(SULEV) level. The 2004 Tier 2 LDV Bin #2 NMOG standard
of 0.01 g/mile is about a 90-95% reduction from current levels (0.125-0.25 g/mile), over 99.8% reduction from the 1990
levels (4.1 g/mi), and 99.9% reduction from precontrol
(est. 10.6 g/mile).
Other hybrid vehicle types have been proposed, such as
diesel-electric or gasoline-hydraulic, or gasoline-flywheel,
but only gasoline-electric are being commercialized at this
time. It is anticipated that both current RFG and 30 p p m sulfur future RFG will be compatible with hybrids, but that the
lower sulfur will provide slightly lower in-use emissions.
Gasoline Direct Injection (GDI) engines (Spark Ignition Direct Injection, SIDI, etc.) have thermodynamic efficiencies
between SI and diesel engines, and may be commercialized
in the near future. Fuel requirements for GDI have not been
established. Exhaust particulate matter may be more critical
for GDI than for current engine/emissions systems.
Engine
Management
Systems
3: MOTOR
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71
Stoichiometry
Energy
Content
CHAPTER
3: MOTOR
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73
and Knock
in
Engines
Ratings
of Fuels
74
MANUAL
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For Anti-Knock
Rating
Fuels
ASTM D 2699
Procedure
Octane Rating
Analyzer
D 2885
On-line octane rating analyzers used in refineries are described in ASTM D 2885, taking a continuously flowing slip
stream of gasoline from current production, and measuring
the RON and MON continuously. The same engines and conditions are used, so consequently results Eire equivalent to the
laboratory MON or RON procedure.
Instead of "bracketing" the test fuel with primary reference
fuels, D 2885 uses "Standard Reference Fuels," commonly
CHAPTER
called "protos" or "gold protos" that are production gasoline
that have been rated by about 20 different laboratories, and
assigned the average value determined by the group. The SRF
is required to be close in octane to the test fuels, so that the
difference in octane n u m b e r can be derived from the difference in knock intensity between the SRF and the test fuel.
Standard Reference Fuels are developed through cooperative exchange programs, usuedly administered in association
with an accredited Standcirds Writing Organization. Examples in North America are National Exchange Group under
the auspices of ASTM, the Canadian Cooperative Exchange
under the auspices of the CGSB, and the Rocky Mountain Exchange, representing refiners in high altitude areas (now associated with the NEG).
Octane Distribution
Throughout
Fuel Boiling
Range
Requirement
(ONR) of
Vehicles
The actual octane requirement of a vehicle is called the Octane N u m b e r Requirement (ONR). It is determined by monitoring for the onset of knock while accelerating the vehicle
3: MOTOR
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75
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MANUAL
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Parameters
Air Temperature
and
Pressure
Increasing the air-fuel charge temperature and pressure increases the peak cylinder temperature and pressure, and thus
the tendency to knock. M o d e m engines generally pre-heat intake air to a controlled temperature above ambient. Throttling the air to a lower manifold pressure results in a much
lower peak cylinder pressure/temperature, and a lesser tendency to knock. Fuel evaporation and PVT expansion across
the throttle plate cool the intake mixture, making it slightly
sensitive to the engine temperature, which adds heat in the
manifold and during the compression stroke. Increasing the
coolant temperature in a CFR engine by about 10C increases
the octane n u m b e r r e q u i r e m e n t by about 2 AKI, so the
coolant temperature must be tightly controlled for octane
rating. Increasing the intake air (RON) or intake mixture
(MON) temperature increases the octane requirement (increases the severity of the test). This is used to advantage in
the RON and MON tests to "temperature tune" engines in different laboratories using Toluene Standardization Fuels
(TSF). This ensures that the test severity of different engines
is a relative constant over a broad range of fuel compositions,
since PRF are low aromatic, and TSF are high aromatic.
ONRCompression
Ratio
and constant volume of the working fluid (for most purposes air is the working fluid, and is treated as an ideal gas).
Thermal efficiency reaches a maximum at a compression
ratio of about 17:1 for gasoline fuels in a SI engine, and
fuel-injected engines with carefully designed mixture charge
concentrations and intake/combustion chamber design has
reached 12:1 on retail fuels with 98-100 RON. Continued
advances in engine technology have allowed gradual increase in compression ratio without increasing ONR from
87 AKI. This has been used to either increase fuel efficiency
in economy cars or to have higher power engines at the
same fuel efficiency in larger cars. These engines have substantially higher compression ratio t h a n the "historical"
curve established with the CRC engine (see History of Octane Rating].
ONRThe
Air-Fuel
Ratio
Stoichiometric combustion (air-fuel ratio = 14.7:1 for a typical non-oxygenated gasoline) is neither maximum power,
which occurs around air-fuel 12-13:1 (Rich), nor maximum
thermal efficiency, w h i c h occurs a r o u n d air-fuel 16-18:1
(Lean). Air-fuel ratio can also be used as a knock control
strategy, although at a severe emissions debit for a three-way
catalyst emission system. Enrichment is also used during full
throttle operation to reduce knocking while providing better
power and driveability. Recent changes in U.S. emissions
testing cycles will promote more control of wide-open throttle mixture settings. Enrichment has also been used as a n
"emergency" strategy in turbocharged cars, as an alternative
to suddenly dropping turbo boost (power) to prevent runaway knock during an emergency or passing maneuver. On
average, there is an increase or decrease in ONR of about 2
AKI for each unit's increase (leaning) or decrease (enriching)
of the air-fuel ratio, respectively. This response varies considerably between engines and at different RPMs. In the CFR
octane n u m b e r tests, the carburetor float bowl level is adjusted to change the air-fuel ratio. The air-fuel ratio that produces the maximum knock intensity for that fuel is then used
to determine the octane n u m b e r of that fuel.
ONREngine
Spark
Timing
GASOLINE SPECIFICATIONS.
ASTM or CGSB gasoline specifications are not legal requirements unless they are required (referenced) in a regulation by
a government authority having jurisdiction.
77
78
MANUAL
HANDBOOK
Index
(AKI)
0.013 (0.05)
1.1 (4.2)
No. 1
0.10
0.15
240
Water tolerance limits in terms of
maximum temperature for
phase separation are given in
Table 13 of the specification.
Volatility
Volatility is measured by the ASTM D 86 distillation, the
Vapor/Liquid ratio Temperature (Tv/1 = 20), and one of
several vapor pressure test methods, most commonly ASTM
D 5191, which is used for regulatory reporting. All of the
volatility measurements are somewhat related thermodynamically, being various combinations of vapor pressure
and cumulative boiling volumes. However the relationships
are not exact, because the standard tests are not ideal
thermodynamic processes. Some examples of various ASTM
D 86 distillation effects are given in Figs. 1-3. An illustration of approximate vapor pressure and volatility relationships is given in Fig. 4, comparing typical fuels with pure
hydrocarbons.
Distillation, Evaporation Temperatures, and Driveability IndexThe distillation volatility of a finished gasoline can be
expressed in several ways. One set uses the temperature at
fixed distillation points, such as the TIO, T50, and T90, related indices such as Volume Average Boiling Point (VABP)
or ASTM Driveability Index (DI)
Driveability Index = DI = 1.5 * TIO + 3 * T50 + 1.0 * T90
Maximum DI limits are specified in ASTM D 4814 for each
Volatility Class, ranging from 569-597C, or 1200-1250F.
Note that the conversion of DI from Centigrade to Farenheit
units is DI(F) = DI(C) * 9/5 + 176, where 176 is the sum of
the coefficients (1.5 + 3.0 -f- 1.0) * 32. Many companies use
volume percent evaporated (%Evap, or D-l-L) at fixed temperatures, which have an advantage over Txx controls, because they blend more linecirly, and are more easily adapted
to linear programming (LP) optimization controls. Both are
in c o m m o n use at the operational level, because ASTM requires Txx type controls while the complex model requires
E200 a n d E300. The complex model spreadsheet has a conversion from Txx to Exxx built into the model.
Vapor Pressure and Tvfl^ASTM vapor pressure specifications
are based on VP measured under standard conditions of 4:1
vapor liquid ratio at 100F and Tv/1 20 to control gasoline
front-end volatility. The Tv/120 is the temperature at which 20
volumes of vapor cire formed from one volume of the original
liquid, measured by ASTM D 2533 or D 5188. The intent is to
produce an isobaric flash prediction, something that is well
within the capabilities of m o d e m thermodynamic equation
of state (EOS) calculations.
A Tv/120 corresponds to about 10% of the gasoline vaporized under conditions of the test (a fully vaporized gasoline
would have a V/L of about 220-280 depending upon the
blend). As a result, there is a good correlation between measured Tv/1 and linear sums of the VP a n d TIO, T20 u p to
T50, so it is much more common to calculate Tv/1 than to
measure it. Some companies use an index based on VP emd
%Evap at lower temperatures, historically 70C (158F).
These are often called Vapor Lock Indices or "Hot Fuel
Handling," a reference to the origined purpose of these specifications. A v/1 of 20 was originally chosen because, on average, a carbureted engine diaphragm type fuel p u m p could
handle about 20 volumes of vapor along with the 0.9 volume
of the remaining liquid (Tv/1 = 20). Any higher temperature
(more vapor) would cause the p u m p to become "vaporlocked," and not be able to satisfy engine fuel dememd, cans-
Max Summer Dl
79
-High Volatility
250
200
Max Summer T90 = 190 J
150u
p
I
100
Typical Summer RUL
Volatility Dl = 1150 .
50
Higliest Summer
Volatility T50 = 70
Max Summer T10 = 70
10
20
30
40
li
50
60
70
80
90
100
Volume % Evaporated
FIG. 1ASTM D 86 distillation and driveability index.
MTBE
Base
250
200
/
/
150
100
50
Significant decrease in T50 caused by
azeotrope effect of ethanol
10
20
30
40
50
60
Volume % Evaporated
70
80
90
100
cation for the finished gasoline. The vapor pressure is controlled below specification maximums by limiting the
amount of butane in winter and northern summer grades,
and butane plus some pentanes in the lowest vapor pressure
summer grades (below about 8 psi VP.)
Ethanol at 10 vol% (gasohol) increases the measured VP at
100F by about 0.8 in a high aromatic gasoline to about 1.2
psi in a low aromatic gasoline. Ethanol is more soluble in
aromatics than saturates so the vapor pressure increase is
slightly influenced by aromatic content of the base fuel.
81
- A S T M D 8 6 P R EOS
250 ^
O 150
^ rhcoieticnl Single pl.itc distilkition cuivc
ffl 100
50
AS1MD86lnili.ii
Boiling Point iJBP)
20
10
40
30
50
70
60
90
80
100
Volume % Evaporated
100000
ASTM V.ipur Pri<s-.iiii- ri-iii^ji'i.iliiip
10000
1000
..-
Ntiiiii.il riu'lini) Piiiiil rii-.<.-iir>-
100
10
0.
CJ
A|iuiuxiiii.1li R.m.ii-! V.i|iiii l>ii-.-iiii'
'C5
CM'
C6
Cq
CIO
- 0.1
-0.01
-100
-80
100
-50
200
Temperature ( C )
FIG. 4Vapor pressure relationships for fuels. Log P versus 1/T.
300
82
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
Several jurisdictions allow a nominal 1 psi waiver to accommodate "splash bending" of ethanol with a base gasoline.
EPA has issued a waiver that does not require conventional
gasoline with 9-10% ethanol to meet the required specifications between 1 May and 15 September (see Nonleaded
Gasoline).
ASTM
Volatility
Class
Specifications
Alkyl lead
Content
The alkyl lead limits remain to cover fuels for off-road vehicles. Leaded fuels can contain u p to 0.1 g Pb/usg (equivalent
0.029 g Pb/L low alkyl lead in Canada), but none are made
commercially. Nonleaded gasoline can contain u p to 0.013 g
Pb per liter in the U.S. (contamination limit with no deliberate addition) and 0.005 g Pb/L in Canada to protect catalytic
converters. (See sections on alkyl lead phasedown and nonleaded gasoline for more detail).
Copper
Corrosion
Copper, silver, brass, and other "soft metal" alloys are susceptible to corrosion from reactive sulfur molecules. The ASTM
D 130 "copper corrosion" test is intended to ensure that fuels
are not corrosive to these trace components under normal use
conditions. More severe conditions could require even lower
levels of corrosive sulfur. The total sulfur content is not correlated with D 130 test performance, and in fact, some additives that are effective at mitigating copper corrosion themselves contain sulfur (see additives). Only the most reactive
types of sulfur molecules cause or contribute to D 130 copper
corrosion. The copper strip test responds to reactive sulfur,
whereas the sulfur content reports the total sulfur content.
The D 130 test is a "static" coupon test, and may overpredict durability for more easily corroded alloys such as silver,
or for rubbing, rolling, or heated soft alloy fuel system components. Field problems have been experienced with some
copper fuel p u m p commutators, silver alloy fuel sender unit
resister arrays and silver plated crankcase bearing cages with
gasoline that passes D 130. In general, silver alloys should not
be used in gasoline fuel systems without provisions for protection from sulfiding. Copper alloy components that are exposed to heat or rolling/rubbing action that removes the protective oxide layer should be tested for long-term durability
with a gasoline containing traces of corrosive sulfur (H2S,
elemental sulfur).
Maximum
Sulfur
Content
Current ASTM and CGSB standards allow 0.10% mass maxim u m sulfur content for nonleaded gasoline, but lower levels
are required by various sulfur regulations (California or
Canadian Sulfur in Gasoline regulation). Sulfur is oxidized to
SO2 over the catalyst, so essentially competes for reactive
sites that could otherwise be effective for HC, CO or NOx conversion. This appears as a temporary decrease in catalyst activity at high fuel sulfur levels, and leads to the requirement
for ultra low sulfur fuels to attain ultra low emissions.
Sulfur can be indirectly limited by RFC composition
controls based on emission models (U.S. EPA complex
model, BC TOx/NOx a n d Canadian CEPA Benzene in
Gasoline regulation Benzene Emission N u m b e r (BEN) requirements. Both Canada and the United States have regulations in place that will reduce sulfur to 30 p p m YPA phased
in between 2002 and 2010, coincident with introduction of
low emission Tier 2 vehicles (See "Reformulated Gasoline"
for more details).
Maximum
Phosphorus
Content
The EPA limits phosphorus in all gasoline to 1.3 mg/L P, because phosphorus is a potent catalyst poison, and this limit
is reflected in the ASTM specification (see alkyl lead
phasedown section for additional details). Typical levels of
phosphorus in nonleaded gasoline are undetectable by the
standard test methods.
Oxidation
Stability
CHAPTER
can diffuse into the liquid (mass transfer controlled oxidation). Some gasolines also require metal deactivators to mitigate catalysis from 10-100 p p b traces of copper (most commonly from trace level corrosion of copper and brass alloys
in contact with the gasoline during manufacture, distribution, or use).
Oxidation stability tests generally expose a heated sample
of gasoline to oxygen for a prescribed period of time to accelerate the rate of oxidation and predict on a relative basis
how long the fuel will be stable under more tj^ical conditions. In the ASTM D 525 Oxidation Stability test, the fuel
sample is heated with oxygen inside a pressure vessel, and the
time until significant oxygen uptake (pressure drop, "break
point") occurs is a relative measure of stability. The criteria
are where the pressure drop exceeds 2 psi per 15 min. The autocatalytic reaction rate increases exponentially, becoming
mass transfer controlled, and consuming all of the remaining
oxygen in only 15-30 min. ASTM D 4814 requires a m i n i m u m
of 240 min (4 h) breakpoint, which is sufficient for most storage and distribution systems. This may require a higher level
at the point of manufacture, since the measured oxidation
stability will decrease over time as the sacrificial anti-oxidant
is consumed. Other procedures not used in D 4814 are to
weigh the oxidative g u m formed after a breakpoint test,
(commonly termed a "4 hour gum"), or longer term storage
time tests at milder conditions to better simulate field storage
conditions.
It is common practice to add sufficient antioxidant to meet
a 360-600 min oxidation stability at the point of production,
so that 240 min is obtained at the point of sale. Factory fill
gasoline generally requires a much-fortified gasoline for this
purpose, as storage times of automobiles prior to Scile can be
several months. This is especially true for some specialty fleet
applications, such as police fleets, that may be made in large
production runs, with the cars stored for six m o n t h s or
more before going into service. Hydrocarbons air oxidation
has been extensively studied, and is well documented in the
literature.
Soluble
Gum")
Gum
(Unwashed
and Solvent
Washed
"Existent
3: MOTOR
GASOLINE
83
additional gum is formed under the relatively mild conditions of the test procedure. It is not predictive of future
quality. It can identify help identify stale "peroxidized" fuels
in the marketplace; Washed Existent gum is often reported
to verify that a high unwashed gum is due to the presence
of Deposit Control Additives that contribute to unwashed
gum. A fuel that has both high ( > 1 0 mg/lOOmls) washed
and u n w a s h e d g u m are generally considered suspect or
unacceptable.
Water
Tolerance
D 6422 Water Tolerance (phase separation) method measures the highest temperature at which phase separation of
gasoline - alcohol blends occur. It is not applicable to hydrocarbon or ether oxygenated fuels. Water tolerance is particularly critical for gasoline containing alcohol. The separated
lower phase alcohol-water-hydrocarbon phase settles to the
bottom of the tank where the p u m p suctions are, and tends
to get moved down the distribution system and into cars if
not found and removed. The remaining gasoline layer is often off-spec after phase separation due to loss of octane from
alcohol and aromatics extracted into the alcohol layer. If dispensed into a vehicle tank, it will not burn in engines, and so
it causes immediate stalls, and requires a complete fuel system draining and cleaning. Like water, aqueous alcohol separated phases contribute to corrosion and pickup of rust/dirt,
etc., and are also associated with accelerated filter plugging.
Methanol has a low solubility in gasoline and requires a
cosolvent if used in gasoline blending for that reason. Adding
methanol to an oxygenated fuel will increase the measured
separation temperature while adding ethanol, IPA, or other
low MW alcohols will decrease the measured separation temperature.
Water tolerance of gasoline with alcohols is very temperature dependent; consequently diverse limits are established
for the U.S. The limits vary according to location and month.
For Alaska, North of 62 latitude, it changes from 41C in
Dec-Jan to 9C in July, but remains 10C all year in Hawaii,
since it never gets that cold. This is the same control strategy
as for s u m m e r t i m e high temperature and Tv/1 or VP, but
using the daily low t e m p e r a t u r e s versus the daily high
temperatures.
Other Nonspecification Properties
Autoignition
Temperature
84
MANUAL
HANDBOOK
hydrocarbons are more resistant, and have higher auto ignition temperatures and octane numbers. However, correlation
is not precise enough to be useful, and several lab rig tests
based on auto ignition temperatures or related "cool flame"
or "pre-flame" properties to predict engine octane numbers
have failed to date. Autoignition temperature of gasoline and
other fuels can be measured by ASTM E 659, Standard Test
Method for Autoignition Temperature of Liquid Chemicals.
Heat of Combustion
and Adiabatic
Flame
Temperature
(LEL and
HEL)
The Lower and Higher Explosive limits (LEL, HEL) are the
m i n i m u m and maximum hydrocarbon vapor concentrations
that will support combustion. The LEL is related the flash
point of distillate fuels. Below the LEL there is too little hydrocarbon fuel to support combustion, while above the HEL
there is too little air (oxygen) to support combustion. The stoichiometric mixture lies between the LEL and HEL, and represents the mixture of complete combustion, maximum adiabatic flame temperature, and maximum energy release from
combustion of explosion. Distillate fuels are handled below
their LEL (Flash Point). Gasoline and naptha fuels are normally handled above their HEL. Mixtures of gasoline and distillate fuels, or fuels with equilibrium vapor pressures that
place the vapor space in the explosive range are extremely
dangerous. Any ignition source can cause Ein explosion in the
vapor space or in fuel lines and vents. Once ignited, a flame
can propagate down any pipe or vent that contains a combustable mixture. Fuels with vapor spaces in the explosive
range require specialized equipment and procedures for safe
handling (flame arrestors, anti-static provisions, gas inerting,
etc.).
The higher and lower explosive limits for gasoline are only
rarely a concern. The vapor pressure of gasoline keeps it well
over the HEL most of the time. It is only in extremely cold
weather that a properly formulated winter gasoline can enter
the HEL explosive range. This can be estimated from PengRobinson Equation of State calculations, since the LEL will
occur when the vapor phase concentration of butane/pentane
hydrocarbons will be in the 1.5-2 vol% range, and the HEL in
the 7-8 vol% range. At 14.7 psia barometric pressure, this
corresponds to a range of 0.1-0.2 psia and 1.0-1.2 psia hydrocarbon vapor pressure for the LEL and HEL respectively.
Using these values, a typical 14.5 VP winter gasoline would
be expected to have an LEL ranging from about 75 to - 6 0 F
and HEL from about 25 to 15F, depending upon composition. A t5^ical 7.8 VP s u m m e r gasoline would be expected
to have an LEL ranging from about 50F to 35F and an
HEL from 5-15F. Canadian CGSB gasoline standards have a
m i n i m u m VP to provide a wide margin between the HEL and
the VP at extreme cold temperatures for various times of
year.
Diluent gases are much more effective at reducing the HEL
than increasing the LEL for all flammable hydrocarbon gas
mixtures. The flammable region disappears with the addition
of about 30% CO2 or 45% N2, and almost all of this change is
due to reduction in HEL and not increase in LEL hydrocarbon concentration [38,39]. From this it can be estimated that
N2 gas containing less than about 10 vol% oxygen is nonflammable with hydrocarbon vapors, a "rule of t h u m b " that
is often useful for developing procedures for safe handling of
gasoline in nonstandard conditions.
Heat Capacity, Thermal
and Heat of
Vaporization
Conductivity,
and
Lubricity
CHAPTER
crease viscosity to about 0.1 cSt, with an increase of 100
centigrade [40]. Lubricity is determined by trace polar
molecule content, b u t is generally very p o o r for gasoline.
Clean absorbent treated gasoline range hydrocarbons (low
polar content) are often used as the "poor" standard in lubricity test calibrations. Pumps for gasoline service must be
chosen carefully due to the low lubricity and propensity for
accelerated p u m p wear. Centrifical, gerotor, internal gear,
and other low contact p u m p designs are preferred over ordinary gear pumps, which are seldom suitable for gasoline service. Similar wear problems can occur in some positive displacement meters. The high vapor pressure of gasoline can
result in localized cavitation in some p u m p designs, with the
damage easily misdiagnosed as corrosion and/or wear. Engine mounted fuel p u m p s are usually diaphragm pumps, and
low pressure in-tank fuel p u m p s are usually turbine (centrifical) p u m p s for these reasons. High pressure automotive in
tank fuel p u m p s are usually two stage turbine/positive displacement pumps, with the second stage tjrpically usually being a roller vane or gerotor type for use in a very "dry" (low
lubricity) fuel.
There are a n u m b e r of standard ASTM viscosity test methods suitable for gasoline, such as D 445, S t a n d a r d Test
Method for Kinematic Viscosity of Transparent and Opaque
Liquids (the Calculation of Djoiamic Viscosity). Adaptations
of several lubricity test m e t h o d s originally developed for distillate fuels can be applied to lighter hydrocarbons, although
not covered with the scope (naptha range solvents are used as
calibrants). These include D 6078 and D 6079, Scuffing Load
Ball on Cylinder and High Frequency Reciprocating Rig Tests.
Conductivity
and Static
Electricity
Density,
Refractive
Index,
3: MOTOR
and Dielectric
GASOLINE
85
Constant
ASTM/IP METHODS
ASTM No.
D 4806
IP No.
D 4814
D86
123
D 130
154
D 323
D 3 81
131
D 525
40
D665
135
D 1266
107
Title
Specification for Denatured Fuel
Ethcinol for Blending with Gasolines
for Use as Automotive Spark-Ignition
Engine Fuel
Specification for Automotive SparkIgnition Engine Fuel
Test Method for Distillation of
Petroleum Products
Test Method for Detection of Copper
Corrosion from Petroleum Products
by the Copper Strip Tarnish Test
Test Method for Vapor Pressure of
Petroleum Products (Reid Method)
Test Method for Existent Gum in Fuels by Jet Evaporation
Test Method for Oxidation Stability of Gasoline (Induction Period
Method)
Test Method for Rust-Preventing
Characteristics of Inhibited Mineral
Oil in the
Presence of Water
Test Method for Sulfur in Petroleum
Products (Lamp Method)
160
D 1319
156
D2276
216
D2533
D2622
D2699
237
D2700
236
D2709
D2885
D3116
D3120
D3227
342
D3231
D3237
D3341
D3348
D3606
D3710
D3831
D4052
D4045
365
HANDBOOK
D 4053
D 4057
D 4294
336
D 4420
D 4815
D 4953
D 5059
228
D 5188
D 5190
D 5191
D 5453
D 5482
D 5580
D 5599
408
D5845
D 6422
BIBLIOGRAPHY
[1] Owen, K. and Coley, T., Automotive Fuels Reference Book, 2nd
ed.. Society of Automotive Engineers, Warrendale, PA, 1995.
[2] Gibbs, L. M., "Transportation FuelsAutomotive Gasoline,"
Encyclopedia of Energy Technology and the Environment, John
Wiley and Sons, NY, 1995, pp. 2675-2698.
[3] Poulton, M. L., Alternative Fuels for Road Vehicles, Computational Mechanics Publications, Wit Press, Southampton, UK,
1994.
[4] Goodger, E. M., Hydrocarbon Fuels, Macmillan, London, 1975.
[5] Goodger, E. M., Alternative Fuels, MacmillEin, London, 1980.
[6] "Alcohol Fuels," "Gasoline and Other Motor Fuels," "Hydrogen
REFERENCES
[1] Owen, K. and Coley, T., Automotive Fuels Reference Book, First
ed.. Society of Automotive Engineers, Inc., Warrendale, PA,
1990.
[2] Gibbs, L. M., "How Gasoline Has Changed," SAE Report No.
932828, Society of Automotive Engineers, Warrendale, 1993.
[3] Purdy, G. A., Petroleum, Prehistoric to Petrochemicals,Copp
Clark Publishing Co., Toronto, 1958.
[4] Kaufman, K. B., "Midgley: Saint or Serpent?," Chemtech, December 1989, pp. 717-725.
[5] Midgley, T. and Boyd, T. A., Industrial and Engineering Chemistry Research, Vol. 14, 1922, pp. 589, 849, 894.
[6] Midgley, T., "Problem + Research -I- Capital = Progress," Industrial and Engineering Chemistry Research, Vol. 31, 1939, pp.
504-506.
[7] Dying for Work: Workers' Safety and Health in 20th Century America, D. Rosner and G. Markowitz, Eds., Indiana University Press,
Bloomington, IN, 1987.
[8] Goodger, E. M., Petroleum and Performance, Butterworths Scientific Publications, London, 1953, p. 166
87
[38]
[39]
[40]
[41]
MNL37-EB/Jun. 2003
Aviation Fuels
Kurt H. Strauss^
HISTORY
Aviation Gasoline
EARLY AIRCRAFT ENGINES WERE OPERATED o n ordinary straight-
r u n motor gasoline well into the 1920s [ 1 ]. Research then isolated uncontrolled combustion as a major source of engine
overheating and failures, prompting a search for ways to cure
the problem. The big step came in 1921 with the invention of
tetraethyl lead (TEL), a n unequaled knock resistance enhancer. The same period saw the development of the heptane-isooctane scale still in use today for rating antiknock
properties in terms of octane numbers. For aviation gasoline,
the concept of rating knock resistance in special single cylinder engines resulted in the Aviation Octane Test Method (D
614), which tested fuels under lean fuel mixture conditions
simulating cruise operation. (In 1970 this method was replaced in the specification by the Motor Octane Method, D
2700.) An aviation gasoline specification, issued by the U.S.
Air Corps in 1938, listed a 68 octane grade containing n o lead
and a 92 octane grade with a m a x i m u m of 6 mL TEL/gallon.
As engine power output was increased by supercharging the
fuel/air mixture, a second rating method, D 909, came into
use to evaluate performance u n d e r rich take-off conditions,
so that by World War II both rating methods were required.
Engine designers soon discovered the performance benefits
of high octane, which permitted a higher octane fuel t o develop more power in a given engine or allowed a reduction in
engine size with the same power output. Research on high
octane fuel thus received a high priority and resulted in a 100
octane fuel by the beginning of World War II. While t h e
heroic performance of the RAF is widely recognized, it would
have been impossible without the 100 octane fuel.
Jet Fuel
Because of different combustion requirements, jet fuel
started as a completely different portion of the petroleum
barrel [2]. Early British engines used domestic kerosine, a
fuel that has not changed drastically over the years. German
engines, also military, were operated on a mixture of kerosine and naphtha, probably to extend fuel availability. The
progression of U.S. military fuels is illustrated in Table 3.
Both JP-3 and JP-4, which are blends of kerosine and naphtha, reflected Air Force concern over fuel availability, while
JP-5 is tailored t o Navy r e q u i r e m e n t s for carrier combat
safety. JP-7 is a supersonic fuel in very limited use. Today, the
Air Force operates almost entirely on JP-8; in fact, this grade
has become the primary battlefield fuel to be used in gas turbine and diesel powered ground vehicles as well as combat
aircraft.
For civil use, ASTM issued specification D 1655 in 1959,
containing three grades. Jet A and A-1 were kerosine-type fuels differing only in freezing point, while Jet B was the civil
version of JP-4. Currently consideration is being given to removing Jet B from D 1655 and placing it into a separate specification. The key properties of Jet A and A-1 are illustrated in
Table 4. Corresponding specifications are issued by the UK
Ministry of Defence as defence standards (Def Stans), with
Def Stan 91 -91 [3] being the technical equivalent of ASTM Jet
A-1. Jet A meeting D 1655 is the civil aviation fuel in the U.S.;
Jet A-1 meeting the combined requirements of D 1655 and
Def StcUi 91-91 is the civil fuel elsewhere. There is no British
grade corresponding to Jet A. The latest effort at a true international jet fuel standard is a series of guidelines [4] issued in
1999 by the IntemationEd Air Transport Association (lATA),
which includes Jet, A, Jet A-1, the Russian TS-1, and a Jet B
grade.
2003 by A S I M International
www.astm.org
Grade 80
Grade lOOLL
Grade 100
80.0
99.5
99.5
87.0
0.13
0.14
0.2
none
2.3
130.0
0.53
0.56
130.0
1.06
1,12
2.7
none
none
2.7
2.8
none
D 3341 or D 5159
Report
D 1298 or D 4052
D86
Report
max
min
max
max
max
min
min
max
max
min
max
max
max
min
max
75
75
105
135
170
135
97
1.5
1.5
38.0
49.0
-58
0.05
43.5
No. 1
max
max
max
max
6
3
D 323 or D 5190
or D5191
D2396
D 1266 or D 2622
D 4529 or D 3338
D323
D873
D 1094
D2624
2
450
Requirement
D2700
min
82.0
purple
max
max
7.5
1.9
max
70
66-121
190
225
2
95
3.0
40.8
-58
62
38
0.013
No. 1
0.07
D2392
D86
max
max
max
min
max
min
max
max
min
max
max
max
0.3
2.7
Grade
Specification
1944
JP-1
1946
1947
JP-l"
JP-S"
1951
JP-4
1952
JP-5
1956
JP-6''
AN-F-32, changed
to MIL-F-5616
not issued
AN-F-58, changed
to MIL-F-5624
MIL-F-5624, now
MIL-PRF-5624
MIL-F-5624, now
MIL-PRF-5624
MIL-F-25656
1980
JP-7
1979
JP-8
MIL-T-38219, now
MIL-PRF-38219
MIL-T-83133, now
MIL-DTL-83133
NATO
Symbol
Volatility
and Freeze Point
l l O ^ F m i n flash
60C max freeze
2 psi max RVP
5-7 psi RVP
F-40
F-44
F-34
"Canceled.
TABLE 4Key specification requirements for jet fuel grades Jet A, A-1, and B.'
Property
Composition
Acidity, total, mg KOH/g
Aromatics, %v
Sulfur, mercaptan, %m
Sulfur, total, %m
Volatilitv
Distillation temp., C
10% recovered, temp.
20% recovered, temp.
50% recovered, temp.
90% recovered, temp
Final boil, point, temp
Distill, residue, %v
Distill, loss, %v
Flash point, "C
Density at 15C, k g W
Vapor pressure, 38C, kPa
Fluiditv
Freezing point, C
Viscosity, -20C, mm^/s
Combustion
Net specific energy, MJ/kg
One of following shall be met:
(1) Smoke point, m m
(2) Smoke point, m m and
Naphthalenes, %v
Corrosion
Copper strip, 2 h @ 100C
Stability
Thermal, 2.5 h at 260C
Filter press, drop, m m Hg
Tube deposit less thsm
Contaminants
Existent gum, mg/100 mL
Water reaction
Interface rating
Additives
Electrical conductivity, pS/m
If Additive is used
If required by purchaser
max
max
max
max
JetB
0.1
25
0.003
0.3
25
0.003
0.3
D3242
D1319
D3227
D 1266, D 1552, D 2622
D 4294 or D 5453
D86
max
max
max
max
max
max
max
min
205
report
report
300
1.5
1.5
38
775-840
meix
max
max
- 4 0 Jet A
- 4 7 Jet A-1
8.0
145
190
245
1.5
1.5
751-802
21
-50
D 56 or D 3828
D 1298 or D 4052
D 323 or D 5191
D 2386, D 4305,
D 5901 or D 5972
D445
min
42.8
42.8
min
min
max
25
18
3.0
25
18
3.0
D1322
D1322
D 1840
max
No. 1
No. 1
D 130
max
25
Code 3
25
Code 3
D3241
max
max
7
lb
D381
D 1094
lb
D2624
max
min
450
50
450
50
HANDBOOK
gine and to increase power output. In addition to these traditional engines, other designs, particularly for ultralight aircraft, are being introduced but are not described in detail in
this chapter. Exhaust gases are discharged through mufflers,
turbochargers or directly into the atmosphere. Compared to
today's automobile engines, all these aircraft engines are relatively simple and unsophisticated.
With rare exceptions, aircraft piston engines are operated
with separate throttle and manual fuel/air mixture controls,
whether carbureted or fuel injected. On high performance
aircraft the pilot also controls the engine speed by means of
separate manual propeller controls. During takeoff and climb
the fuel/air mixture is maintained "rich;" the purpose of the
excess fuel is to help cool the engine at high power conditions. The fuel/air mixture is "leaned out" during cruise for
optimum fuel consumption. "Rich" in this context refers to a
mixture in which the fuel/air ratio is well above the stoichimetric ratio, while lean operation is run as close as possible
to stoichimetric without overheating the cylinders.
Jet Fuel
Jet engines operate on a completely different principle. Air
flows through a compressor, is guided into a combustion section where fuel is injected and burned and the resulting exhaust gases are expanded in the turbine section, and then expelled into the atmosphere. The turbine section drives the
compressor, while the remaining energy in the exhaust
stream either reacts on the engine parts to push the engine by
"jet propulsion" or is used to drive a propeller in "turboprop"
fashion. For more efficient operation, a large single stage
compressor or "turbofan" may be mounted in front of the engine. This fan is driven by its own turbine section by a shaft
running through the core engine. Military engines may add
extra thrust by injecting fuel into the exhaust stream and
burning it in an afterburner at the expense of greatly increased fuel consumption. Unlike reciprocating internal
combustion engines, these engines operate with continuous
combustion where an igniter serves only to start combustion
and is then turned off. Gas turbine engines operate with lean
fuel/air ratios well below stoichimetric (with considerable excess air) to provide turbine inlet gas temperatures below the
normal combustion temperatures.
The fuel system of a modem transport aircraft is illustrated
in Fig. 1. The fuel is carried mostly in the wing structure
where metal junctions are sealed with an elastomer and the
entire inside surface is coated with epoxy paint to prevent
corrosion. Elastomeric bags are generally not used for fuel
storage, mostly to save weight. From the tankage, fuel is
pumped by boost pumps to the engine high pressure pump.
The engine pump normally builds fuel pressure in two stages
with the first stage a centrifugal pump and the second stage
a gear pump capable of delivering fuel at pressures as high as
10 MBCa (1400 psi.). The fuel control, the heart and brains of
the fuel system, then meters the proper amount of fuel to the
combustion system with the excess fuel being bypassed back
to the second stage pump inlet. Fuel enters the combustion
system through a fuel manifold, which distributes fuel
around the engine and into fuel nozzles in the combustion
chamber. Note that the fuel passes through a series of heat
exchangers, which reject heat from the hydraulic system,
from the engine oil system, and from the auxiliary power sys-
Fueltank
Fuel quantity
gage
Nozzles
uiuaiiuu
umiij
lanifold /
ssembly /
A/Cheat
exchanger
Fuel bypass
Fuel
Control
FilterX
Engine Pump
Assembly
FIG. 1Turbofan fuel system.
Integrated
gen. drive
oil heat exch.
93
Horizontal
Stabilizer
I Tank (optional)
Surge Tank
\y<
>y
DryBay
/
MainTankNo.l f
Tank
Gallons
47 675
17 030
65 220
5020
12 540
12 594
4499
17 229
1326
3313
217 211
57 381
tern. (In some systems the heat from the hydraulic system is
rejected in the fuel tanks.) Additional heat is added to the fuel
by energy losses in the pump and by fuel recirculation
through the pump. More heat goes into the fuel from the
compressor discharge air, which the fuel passes through to
get into the combustion system. This heat path highlights another important function of the fuel, to serve as the heat sink
that carries away excess heat from other systems and allows
other systems to operate.
Figure 2 illustrates the tankage arrangement of a Boeing
747-400 aircraft. At takeoff, each engine is supplied fuel from
its own tank. After takeoff, fuel is taken selectively from the
center wing tank first to control wing stresses. For a typical
flight each engine is started by rotating the compressor spool
to start air flowing. When airflow is sufficient to start combustion, fuel is injected and the fuel/air mixture is ignited.
The engine then accelerates under its own power to idle operating speed and above. Maximum power at take-off is limited by either throttle demand or turbine inlet temperature
limits. Take-off power is reduced as the aircraft climbs and is
further reduced at cruise altitude to minimize fuel consumption. At the end of cruise, power is further decreased to near
idle for descent. Because heat rejection is almost constant
but fuel flow is near minimum, the descent portion of the
94
MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
-50
-30
-10
10
Gasoline
Aviation gasoline low temperature performance tends to center on engine starting. While fuel volatility is the key to fuel
evaporation a n d engine starting, the tight volatility limits
allow little flexibility and force solutions other than fuel selection. Starting difficulties at low temperatures are com-
30
50
70
Ten^rature, C
FIG. 3Typical viscosities vs. temperature.
90
110
0.06
95
0.04
0.02
:
o
"2
II
0.007
0.006
20
40
60
80
100
Ten^rature, C
FIG. 4Water solubility vs. temperature.
pounded by increased lubricating oil viscosities and decreased battery performance. High altitude operation does
not normally present a low temperature problem because
gasoline has a very low freezing point and most piston engine
aircraft do not fly at extremely high eJtitudes.
Low TemperatureWater Related
All hydrocarbons can dissolve a very limited amount of water. Saturation limits for jet fuel and for aviation gasoline are
shown in Fig. 4 [9]. When water-saturated fuel is cooled, water comes out of solution as free water. These low levels of
free water do not present cin operating problem. However, as
the fuel temperature goes below 0C or 32F, this free water
freezes into ice crystals that can plug filters and other fine
passages. The problem is avoided by placing filters into a
warmer part of the fuel system, by applying heat to critical filters when water freezing temperatures are noted, or by including an anti-icing additive in the fuel. Diethylene glycol
monomethyl ether (diEGME), as described by specification
D 4171, Type III, can be added to jet fuel or aviation gasoline
as an anti-icer in concentrations of 0.10-0.15% by volume.
Ethylene glycol monomethyl ether (EGME) is no longer
listed in D 4171, but is still in limited use. Isopropyl alcohol,
per D 4171 Type II, may only be added to aviation gasoline.
Here specification D 910 warns that the addition of isopropyl
alcohol to the 100 grade may lower its knock ratings. Both
additives only keep limited amounts of free water from freez-
ing and neither affects wax precipitation. Water concentrations significantly exceeding saturation levels Ccin overwhelm
these additives. Techniques for monitoring free water levels
etnd keeping excess water out of aircraft are discussed later
under Quality Control. The freezing of atmospheric moisture
on the throttle plate causes carburetor icing in piston engines; it is due to evaporative cooling by gasoline and trace
levels of water in fuel play no part.
High Temperature
Exposure to high temperatures represents one major difference between aviation gasoline and jet aircraft fuel systems,
in fact, high temperature exposure has not occurred in aviation gasoline-powered aircraft. Jet fuel presents a completely
different picture. The first incidents, in the early 1950s, took
place in military J57 engines that suffered plugging of nozzle
filter screens by fuel-caused carbon deposits [11]. Such plugging radically altered the exhaust gas temperature pattern at
the turbine inlet and resulted in turbine blade failures. In this
engine the fuel manifold that distributed fuel to the individual nozzles was located in the hot compressor discharge air
and some fuels formed carbon deposits in the manifold under reduced fuel flow conditions. These deposits broke off
and plugged fuel nozzles. The particulsir problem was solved
by manifold redesign, but it also alerted the industry to the
need for tailoring high temperature performance into the
fuel.
HANDBOOK
ratings by the old Aviation method, D 2700 contains conversion tables from the Motor method to the Aviation method. It
is noted in passing that the Motor Method is the only rating
method used for both aviation and motor gasolines.
The rich rating method, D 909, is more complex. Engine
output is measured and controlled by a dynamometer. Air
into the engine is compressed Eind cooled. Both fuel and air
flow to the engine are metered. Engine loading by the dynamometer is increased at constant fuel/air ratio until knock
occurs. The same process is repeated at increasing fuel/siir ratios to develop a curve of knock-limited engine output against
fuel/cdr ratio. This curve is bracketed by similar curves using
isooctane with varying concentrations of TEL as reference
fuels. The test fuel rating is established by interpolation between reference fuel curves cind is usually expressed in terms
of performzince numbers, which are directly proportional to
the engine power output. Thus, with a fuel having a performance number of 130 the engine developed 30% more power
than on straight isooctane.
There are currently several research programs [17] related
to knock testing and combustion requirements of aviation
piston engines. The first program is establishing the octane
requirements of a great variety of current production engines
to get an up-to-date definition of the relationship of the single cylinder laboratory engines to fl5'ing hardware. As part of
this effort, an Engine Octane Rating method has been issued
as D 6424. Preliminary results indicate that, while the old,
large radicd engines are sensitive to both lean and rich knock
characteristics, the flat or pancake engines seem to be critiCcJ in the cruise or lean operating mode only. The second program is pointed toward the development of a high octane, unleaded aviation gasoline. That search is driven by the fact that
100 octane aviation gasoline is the only lead-containing fuel
left in the U.S. petroleum inventory and there is environmental pressure to eliminate lead wherever it exists. Ultimately,
the two programs should indicate the practicality of developing an unleaded gasoline, which will satisfy the current inventory of engines requiring high octane fuel.
Jet Fuel
A typical jet fuel combustion system is illustrated in Fig. 6.
Air is discharged from the compressor at pressures up to 20
Inner liner
Turbine
inlet
Jet igniter
Primary comlnistion
zone
97
Secondary
zone
HANDBOOK
gine smoke or soot but are not permitted because of ash formation. [20].
The level of sulfur oxides in the exhaust is directly related
to the total sulfur content of the fuel and any required reduction of these oxides has to be achieved by reducing total sulfur content below currently allowed levels. Nitrogen oxides,
on the other hand, are purely an engine design function depending primarily on the maximum combustion temperatures, the amount of mixing in the primary combustion zone,
and the time at maximum temperature. Fuel characteristics
play no part [19]. The same can be said for carbon monoxide
emissions in which fuel does not play a significant role [19].
Because the ultimate purpose of fuel is to furnish heat energy, the minimum heat content or specific energy is controlled. Water vapor formed during combustion is not condensed in any aviation engine, therefore the net specific
energy is specified. As mentioned in D 910, the minimum
specification level for aviation gasoline is high enough to effectively limit the total amount of aromatics to about 25%.
Specific energy (formerly called heat content) can be measured in a calorimeter per D 4809, where a small amount of
fuel is burned in a pressure vessel, which in turn is immersed
in a water bath. The released energy is calculated from the
temperature increase of the water bath. Extremely precise
thermometry is required for the desired accuracy of the results. Specific energy can also be estimated by equations
based on pertinent fuel characteristics. One estimation
method, D 4809, uses fuel density and aniline point; another,
D 3338, includes density, boiling point and aromatic content
as variables. D 3338 is gaining in popularity because of aniline toxicity and because the required variables are already
being determined to assure overall specification compliance.
Volatility and Flammability
Volatility, a fuel's tendency to evaporate, plays a significant
part on the ground and in the air. Some performance requirements overlap between the two fuel t5rpes, others do not.
Aviation Gasoline
Aviation gasoline volatility is a major factor in engine operation because proper ignition requires fuel in vapor form. The
fuel, therefore, has to evaporate in the intake manifold before
reaching each cylinder. This is particuleirly important during
starting. Volatility also affects vapor formation in fuel lines,
which occurs when line pressure drops below the vapor pressure of the fuel, usually due to local overheating at low line
pressures. Vapor lock takes place when the combined volumes of vapor and liquid in the line exceed the volumetric capacity of the engine pump so that the engine no longer gets
the required amount of fuel. As a result, the engine will not
run until liquid fuel flow is restored. Lastly, volatility determines the flammability of the vapor space (ullage space)
above the fuel. This property is discussed later in this section.
Jet Fuel
Fuel volatility tends to have different effects on jet fuel operation. Too high a volatility CcUi cause excessive evaporation or
even boiling in aircraft tankage during rapid climb when fuel
vapor pressures equal the rapidly decreasing atmospheric
pressures at altitude. That problem caused the 1950s shift
260
240
220
200
180
160
140
120
100
80
60
40
20
0
99
Jet A
JetA-l,JP-8
JetB,JP-4
\
\
'
1
20
1_
40
Avgas
60
80
100
Percent Evaporated
from JP-3 to JP-4 fuel by the U.S. Air Force [2]. Ullage
flammability in aircraft tankage is of concern and depends on
fuel type as well as in-tcink temperatures and pressures. Aside
from some effect on engine stcirting at very low temperatures,
fuel volatility is not a major factor in jet engine operation.
Fuel volatility is normally defined by the product's boiling
range and its vapor pressure. The boiling range is measured
in a simple distillation apparatus, D 86, in which fuel is
boiled off and then condensed at atmospheric pressure under
closely controlled conditions. The test result is a relationship
of boiling temperatures to fuel percent evaporated. Typical
results for Jet A [21 ], Jet A-l/JP-8 [23], Jet B/JP-4 [21 ] and aviation gasoline [22] are plotted in Fig. 7. The boiling range distribution can also be measured by gas chromatography, D
2887, where the molecular distribution of a sample is compared to a standard mixture of known boiling points.
Fuel vapor pressure is routinely measured at 38C (100F)
by D 323 or D 5191. The resuh of the test, called the Reid vapor pressure (RVP), is the sum of the partial pressures of the
fuel constituents plus the partial pressures of dissolved air
and water measured at a vapor to liquid ratio of 4:1. A true,
absolute vapor pressure where the vapor space approaches 0
can be obtained at any temperature with D 6378. A summary
of typical absolute vapor pressures against temperature is
shown in Fig. 8 [9], but absolute vapor pressure is not determined on a routine basis.
Reid vapor pressure is specified for aviation gasoline and
Jet B but not for Jet A or A-1 because for these fuels the RVP
results are too low to be reliable. Instead, volatility for the
kerosine-type fuels is measured by the flash point test. Fuel
in a closed cup is immersed in a water bath, which is warmed
at a specified rate. Starting 10C (18F) below the expected
flash point temperature, a small flame is repeatedly inserted
into the cup, which is closed between flame immersions. The
fuel temperature at which a flash of flame appears and disappears is reported as the flash point. The standard test in D
1655 is the Tag Closed Cup method, D 56, but other flash
point tests are also in use. Because of differing surface to volume ratios and different heating rates these tests often give
consistently different results and these differences have to be
considered when comparing test results [24].
Vapor pressure and flash point, while related, do not measure the same property. The former measures the pressure
exerted by a fuel at a specific temperature, while the latter indicates the lowest temperature at which a flammable fuel/air
mixture is created. Typical fuel flammability ranges at sea
level are summarized in Table 5 [9]. Below the lean limit
there is not enough fuel vapor in the air for combustion,
while above the rich limit there is not enough air. Only within
the flammability limits is the mixture ignitable with an energy source like a spark or flame. The drastic differences between aviation fuels are apparent. These flammability limits
are not absolute but are influenced by the test equipment and
test conditions and serve only as general guides with regard
to vapor space flammability. For example, the fuel/air ratio in
a large storage tank is maximum at the fuel surface and decreases with increasing distance above the fuel. Tank vapor
space or ullage flammability therefore can vary in a tank, particularly because temperature is also not usually uniform.
Flammability limits are also strongly influenced by the effect
of ambient pressure on evaporation rate. Thus the change in
flammability limits with increasing altitude (decreasing pressure) is shown in Fig. 9. The subject of aircraft tank flammability is being revisited as the result of the 1997 crash of TWA
Flight 800, which is attributed to the explosion of the "empty"
center tank in the fuselage [25].
Fuel Metering
The measurement of fuel quantity and fuel flow is important
both for ground and for flight operations. On the ground
Avgas
JetB
Jet A
JP-5
1.2
7.0
1.3
8.0
0.6
4.7
0.6
4.6
-44
-12
-23
18
53
77
64
102
>
20
40
60
80
100
120
HO
Temperature, "C
FIG. 8Typical vapor pressures vs. temperature.
Copper
One of the early compatibility problems has been fuel attack
of system metals, particulcirly copper or copper-containing
materials. In aircraft fuel systems this frequently involved
fuel attack on bronze pump bearings. The primary fuel constituents involved in copper corrosion are elemental sulfur
and hydrogen sulfide, although acidic components may also
play a part. The most common source of hydrogen sulfide has
been incomplete stripping of the gas after refinery hydrotreating. Elemental sulfur (S), which is sulfur uncombined with other elements, has tended to result from the
chemicEd reduction of water-soluble sulfates in tank bottoms
by sulfate reducing bacteria or by the oxidation of hydrogen
sulfide. Elementcil sulfur has also been a byproduct of older
101
80
Temperature, C
FIG. 9Flammability limits vs. altitude.
100
HANDBOOK
sion requirement in the specification, but fuel passing tfiis requirement can dissolve the very low levels of copper, which
in turn can wreck thermal stability. At present the most reliable way to avoid pickup is to avoid contact with the metal or
to add an approved metal deactivator to chelate and deactivate the trace levels of copper in fuel.
Cadmium
The corrosion of cadmium-plated parts has been attributed
to mercaptan sulfur compounds, particularly in the presence
of water [28]. Mercaptan sulfurs are measured by D 3227 or
are limited qualitatively by the Doctor test, D 4952.
Steel
A form of corrosion in which the fuel plays an indirect role is
the rusting of mild steel by free water in fuel. Such corrosion
shortens the life of steel components but also is the source of
solid contamination, which ultimately has to be removed
from aviation fuels. U.S. military jet fuels require the presence of fuel-soluble corrosion inhibitors, generally dibasic
acids, which form a protective molecular layer on the steel
surface. MIL-PRF-25017 defines the requirements for this
t3^e of additive and approved additives are listed in the Qualified Products List for the specification. The dual function of
these additives as lubricity agents as well as corrosion inhibitors is discussed later in this chapter. Because these materials are surface-active and can interfere with water removal in the filter-coalescing process, their use in civil fuels
is very limited. Multi-product pipelines are protected by placing the additive into the non-aviation products. Fuel systems
at airports are usually internally coated to prevent rusting.
Galvanizing or zinc coating is not an acceptable method for
rust prevention in aviation systems because of the sacrificial
nature of zinc, which can react with the TEL in aviation gasoline or dissolve into jet fuel to form an ash during combustion.
Storage Stability
Petroleum products in long term storage are subject to low
temperature oxidation, which may cause the formation of
high molecular weight products that become insoluble and
precipitate out. Olefins formed during cracking are particularly prone to such degradation and are avoided in aviation
fuels. Straight-run jet fuels have excellent storage stability
due to the presence of natural oxidation inhibitors. However,
processes such as hydrocracking or high pressure hydrotreating destroy these inhibitors, leaving the product vulnerable to oxygen attack. In jet fuels such peroxide formation
[29] has led to repeated localized incidents of nitrile rubber
deterioration in military service [28]. Such elastomer attack
has not been reported with civil fuel in the U.S., probably due
to the greater amount of fuel commingling. Similar degradation tends to occur in aviation gasoline, which contains no
natural oxidation inhibitors and is therefore routinely inhibited with oxidation inhibitor additives.
Peroxide formation is prevented by oxidation inhibitors,
normally hindered phenols, which scavenge free radicals that
are the first step in the complex oxidation process [12]. Acceptable inhibitors are listed by composition in the jet fuel
and aviation gasoline specifications. To be effective, these in-
103
tion:
Catalyst
C4 olefins + isobutcuie
Alkylate
104
MANUAL
HANDBOOK
Leading to
Better combustion quality
Better low temperature properties
Higher gravimetric heat content
Poorer handling safety
Lower volumetric heat content
Leading to
Lower combustion quality
Poorer low temperature properties
Lower gravimetric heat content
Higher volumetric heat content
Unchanged handling safety
compatibility with system materials. However, the procedures do not disclose whether an additive will affect performance that has to be evaluated by other testing. A similar
protocol does not exist for aviation gasoline, which has seen
very few additive changes over the years.
It should be noted that ASTM does not confer additive approval. Such approval must be initiated by the airframe and
engine manufacturers and approved by the airworthiness
agencies. Additive listing in ASTM aviation fuel specifications simply recognizes such approvals.
Specific Additives
Most additives are described in earlier sections of this chapter under specific properties, but Table 8 lists all jet fuel additives contained in D 1655 together with their permitted
dosages. Oxidation inhibitors, metal deactivator, and conductivity improver may be added at the discretion of the refiner. Other additives, such as fuel system icing inhibitors,
can only be added with the agreement of the purchaser. The
fuel manufacturer or fuel handler must declcire all additives
and their concentration. Several military specifications make
mandatory the addition of oxidation inhibitor, conductivity
improver, icing inhibitor, and corrosion inhibitors. Two new
additive categories are u n d e r active consideration by the
ASTM committee and could be in the specification by the
time this article is printed. These additives are leak detection
materials smd biocides.
ADDITIVES
General
Allowable additives in aviation fuels are tightly controlled for
safety and operational reasons. The procedures for evaluating the compatibility of additives with aviation turbine fuels
a n d with aircraft fuel system materials are spelled out in
ASTM Practice D 4054. The primary purpose of this practice
is to standardize additive testing requirements so that an additive manufacturer does not have to repeat the process for
each engine or airframe manufacturer. The testing procedures are very detailed and lengthy to assure satisfactory
Alaska
California
Boiling Range, C
Yield, %v
Density, kg/m^
Sulfur, %m
Smoke point, m m
Freezing point, C
Indonesia
Arabia
Libya
8.7
801
0.009
28
-32
12.3
817
0.214
24
-40
13.5
200-260
10.3
828
0.093
20
-44
5.7
0.43
17
-70
0.04
23
-40
CHAPTER
TABLE 8Jet fuel additives listed in D 1655-98b.
Antioxidants, 24 mg/L maximum
2,6-ditertiary-butyI phenol
2,6-ditertiary-butyl-4-methyl phenol
2,4-dimethyl-6-tertiary-butyl phenol
75% min. 2,6-ditertiary-butyl phenol, plus 25% max. mixed tertiary
and tritertiary-butyl phenols
55% min. 2,4-dimethyl-6-tertiary-butyl phenol, plus 15% min, 2,6ditertiary-butyl-4-methyl phenol, remainder as monomethyl and
dimethyl tertiary-butyl phenols
72% min. 2,4-dimethyl-6-tertiary-butyl phenol, 28% max. monomethyl and dimethyl tertisiry-butyl phenols
Metal deactivator, 2mg/L max at mainufacture of fuel, for retreatment
to total of 5.7 mg/L max N,N-disalicylidene-] ,2-propane diamine
Electrical conductivity additive, 3 mg/L max at manufacture of fuel,
for retreatment to total of 5 mg/L max
Stadis 450
Fuel system icing inhibitor, 0.10-0.15%v
Diethylene glycol monomethyl ether (diEGME)
Leak detection additive, 1 ppm max
Tracer A
idation inhibitor, metal deactivator and proprietary detergents and dispersants. Because the combination contains
powerful surfactants, currently only water-absorbing type filter media (commonly called filter-monitors) will operate in
the presence of water and the additive. However, a major effort to develop filter-separators capable of handling the additive holds considerable promise.
Table 9 shows the aviation gasoline additives and their permitted dosages as listed in D 910. They include tetraethyl lead
fluid, which must contain two atoms of ethylene dibromide
per atom of lead as well as one or more of three different
color dyes. Blending two or more of the approved dyes makes
additional colors. While dyes were originally required to
identify any fuel containing lead, today they serve both to
identify lead-containing fuel and to distinguish between the
several grades of aviation gasoline. Oxidation inhibitors, conductivity improver and fuel system icing inhibitors are also
permitted. Note that aviation gasoline can include isopropyl
alcohol as an icing inhibitor, but jet fuel Cctnnot.
TRANSPORTATION
Pipelines
In the U.S. most jet fuel is moved from the refinery by large
multi-product pipelines handling all fuels from gasoline to
diesel fuel. Lines with diameters as large as 40 in (100 cm) are
employed. These lines are normally operated on a fungible
basis where each product meets a single specification. All
suppliers meet that specification, the products then commingled and supplier identity is lost. Differing products are not
physically separated from each other, but operating the line
under turbulent flow conditions minimizes product mixing
at the interface between products. Each pipeline product cycle has its own product sequence to minimize interface material, which is an off-specification mixture of at least two
dissimilar fuels. Pipeline flow is maintained by controlling
pressure a n d flow volume while p r o d u c t s are constantly
added and removed. Products move at a speed of approximately 5 m p h (8 km/h) and, in one pipeline, take about two
4: AVIATION
FUELS
105
HANDBOOK
gets into the aircraft through one or more hoses coupled directly to the aircraft fuel system. The entire hydrant system,
from the storage onward, is pressurized by a series of pumps
that maintain operating pressure right up to the aircraft. Underground pressures of 700-1000 kPa (100-150 psi) are common but must be reduced to 315 kPa (45 psi) maximum at the
aircraft inlet [36]. Unlike a fueller there is no pump abocird
the hydrant vehicle. A hydrant system avoids ramp congestion but permzinently fixes the location of fueling stations. All
major airports and many smaller ones incorporate hydrant
systems. VirtUcdly all airport fuel systems are commingled
systems where each fuel grade meets the same specification
and there is no segregation by individual suppliers.
B o n d e d Fuel
A separate fuel designation, applicable only to international
transportation, is "bonded fuel." Legally such fuel enters a
country under bond and must leave the country in international transportation use. Bonded fuel is not subject to domestic taxes such as excise or sales taxes. Depending on customs regulations, bonded fuel must be handled as a
completely segregated product in its own handling systems
while the fuel is in the country or it can be handled in regular distribution systems as long as its entire volume is accounted for. While originally developed for marine transport,
the concept is equcdly applicable to aviation and is used in
some airports for intemationsJ flights. Its use is limited by
economics as well as local customs regulations.
QUALITY C O N T R O L
General Philosophy
Quality control is intended to protect the fuel properties
needed for safe aircraft operation. Toweurd that purpose aircraft certification requires the fuel to fully meet the specification to which the aircraft was certified. This process starts
at the refinery where aviation fuel must fully meet the pertinent specification. In addition, fuel quality also has to meet
other requirements not in the specification. In their simplest
form those requirements are expressed as "clean and dry."
However, on its way from the refinery to the airport fuel is exposed repeatedly to water, solid contaminants and to other
fuels in multiproduct systems. Quality control therefore becomes an exercise in avoiding that type of contamination,
which cannot be corrected in the field, and removing other
contaminants at reasonable expense by placing appropriate
removal equipment at critical points in the system.
Contaminants
Any material not originally part of the fuel is considered a
contaminant. That definition includes free water, solids such
as rust or sand, microbial material, other fuels, unapproved
additives as well as more unusual materials such as solvents,
fertilizers, plastics, or paints soluble in aviation fuels.
Because aviation gasoline and jet fuel have different critical properties, quality control procedures as well as contamination removal equipment differ for each fuel type and are
described separately in the following sections.
107
els or other materials soluble in jet fuel. Unlike aviation gasoline, a major concern is over contamination with more
volatile materials that will lower the flash point. Solid and
water removal are more difficult with jet fuel because both
the density and viscosity of jet fuel are higher than those of
aviation gasoline. The equipment to remove contaminants as
well the quality control procedures are therefore more elaborate. In addition, a number of specialized field contamination detection procedures are in use.
Contamination Removal Equipment
Filter-Separators
The heart of contamination removal equipment is the filtersepcirator, shown diagrammatically in Fig. 10. Two sets of
cylindrical filter elements are mounted on a deck plate or a
meinifold in the case. First stage elements are termed coalescers, the second stage are separators. Both types usually
have a 6 in (15 cm) diameter; the total element length is proportioned to the maximum rated flow. Fuel flow in the first
stage elements is from inside to outside and outside to inside
in the second stage. In the first stage, at least one filtration
layer consists of tightly packed, hydrophobic glass fibers,
which force smeJl free water droplets to coalesce into leirger
droplets as fuel pushes the water droplets through the layer
[38]. Other layers remove and hold solid particulates. Most of
the coeJesced droplets slide down the outside of the first stage
elements. Those water droplets too small to settle between
stages Eire prevented from exiting with the fuel by the second
stage, which is also hydrophobic. This second stage is made
of Teflon-coated wire mesh or a special synthetic fabric supported by a perforated meted cylinder. The coalesced free water collects in a sump at the bottom of the case and is removed by manually opening a drain valve. A high water
indicator, usually a float or an electronic water level probe in
the sump, shuts off the entire fuel flow if the water level rises
too high and threatens to be carried out with the clean fuel.
A direct reading differential pressure gauge measures the total pressure drop across both sets of elements.
Filter-separators are designed to keep operating when subjected to contaminated fuel. Their minimum performance is
governed by an industry specification issued by the American
Petroleum Institute as API Specification 1581. This specification delineates the solid and free water concentrations
added during qualification testing and dictates the maximum
levels of both contamineint types permitted in the effluent.
The latest version of the specification, Issue 4, was published
in early 2000 and to take effect in January 2002. It contains
three test fuel types. Category C is Jet A plus a conductivity
improver, a corrosion inhibitor aind a sulfonate. Category M
is JP-8 or JP-5 containing military additives. Category MlOO
is Category M plus the JP-8 + 100 additive. Category C is intended for civil use, while the other two categories are for the
U.S. military. Two performance levels are called out. Type S
is to be used where significant solids and water are expected.
Type S-LD, with a lower dirt holding capacity, is intended
where significcint water but low solids are expected. The standard solid contaminant is 90%m A-1 ultrafine dust and 10%
m Copper as red iron oxide. These are major changes from Issue 3 which specified Fischer red iron oxide of about 0,1 micron particle size as the solid contamineint and did not in-
HANDBOOK
iST STAGE
COALSECER ELEMENTS
(INSIDE TO OUT fLOW)
2ND STAGE
SEPARATOR ELEMENTS
(OUTSIDE TO IN FLOW)
INLET MANIFOLD
UTLET MANIFOLD
INLET
OUTLET
109
Filter Locations
Although there are no industry standards for terminal installations, fuel receipts tend to go through a micronic filter into
tankage. When going out of terminaJ tankage to an airport
the fuel passes through em optional micronic filter, followed
by a clay treatment vessel and last through a filter-separator.
At the airport the minimum filtration is through a filter-separator into storage, a filter-separator out of storage into fueling trucks, or into a hydrant system and through a final filterseparator on the fueling vehicle into the aircraft. Filtration
into storage may be supplemented by a micronic or a clay
unit, while the final filtration unit may be a monitor in place
of or in addition to the final filter-separator.
Contamination Detection Equipment
Much of the following equipment, while in extensive worldwide use, has not been standardized by ASTM, but is described in detail in ASTM Manual 5 [39].
Visual Appearance
The appearance of jet fuel is routinely checked in either a
one-liter jar made of clear glass or a white porcelain or stainless steel bucket. The glass is more likely to disclose the presence of fine, suspended material, while the bucket allows the
examination of a larger sample easily taken from a large
drain line. In addition, the white bucket has proven most sensitive to product color, which can indicate contamination
with other darker or dyed fuels. However, such appearance
checks are only a gross measure of possible contamination
and do not disclose levels of solids or free water that are not
visible to the neiked eye. More sensitive tests for contamination are described in the following sections.
Product Color
Quantitative color measurement can be used for the detection of other petroleum products having darker colors, jet
HANDBOOK
such precautions. An alternative is the use of approved biocides mentioned earlier, but the possible adaptation of specific microbes to a biocide has to be kept in mind. The simplest form of detection is a visual and olfactory examination
of water samples from jet fuel systems. Dark or black water,
together with a foul or rotten odor, are usually indicative of
microbial activity. Laboratory testing can indicate the viability and type of microorganisms, but system inspection is usually the best indicator of whether cleaning is required. Much
more detailed information on the subject of microorganisms
in hydrocarbon systems will be found in a new standard
guide, D6469.
Quality Control Procedures
U.S. Procedures
Similcir to aviation gasoline, jet fuel is fully certified against
pertinent specifications at the time of manufacture. In the
U.S. this is normally D 1655, Grade Jet A. Quality is often
rechecked after arrivEil in the terminal with the tests listed in
Table 11. However, this test lineup is experience-based and
Ccin differ significantly from one company to einother; thus,
some shippers require complete specification recertification
of product introduced into their system. Product is settled in
storage for one hour per foot of fuel depth [37]. The pressure
drop across each filter is checked daily. Sumps are drained at
least weekly and after receipt of product. Periodically, usually
once a month, the proper operation of the filter-separator is
checked by rurming a membrane test emd a free water check.
Once approved and settled, the product is shipped to the
airport by transport or pipeline. However, none of these operations are governed by industry standcirds and it is the responsibility of the operating company to furnish on-specification, "clear and bright" fuel to the airport.
Airport quality control is more systematic. The Air Transport Association of America (ATA) has issued a specification,
ATA 103, which is recommended for its member airlines or
virtually EJI U.S. eind Canadian airlines. Additionally, member airlines can require the specification to be followed by independent airport biel dealers who supply these airlines. All
jet fuel delivered to U.S. airports must meet ASTM D 1655 in
order to meet the certification requirements of the various
aircraft. As indicated in Table 12, when ATA 103 is to be followed, certain tests must be furnished by the shipper on the
specific shipment. Other tests are conducted at the airport
during and after product receipt. Additional periodic testing
to be carried out at the airport is listed in Table 13. Failure to
meet any of these requirements is cause for immediate investigation.
CHAPTER
It should be noted that ATA 103 includes other aspects of
airport quality control as well, but these do not directly involve fuel quality.
International
Procedures
Visual-white bucket
API Gravity @ 60F (15C)
Distillation
Flash point
Freeze point
Water reaction
Copper corrosion
Existent gum
Visual-white bucket
API gravity eO^FClS^C)
FUELS
111
tional Air Transport Association (lATA) to be used by individual airline members as part of contractual requirements
with suppliers. Ultimately, it is hoped to merge ATA 103 with
the LATA Guidelines to create a single set of worldwide airport quality control procedures, but the success of this endeavor cannot be predicted at this time.
Aircraft
Procedures
4: AVIATION
From compartment
before unloading
Visual-white bucket
API gravity (within 1)
Visual-white bucket
API Gravity @ eCF (15C), within 1
Distillation, within 8C
Flash point, within SX"
Freezing point, within 3C
''Variability allowed from supplier's certificate.
TABLE 13Airport fuel quality requirements per ATA 103, other required checks.
Daily Required Checks
Filter pressure drop
Change elements at 15 psi
Monitor pressure drop
Change elements at 25 psi
Drain filter sumps
Inspect with white bucketone gallon sEimple minimum
Drain storage tank sumps
Inspect with white bucketone gallon sample minimum
Drain fueling truck
Inspect with white bucketone gallon sample minimum
Monthly Required Checks
Free water
Membrane color
Particulate assessment
15 ppm max
2 dry/gal or 3 wet/gal
A max
HANDBOOK
lems can have an impact on legal issues such as the assignment of liability and can have large financial consequences.
The complexities of the interactions between the technical,
legal, and financial aspects associated with aviation fuels can
therefore make it difficult at times to resolve problems, but
such problems must be addressed to maintain and, if possible, improve the reliability of the entire system.
ASTM STANDARDS
Unless otherwise indicated all of the following standards are
current.
No.
Title
D 56
D 86
D 130
D 156
D 323
D 445
D 614
D 618
D 873
D 909
D 910
D 1250
D 1298
D 1319
D 1322
D 1655
D 1740
D 1840
D 2386
D 2392
D 2700
D 3227
D 3240
D 3241
D 3338
D 3701 Test Method for Hydrogen Content of Aviation Turbine Fuels by Low Resolution Nuclear Magnetic
Resonance
D 3948 Test Method for Determining Water Separation
Characteristics of Aviation Turbine Fuels by
Portable Separometer
D 4052 Test Method for Density and Relative Density of
Liquids by Digital Density Meter
D 4171 Specification for Fuel System Icing Inhibitor
D 4305 Test Method for Filter Flow of Aviation Fuels at
Low Temperatures
D 4809 Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision
Method)
D 4865 Guide for Generation and Dissipation of Static
Electricity in Petroleum Fuel Systems
D 4952 Test Method for Qualitative Analysis of Active Sulfur Species in Fuels and Solvents (Doctor Test)
D 5001 Test Method for Measurement of Lubricity of Aviation Turbine Fuels by the Ball-On-Cylinder Lubricity Evaluator (BOCLE Test)
D 5191 Test Method for Vapor Pressure of Petroleum Products (Mini Method)
D 5842 Practice for Sampling and Handling of Fuels for
Volatility Measurement
D 5901 Test Method for Freezing of Aviation Fuels (Automatic Optical Method)
D 5972 Test Method for Freezing of Aviation Fuels (Automatic Phase Transition Method)
D 6045 Test Method for Color of Petroleum Products by the
Automatic Tristimulus Method
D 6227 Specification for Grade 82 Unleaded Aviation Gasoline
D 6304 Test Method for Determination of Water in
Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fisher Method
D 6378 Test Method for Determination of Vapor Pressure
(VPx) of Petroleum Products, Hydrocarbons and
Hydrocarbon-Oxygenate Mixtures (Triple Expansion Method)
D 6424 Test Method for Octane Rating Naturally Aspirated
Spark Ignition Aircraft Engines
D 6469 Standard Guide for Microbial Contamination of Fuels and Fuel Systems
OTHER STANDARDS
U.S. Military Aviation Turbine Fuel and Additive
Specifications^
No.
Title
MIL-PRF-5624
U. K. M i l i t a r y A v i a t i o n T u r b i n e F u e l a n d A d d i t i v e
Specifications
These standards are available from Ministry of Defence, Directorate of Standardization, 65 Brown Street, Glasgow G2
SEX.
No.
Title
ATF High Flash AVCAT/FSII
ATF Wide Cut AVTAG/FSII
AVGAS Gasoline Aviation 80 and
lOOLL (low lead)
Turbine Fuel, Aviation Kerosine
Defence Standard 91-91
Type, Jet A-1
Defence Standard 91-251 Fuel System Icing Inhibitor
(FSII)
Defence Standsird 68-251 Fuel Soluble Pipeline Corrosion
Lubricity Improving Additive
Defence Standard 91-86
Defence Standard 91-87
Defence Standard 91-90
Industry Specifications
API/IP 1581 Specifications and Qualification Procedures for
Aviation Jet Fuel Filter/Separators
API/IP Specification for Similarity for API/IP 1581 Aviation
Jet Fuel Filter/Separators
API/IP 1583 Specifications and Qualification Procedures for
Aviation Fuel Filter Monitors with Absorbent T5rpe Elements
API/IP Specifications and Qualification Procedures for Aviation Fuel Microfilters
ATA 103, Standards for Jet Fuel Quality Control at Airports
LATA Guidance Material for Aviation Turbine Fuels Quality
Control and Operating Procedures, Incorporating Joint Inspection Group Guidelines for Joint Airport Depots and
Joint into Plane
lATA Guidance Material for Aviation Turbine Fuels
REFERENCES
[1] Ogsten, A. R, "A Short History of Aviation Gasoline Development, 1903-1980," Preprint No. 810848, SAE, West Coast International Meeting, Seattle, WA, 3-6 August 1981, Society of Automotive Engineers, Warrendale, PA.
[2] Dukek, W. G., "Aviation Fuel: Its Energy has Knit the World,"
Standardization News, ASTM International, West Conshohocken, PA, April 1998.
[3] Defence Standard 91-91: Turbine Fuel, Aviation Kerosine, Type
Jet A-1, Issue 3, Ministry of Defence, Directory of Standardization, Glasgow, FG2 SEX, United Kingdom, November 1999.
[4] Guidance Material for Aviation Turbine Fuel, fourth edition. International Air Transport Association, Montreal, Canada, March
1999.
[5] Winkle, T. L., Affens, W. A., Beal, E. A., Hazlett, R. N., and
DeGuizeman, R., "The Distribution of Higher n-Alkanes in Partially Frozen Middle Distillate Fuels," NRL Report 8869, Naval
Research Laboratory, Washington, DC, 10 April 1985.
[6] Smith, M., Aviation Fuels, G. T. Foulis & Co Ltd, Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 272-278.
[36] Smith, M., Aviation Fuels, G. T. Foulis & Co. Ltd., Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 192-196.
[37] Robertson, A. G., "Jet Fuel Settling," Shell Aviation News, Vol.
351, 1967, pp. 17-28.
[38] Hughes, V. B., "Aviation Fuel Handling: New Mechanistic Insight into the Effect of Surfactants on Water Coalescer Performance," Proceedings of 6th International Conference on Stability a n d Handling of Liquid Fuels, Vancouver, 12-17 Oct. 1997.
[39] Manual of Aviation Fuel Quality Control Procedures, Second
Edition, ASTM Manual 57, R. Waite, Ed., ASTM International,
West Conshohocken, PA, 1995.
[40] "Aircraft Use of Dyed Fuel," Boeing Service Letter for 707, 727,
737, 747, 757, 767, and 777 Series, 22 Nov. 1996.
[41] Unpublished minutes of the CRC Group o n Dye In Aviation Turbine Fuels, Coordinating research Council, Atlsinta, GA, 1996 to
date.
[42] Churchill, A. V., "Microbial Fuel Tank Corrosion: Mechanisms
andContributoryFactors,"MaferJaisProtecft'ora, Vol. 2,1963, p. 18.
MNL37-EB/Jun. 2003
The diesel engine is now fully established in a variety of applications on land and in marine use. On land, it serves to
power trains, buses, trucks, and automobiles; to run construction, petroleum drilling, and other off-road equipment;
and to be the prime mover in a wide range of power generation and pumping applications. At sea, it serves both to provide main propulsion power and run auxiliaries.
Gas turbine engines also serve in a wide range of applications. Over half the larger industrial gas turbines are in electric-generation use. Other uses include gas pipeline transmission, co-generation systems, and transportation. In the
military, gas turbines power a number of combatant ships
both as main propulsion units and as the power source for
auxiliary uses. Gas turbines are also used to power some military ground vehicles such as main battle tanks.
The quality criteria and methods for testing fuels for land
and marine diesel engines and for non-aviation gas turbines
are sufficiently similar to address in a common chapter. Obviously, certain criteria and tests will apply to one or the
other rather than both. For example, the cetane number,
which is a critical property for diesel fuels, is of limited significance for gas turbine fuels. Conversely, sodium and vanadium content are important in assessing gas turbine fuels,
but not those used in diesel engines. This chapter presents information regarding fuels for both automotive diesel engines
and gas turbines.
The petroleum industry started in the 1850s. Two factors
were especially important as impetus. Machines were being
developed and they needed oil for lubrication. Also, oil lamps
were being used to light homes and offices and the whale oil
traditionally burned in these lamps was growing increasingly
expensive. James Young, a Scotsman, had recently patented
a process for converting coal to coal oil. Coal oil was less expensive than whale oil but smoked and produced a foul smell
when burned. Then, in 1857, lamp maker A.C. Ferris produced clean-burning kerosine that did not have a bad smell
[1]. The oil used for making the kerosine was being skimmed
from natural crude oil seeps until Colonel Edwin Drake
drilled into one of the seeps, near Titusville, Pennsylvania, using a rig of the type used for drilling brine wells. An oil boom
was bom.
During the 1860s, oil exploration and drilling expanded to
Ohio, Termessee, New York, Kentucky, Colorado, and Califor-
nia. From this time until about 1900, kerosine for oil lamps
was the most valuable fraction of the petroleum barrel. The
fraction now known as gasoline was considered surplus and
burned. The heavier residual fraction was typically dumped
into pits or other convenient dumping grounds. The middle
distillate fraction, which would eventually be used in diesel engines, was used in the town gas industry. It was used "either as
a source of domestic gas, or for enriching or carburetting water gas, or as an absorbing agent or 'wash oil' for removing condensable constituents from coal gas" [2]. This is the reason
that this fraction is still often referred to as gas oil. Throughout this time, the middle distillate fraction of the petroleum
barrel was primarily a leftover product with no leirge market.
The invention of the diesel engine changed that for the better.
Compression Ignition Engines
' Manager, Petroleum Products Technology, Southwest Research Institute, P.O. Drawer 28510, San Antonio, TX 78228.
^ Consultant Engineer, Gas Turbine Combustion & Fuels, Retired,
3760 Sioux Avenue, San Diego, CA 92117.
Since it's beginning in the 1890s, the diesel engine quickly became the engine of choice for many industrial and marine applications, applications where the larger, heavier, slower
speed engine excelled in cost and performance when compared to alternative power plants of the time. However, the
diesel engine saw only limited use in automotive and aviation
applications. After World War I, shortages of gasoline in Germany helped stimulate work on the diesel engine, especially
as an automotive engine. Diesel engines were used for
propulsion on the Hindenburg.
Suppljdng fuel to the engine was the major obstacle to a
higher-speed, lower-weight engine suitable for automotive
use. Compressed air injection was complicated and the required air pump could not be substantially reduced in either
size or weight. In 1922, Robert Bosch set out to develop a
fuel-injection system for diesel engines [3]. By early 1923,
about a dozen different designs had been developed and initial trials were underway by mid-1923. A final design was approved in 1925 and the first series production fuel-injection
pump was on the market.
The fuel-injection system opened the door for wide spread
use of the diesel engine in previously untried applications. By
the mid-1930s there were large numbers of diesel-powered
trucks and buses in service; but only small numbers of dieselpowered automobiles. By the beginning of World War II in
1939, the diesel engine was in widespread use as an automobile engine. The German military also used diesel engines for
many of their vehicles, including some aircraft [4]. Gasoline
engines, because of the logistics problems faced with a twofuel supply system, powered the Allied Forces almost exclusively. Following World War II; the greater fuel economy of
115
Copyright'
2003 by A S I M International
www.astm.org
>.
(0
Q
a.
m
CD
0 J
1950
1960
1970
1980
1990
2000
Year
Source: U.S. Energy Information Administration
FIG. 1Diesel fuel supplied to the transportation sector.
the diesel engine caused a rapid increase in the use of the engine for automotive applications throughout Europe. The
abundance of inexpensive gasoHne in the United States lowered incentives for adopting the diesel engine in trucks and
automobiles. Even still, throughout this period, the diesel engine climbed in popularity for use in railroad, marine, and
heavy-construction equipment applications. The use of the
diesel engine increased until virtually 100% of current marine, trucking, railroad, construction, and much of the stationary power generation applications operate on diesel engines. The fuels used in these engines have, over time, varied
from natural gas to crude oil but the middle distillate, number 2 grade liquid fuel, is the fuel of choice for many of these
applications. Figure 1 shows the increase in diesel fuel usage
for transportation since 1949 [5].
D 975-48 T
D 975-98b
No. 1-D
A volatile distillate
fuel oil for engines
in service requiring
frequent speed and
load changes.
A special-purpose, light
distillate fuel for
automotive diesel engines
in applications requiring
higher volatility than that
provided by Grade No.
2-D fuels.
Low Sulfur
No. 1-D
Not Applicable
A special-purpose, light
distillate fuel for
automotive diesel engines
requiring low sulfur fuels
and requiring higher
volatility than that
provided by Grade Low
Sulfur No. 2-D.
No. 2-D
A general-purpose, middle
distillate fuel for
automotive diesel engines,
which is also suitable for
use in non-automotive
applications, especially in
conditions of frequently
varying speed and load.
Low Sulfur
No. 2-D
Not Applicable
A general-purpose, middle
distillate fuel for automotive diesel engines
requiring low sulfur fuel.
It is also suitable for use
in non-automotive
applications, especially in
conditions of varying
speed and load.
No. 4-D
Density
Density is the mass per unit volume of the fuel. This property
is not specified in D 975. However density is a fundamental
physical property that can be used in conjunction with other
properties to characterize both the light and heavy fractions
of petroleum cind petroleum products. Accurate determination of the density of petroleum products is also necessary for
the conversion of measured volumes to volumes at the standard temperature of 15C (60F). While density is a factor
governing the quality of crude petroleum, it is an uncertain
indication of petroleum product quality unless correlated
with other properties.
The two methods most commonly used to measure density
are:
ASTM D 1298, Standard Test Method for Density, Relative
Density (Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products by Hydrometer
MethodThe sample is brought to the prescribed temperature a n d transferred to a cylinder at approximately the
same temperature. The appropriate hydrometer is lowered
117
HANDBOOK
Property
Flash Point, C, min.
Water and Sediment, % vol, max
Distillation Temperature, C 90 % % vol
Recovered
min
max
Kinematic Viscosity, mm^/S at 40C
min
max
Ash % mass, max
Sulfur, % mass, max^
Copper strip corrosion rating mjix 3 h
at SOX
Cetane number, min''
One of the following properties must
be met:
(1) Cetane index, min.
(2) Aromaticity, % vol, msix
Cloud point, C, max
Ramsbottom carbon residue on 10%
distillation residue, % mass, max
ASTM Test
Method^
Grade Low
Sulfur
No. 1-D^
Grade Low
Sulfur
No. l-D"''
Grade
No. 1-D'
Grade
No. 2-0*'
38
0.05
52
0.05
38
0.05
52
0.05
D93
D2709
D 1796
D86
Grade
No. 4-D'
55
0.50
282'^
338
288
288
282^*
338
D445
D482
D 2622
D129
D130
1.3
2.4
0.01
0.05
1.9
4.1
0.01
0.05
No. 3
D613
916f
1319'"
2500
524
1.3
2.4
0.01
1.9
4.1
0.01
5.5
24.0
0.10
0.50
No. 3
0.50
No. 3
2.00
No. 3
40"
40"
40'
40'
40
35
40
35
0.15
0.
0.15
30'
0.35
"To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer.
''The test methods Indicated are the approved referee methods. Other acceptable methods are Indicated in 3.1.
"Under United States regulations. If Grades Low Sulfur No. 1-D or Low Sulfur No. 2-D are sold for tax exempt purposes then, at or beyond terminal storage
tanks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid
dye standard Solvent Red 26, or the tax must be collected.
''when a cloud point less than 12C is specified, the minimum flash point shall be 38C, the minimum viscosity at 40C shall be 1.7 mm^/s, and the minimum
90% recovered temperature shall be waived.
'Under United States regulations. Grades No. 1-D, No. 2-D, and No. 4-D are required by 40 CFR Part 80 to contain a sufficient amount of the dye Solvent Red
164 so Its presence Is visually apparent. At or beyond terminal storage tanks, they are required by 28 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid dye standard Solvent Red 26.
'^Other sulfur limits can apply In selected areas in the United States and In other countries.
^These test methods are specified in 40 CFR Part 80.
''Where cetane number by Test Method D 613 Is not available, Test Method D 4737 can be used as an approximation.
'Low ambient temperatures as well as engine operation at high altitudes may require the use of fuels with higher cetane ratings.
'It is unrealistic to specify low temperature properties that will ensure satisfactory operation at all ambient conditions. In general, cloud point (or wax appearance point) may be used as an estimate of operating temperature limits for Grades Low Sulfur No. 1; Low Sulfur No.2; and No.l and No. 2 diesel fuel oils.
However, satisfactory operation below the cloud point (or wax appearance point) may be achieved depending on equipment design, operating conditions, and the
use of flow-improver additives as described in X4.1.2. Tenth percentile minimum air temperatures for U.S. locations are provided in Appendix X4 as a means of
estimating expected regional temperatures. This guidance Is general. Some equipment designs or operation may allow higher or require lower cloud point fuels.
Appropriate low temperature operability properties should be agreed upon between the fuel supplier and purchaser for the Intended use and expected ambient
temperatures.
119
minimum cetane number of 40 [8] and this is the requirement in D 975. Many engine manufacturers are now pushing
to raise the specification minimum limit to 50 cetane in order to meet new engine emission requirements (see the discussion of the Worldwide Fuels Charter below).
Cetane Index
Two ASTM test methods for calculating approximate cetetne
numbers were also developed for situations when performing
the engine test was not feasible. Two ASTM methods, and the
equations for each, are:
ASTM D 976, Standard Test Method for Calculated Cetane
Index of Distillate Fuels
Calculated Cetane Index = 454.74 - 1641.416 D
+ 774.74 0^-0.554 5 + 97.803 (log 5)^
Where:
D = density at 15C, g/mL, determined by Test
Method D 1298, and
B = mid-boiling temperature, C, determined by
Test Method D 86 and corrected to standard
barometric pressure.
ASTM D 4737, Standard Test Method for Calculated Cetane
Index by Four Variable Equation
CCI = 45.2 + (0.0892)(rioN) + [0.131 + (0.901)B][r50N]
+ [0.0523 - (0.420)B][r90N]
+ [0.00049][(rioN)^ - (T'OTN)^] + 1075 -H 605^
Where:
CCI - Calculated Cetane Index by Four Variable Equation,
D = Density at 15C, determined by Test Method D
1298,
DN =D- 0.85,
B
= [e(-3-5XDN)] _ 1^
120
MANUAL
HANDBOOK
Volatility / Distillation
The distillation characteristics of a diesel fuel exert a great influence on performance. Two methods are commolily used to
measure distillation characteristics:
ASTM D 86, Standard Test Method for Distillation
of
Petroleum Products^A 100 mL sample is distilled u n d e r
prescribed conditions that are appropriate to its nature.
Systematic observations of thermometer readings and volumes of condensate are made, and from these data, the results of the test are calculated and reported.
ASTM D 2887, Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
The boiling range distribution determination by distillation is simulated by the use of gas c h r o m a t o g r a p h y . A
non-polar packed or open t u b u l a r (capillary) gas chromatographic column is used to elute the hydrocarbon components of the sample in order of increasing boiling point.
The column temperature is raised at a reproducible lineeir
rate and the area u n d e r the c h r o m a t o g r a m is recorded
throughout the analysis. Boiling points are assigned to the
time axis from a calibration curve obtained under the same
chromatographic conditions by analyzing a known mixture of hydrocarbons covering the boiling range expected
in the sample. From these data, the boiling range distribution can be obtained.
Method D 86 is the specified method in D 975 for measuring distillation characteristics. Figure 2 is a plot of distillation
data for a single, typical diesel fuel using both methods. It is
obvious from this plot that the two methods can give quite
different results. For most fuels, results like these are typical;
with more deviation at the beginning and end of the distillation Eind less deviation at the center. For this reason, D 2887
is not Ein accepted eJtemative to D 86 for specification purposes. That will remain the case until a suitable correlation
(correction factor) between the two is determined.
Figure 3 is the D 2887 gas c h r o m a t o g r a m for the fuel
shown in Fig. 2. The chromatogram illustrates the usefulness
of the D 2887 method. The time axis can be correlated to carbon n u m b e r by using a known standard. Therefore, it is possible to obtain a "picture" of the carbon n u m b e r distribution
in a given fuel. This method is also useful for identifying contaminants such as gasoline a n d engine oil.
The average volatility requirements of diesel fuels vary
with engine speed, size, cind design. However, fuels having
too low volatility tend to reduce power output Eind fuel economy through poor atomization, while those having too high
volatility m a y reduce p o w e r o u t p u t a n d fuel economy
through vapor lock in the fuel system or inadequate droplet
penetration from the nozzle. I n general, the distillation range
should be as low as possible without adversely affecting the
flash point, burning quality, heat content, or viscosity of the
fuel. If the 10% point is too high, poor starting may result. An
excessive boiling range from 10-50% evaporated may increase warm-up time. A low 50% point is desirable to minimize smoke and odor. Low 90% cind end points tend to ensure low carbon residuals and minimum crankcase dilution.
The temperature for 50% evaporated, known as the midboiling point, usucdly is taken as a n overall indication of the
fuel distillation chziracteristics when a single numerical value
is used alone. For example, in high-speed engines a 50%
point above 302C might cause smoke formation, produce
objectionable odor, cause lubricating oil contamination, and
promote engine deposits. At the other extreme, a fuel with excessively low 50% point would exhibit too low a viscosity eind
heat content per unit volume. Therefore, a 50% point in the
range of 232-280C is desirable for the majority of higher
speed diesel engines. This t e m p e r a t u r e range usually is
broadened for Icirger, slower speed engines [12].
100
D86
D2887
80
I
40
on
20 -
0-"
100
150
200
250
300
350
400
450
Distillation Temperature, C
FIG. 2Distillation curves for a typical no. 2 diesel fuel (methods D 86
vs. D 2887).
Time
FIG. 3D 2887 gas chromatogram of a typical diesel fuel.
121
HANDBOOK
1 and No. 2 diesel fuel oils. However, satisfactory operation below the cloud point (or wax appearance point) may
be achieved depending on equipment design, operating
condition, and the use of flow-improver additives... Tenth
percentile minimum air temperatures for U.S. locations
are provided.. .as a means of estimating expected regional
temperatures. This guidance is general. Some equipment
designs or operation may allow higher or require lower
cloud point fuels. Appropriate low temperature operability
properties should be agreed upon between the fuel supplier
and purchaser for the intended use and expected ambient
temperatures.
The tenth percentile temperatures Eire presented for each
U.S. state, except Hawaii, for each month from October to
March. They are presented in both tabular format and in
maps. Figure 4 is an example of one of the maps.
Realistic options to reduce the cloud point include:
1. Dilute the fuel with a low wax fuel such as grade No. 1 or
kerosine.
2. Treat the fuel with special additives.
3. Refine the fuel from crude(s) with lower wax content or refine the fuel to a lower end point.
4. It is also possible to add insulation and heaters to the vehicle fuel system. This will not change the cloud point of
the fuel but will improve the low temperature operation.
Pour Point
Before a fuel can be burned in an engine it must first be
pumped from the fuel tank. The lowest temperature at which
a fuel can be pumped is known as the pour point of the fuel.
Test methods for measuring pour point include:
ASTM D 97, Standard Test Method for Pour Point of
Petroleum ProductsAfter preliminEiry heating, the sample
is cooled at a specified rate and examined at intervals of
3C for flow characteristics. The lowest temperature at
which movement of the specimen is observed is recorded
as the pour point.
The following methods are variations of D 97, including,
both automatic and automated methods.
ASTM D 5949, Standard Test Method for Pour Point of
Petroleum Products (Automatic Pressure Pulsing Method)
ASTM D 5950, Standard Test Method for Pour Point of
Petroleum Products (Automatic Tilt Method)
ASTM D 5985 Standard Test Method for Pour Point of
Petroleum Products (Rotational Method)
The pour point should be considered only a guide to the
lowest temperature at which a fuel can be used. In general,
pour points are from 3-6C below the cloud point for a given
fuel; however, it is not uncommon for the difference to be as
much as 11 C.
ture, expressed as a multiple of 1C, at which a test specimen can be filtered in 60 s or less. Alternatively, a single
specimen may be cooled and tested at a specified temperature to determine whether it passes or fails at that temperature.
Figure 5 is a diagram of the LTFT test apparatus. The LTFT
was designed to yield results indicative of the low temperature
flow performance of the test fuel in some diesel vehicles. The
test method is especially useful for the eveiluation of fuels containing flow improver additives. Please refer to Report No.
528 from the Coordinating Research Council for a more detailed discussion [15]. The LTFT was developed in the United
States to simulate the low temperature behavior of diesel fuel
in the fuel tank of a diesel truck left overnight, in a cold environment, with its engine off. J. E. Chandler, zmd others, have
demonstrated that this test has shown excellent correlation
with field studies [16-18]. In spite of the demonstrated correlation to field performance, the LTFT is not as widely used as
some other tests. The primary reason for this is the slow cooling rate (1C per hour), which means that the time required
completing an analysis can range from 12-24 h. Such test
times are generally impractical for routine fuel testing.
Cold FUter Plugging Point
The Cold Filter Plugging Point, CFPP, was developed for use
in Europe. The Institute of Petroleum publishes the method
under the designation IP 309. It is similar to the LTFT with
the following exceptions:
The fuel is cooled by immersion in a constant temperature
bath, making the cooling rate non-linear but comparatively
much more rapid (about 40C per hour).
The CFPP is the temperature of the sample when 20 mL of
the fuel first fails to pass through a wire mesh in less than
60s.
Glass Tubing
6 10 Min Throughout
Vacuum Gage
Point A
Storage Lid
200 ML Sample
Glass Stem
Quality Flex lObing
Sample Container
300 ML Tall-Form
Beaker
123
Sample Receiver
400 ML Tall-Form
Beaker
HANDBOOK
considered a combination of the best features of the two previous methods. It is sensitive to small amounts of particles
and is even capable of detecting microscopic particulates. It
is also a quantitative measure of the cleanliness of the fuel.
The quantitative measure is milligrams of particulate (contamination) per liter of fuel. Currently there is no consensus
standard with a specification limit for D 6217. Many user
specifications, including some federal and military diesel fuel
specifications, include a limit of 10 mg per liter for the results
of this analysis. Most users have found fuel that meets this
limit to give satisfactory performance in the vehicle.
ASTM D 6217, Standard Test Method for Particulate Contamination in Middle Distillate Fuels by Laboratory Filtration^A measured volume of about 1 L of fuel is vacuum filtered through one or more sets of 0.8 /u,m membranes.
Each membrane set consists of a tared nylon test membrane and a tared nylon control membrane. When the level
of particulate contamination is low, a single set will usually
suffice; when the contamination is high or of a nature that
induces slow filtration rates, two or more sets may be required to complete filtration in a reasonable time. After the
filtration has been completed, the membranes are washed
with solvent, dried, and weighed. The particulate contamination level is determined from the increase in the mass of
the test membranes relative to the control membranes, and
is reported in units of glw? or its equivalent mg/L.
ASTM D 2068, Standard Test Method for Filter Plugging Tendency of Distillate Fuel OilsA sample of the fuel to be
tested is passed at a constant rate of flow (20 mL/min)
through a glass fiber filter medium. The pressure drop
across the filter is monitored during the passage of a fixed
volume of test fuel. If a prescribed maximum pressure drop
is reached before the total volume of fuel is filtered, the actual volume of fuel filtered at the time of maximum pressure drop is recorded.
The primary weakness of visual and gravimetric method is
that there is no generally accepted correlation between the
results of the test and the performance of the fuel in a vehicle
fuel system. That is, how long could the vehicle operate on
that fuel before the fuel filter plugs or the water separator
fails? The British Navy first developed D 2068 as a dynamic
test of the cleanliness of fuel for shipboard gas turbine engines [21]. The test was designed around the specific requirements of gas turbine powered ships in the British Navy. The
most important requirement was that the shipboard fuel filters had a nominal porosity of 1 /am. As such, a 1 /u,m pore
size glass fiber laboratory filter is used in the test. Over the
years the test apparatus was upgraded, making it more automated.
ASTM D 6426, Standard Test Method for Determining Filterability of Distillate Fuel Oils^A sample is passed at a constant rate (20 mL/min) through a standard porosity filter
medium. The pressure drop across the filter and the volume of filtrate are monitored. The test is concluded either
when the pressure drop across the filter exceeds 170 kPa
(25 psi) or when 300 mL have passed through the filter. Results are reported as either the volume that has passed
through the filter when a pressure of 170 kPa (25 psi) has
been reached or the pressure drop when 300 mL have
passed through the filter. In the latter case, the volume, if
and when 105 kPa (15 psi) was exceeded, is also recorded.
(D)
DISPLAYS
PRESSURE VOLUME VOLUME
(psi) ((Si 0-25 psi) ((a! 0-15 psi)
PRESSURE
TRANSDUCER
PERISTALTIC PUMP
\
PULSE
\
DAMPENrNG
/lECIIANISM
ay
PLA,STIC TIP
TYGON
TUBING
RUBBER STOPPER (VENTED)
FILTER CELL
"FUEL SAMPLE
FUEL FLOW
COLLECTION
CONTAINER
PROCESSED FUEL
Stability
For the purposes of this discussion, fuel stability is defined as
the resistance of the fuel to physical and chemical changes
brought about by the interaction of the fuel with its environment.
The chemistry of diesel fuel stability (instability) is complex. In general, it involves the chemical reaction of precursor species to form molecules of higher molecular weight.
The higher molecular weight species then become insoluble
deposits in the form of either gums or particulates. The precursor species are usually sulfur and/or nitrogen containing
compounds, olefins, and organic acids. The reactions are often initiated by the oxidation of the precursors. Some dissolved metals, especially copper but also zinc and even iron,
are known to catalyze the oxidation reactions. In the case of
copper, as little as 10-30 parts per billion of dissolved copper
is sufficient to catalyze deleterious reactions, depending on
the fuel. The mechanism proposed by Pedley [23] (shown in
Fig. 7) is perhaps the most cited example of these types of reactions. Although this mechanism explains many of the earlier findings on diesel stability, it does not account for the for-
oxldatlon
Phenalenes
125
1
Phenalenones
Indoles
Acid
Indolylphenalenes
Acid/Oxidation
Fuel Insolubles
126
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
20
""" /
/ /
/ -^ '
18
16
M
tX
s,
s'
10
//
/ ""^
\
/
Thermal Stability
V^
/
//
/
^
ujl2
,y
\&
MULTILABORATORY
VISUAL RATINGS
y
/^
100
>
VISUAL RATINGS IN
ONE LABORATORY
'
80
60
"JO
20
PERCENT REFLECTION
(PHOTOVOLT MODEL 670 REFLECTION HETER WITH SEARCH UNIT W)
Arguably, this test is the most often used method to monitor/predict fuel stability. The primary reason for its popularity is the short test time and simple equipment requirements.
This has made the 150C test, in one form or another, especially popular with many pipeline companies and others with
the need to monitor the quality of fuel but do it rapidly. Stavinoha and Westbrook demonstrated that this test has poor
correlation to the generally accepted test for storage stability
of diesel fuel (see D 4625 below) [31]. Bacha [32] and Henry
[33] reported that the 150C test provides an indication of
thermal stability of distillate fuels exposed to high temperatures. The test method can be useful for investigation of operational problems related to fuel thermal stability. When D
6468 is used to m o n i t o r fuel in production or storage, a
change in filter rating can indicate a relative change in inherent stability of the fuel. No quantitative relationship exists
between pad ratings and the gravimetric mass of filterable insolubles formed during the test. Additional information on
the interpretation of results is found in Appendix XI of the
test method.
Oxidation Stability
Oxidation stability is the resistance of the fuel to change under severely oxidizing conditions. In addition to exposing the
fuel to excess amounts of oxygen, oxidation stability tests
usueJly incorporate elevated test temperatures to accelerate
reaction rates. The method commonly used to measure oxidation stability of diesel fuel is:
ASTM D 2274, Standard Test Method for Oxidation Stability
of Distillate Fuel Oil (Accelerated Method)^A 350-mL volu m e of filtered middle distillate fuels is aged at 95C
(203F) for 16 h while oxygen is bubbled through the sample at a rate of 3 L/h. After aging, the sample is cooled to ap-
CHAPTER
proximately room temperature before filtering to obtain
the filterable insolubles quantity. Adherent insolubles are
then removed from the oxidation cell and associated glassware with trisolvent. The trisolvent is evaporated to obtain
the quantity of adherent insolubles. The sum of the filterable and adherent insolubles, expressed as milligrams per
100 mL, is reported as total insolubles.
Because for m a n y years this was the only standardized
method to measure stability of middle distillate fuels, it became a part of n u m e r o u s fuel specifications (mostly government/military) and was widely used as a predictor of fuel
storage stability. Despite the wide acceptance as a storage
stability test, most researchers agreed that, in fact, the results
of D 2274 had very poor correlation to actual, ambient storage of the fuel. In addition, the precision of the test was extremely poor. Many researchers have worked to improve the
test. Chief a m o n g these is E. W. White of the U.S. Navy
[34,35]. Some of the factors he identified as having an effect
on the results of the test are: the purity of the oxygen, stray
light impinging the sample during aging (especially ultra-violet light), contact with metal surfaces (especially copper),
filter drying time, and heating bath configuration. Based on
the work of White and others, many needed improvements
were made to the method. The precision of the test is better
now than when it was first published by ASTM. However, despite the improvements, the results continue to have poor
correlation to ambient storage. Because this poor correlation
is now more widely known, the use of the method to assess
the stability of diesel fuels is very low.
5: GAS TURBINE
FUELS
127
Microbiological
contamination
Commingling of fuels
Storage Stability
Storage stability is generally defined as the fuel's resistance to
change during storage at ambient temperature and conditions. Ambient storage is storage of the fuel in drums, storage
tanks, vehicle fuel tanks, or similar containers in the out-ofdoors. There are many factors that can influence the storage
stability of a given fuel. The most c o m m o n factors are listed
in Table 4. The two tests for storage stability are:
ASTM D 4625, Standard Test Method for Distillate Fuel Storage Stability at 43C (nOF)Four-hundred
mL volumes
of filtered fuel are aged by storage in borosilicate glass containers at 43C (110F) for periods of 0, 4, 8, 12, 18, and 24
weeks. After aging for a selected time period, a sample is removed from storage, cooled to room temperature, and analyzed for filterable insolubles and for adherent insolubles.
ASTM D 5304, Standard Test Method for Assessing Distillate
Fuel Storage Stability by Oxygen OverpressureA 100-mL
aliquot of filtered fuel is placed in a borosilicate glass container. The container is placed in a pressure vessel that has
been preheated to 90C. The pressure vessel is pressurized
with oxygen to 800 kPa (absolute) (100 psig) for the duration of the test. The pressure vessel is placed in a forced air
oven at 90C for 16 h. After aging and cooling, the total
amount of fuel insoluble products is determined gravimetrically and corrected according to blank determinations.
All petroleum fuels u n d e r g o chemical reactions during
storage. The results of these reactions are usually g u m s ,
acids, and/or particulates. The n u m b e r and rate of these deleterious reactions depends on the concentrations of reaction
precursors, the concentration of oxygen available for oxida-
tion reactions, the presence of catalytic species such as metals, the a m o u n t of light, and the storage temperature. As
mentioned above, the resistance of the fuel to these reactions
is defined as its storage stability. Most researchers cJso go a
step further and define inherent storage stability as the resistance to change in the absence of environmental factors such
as metals and contaminants (i.e., in the absence of catalytic
effects).
The inherent stability is important because it is a measure
of the useful storage life of the fuel. For most diesel fuels under normal storage conditions,it may take several months or
even years for the deleterious reactions to generate enough
by-products to cause fuel-related p r o b l e m s . A user w h o
would like to store fuel would like to know what that length
of time is prior to putting the fuel in storage. To predict the
storage stability, therefore, we must simulate the storage and
measure the quantities of insolubles formed. To accelerate
the process, the test must be performed at an elevated temperature. The question is how high above ambient to conduct
the test so as to accelerate the reactions and still keep the results representative of storage at ambient temperature. The
Arrhenius [36] equation described in Fig. 9 can be used to estimate the reaction rates for fuels stored at ambient to
slightly above ambient temperatures. Under this relationship, the reaction rate is accelerated approximately 1.7-3
times for every 10C rise in temperature. The problem is that,
as the temperature rises, reactions that would not normeJly
occur during ambient storage (or would occur with very low
probability) now begin to occur. The high-temperature reactions result in other types of compounds, which can skew the
128
MANUAL
k = Ae'^''
or
HANDBOOK
k=A,J^
where:
Ea = activation energy
R = gas constant
T = absolute temperature
A = frequency factor (collision frequency)
Taking the natural logarithm of both sides and rearranging gives:
lnfe=(-Ea/RXl/T) + lnA
Therefore, a plot of In A: versus 1/T gives a straight line whose slope is
equal to -Ea/R and whose intercept is In A
FIG. 9Arrhenius equation.
results of the aging test. Two early studies [37,38] demonstrated the correlation between storage at 43C and ambient
storage. They determined that 13 weeks at 43C is equivalent
to one year at ambient. Over the years, this relationship has
been redefined as 1 week at 43 C is equal to 1 month at ambient. These studies also established storage at 43C as the
standard accelerated storage test, against which all other accelerated storage stability tests are compared. This test works
so well because the test temperature is such a small increase
over ambient that the relative importance of the various reactions that create insolubles are not appreciably changed.
This makes the 43C storage test an ideal research tool for
studying storage stability of diesel fuels.
Ironically, that which makes the 43 C test such a useful research tool also makes it useless for quality assurance and
quzility control applications because of the long test times.
For this reason, m u c h effort has been expended over the past
25-30 years to develop a rapid test for fuel storage stability.
In this context, rapid is generally defined as test times of 16
hours or less. Very little success came of these efforts, with
one exception. The U.S. Navy developed a test method that
was eventucdly standardized as ASTM D 5304 \39'\. The applicability of the test method was demonstrated in a project
conducted during 1992-1993 [40].
Flash Point
Flash point is specified in D 975 primEuily for safety during
transport, storage, and handling. A low flash point fuel can be
a fire hazard, subject to flashing, with possible continued ignition and explosion. Low flash point can also indicate contamination with low-flash fuels such as gasoline. The flash
point of a fuel has no significant relation to the performance
of the fuel in the engine. Auto-ignition temperature is not influenced by variations in flash point.
There are five ASTM test m e t h o d s for measuring flash
point of diesel fuels:
ASTM D 56, Standard Test Method for Flash Point by Tag
Closed TesterThe specimen is placed in the cup of the
tester and, with the lid closed, heated at a slow constant
rate. An ignition source is directed into the cup at regular
interveJs. The flash point is taken as the lowest temperature at which application of the ignition source causes the
vapor above the specimen to ignite.
ASTM D 93, Standard Test Methods for Flash Point by Pensky-Martens Closed Cup Tester^A brass test cup of specified dimensions, filled to the inside msirk with test specimen and fitted with a cover of specified dimensions, is
heated and the specimen stirred at specified rates by either of two defined procedures (A or B). An ignition
source is directed into the test cup at regular intervals
with simultaneous interruption of the stirring until a flash
is detected.
ASrM D 3828, Standard Test Methods for Flash Point by
Small Scale Closed Tester Method AFlash/No Flash Test
A specimen of a sample is introduced by a syringe into the
cup of the selected apparatus that is set and maintained at
the specified temperature. After a specific time a test flame
is applied and an observation made as to whether or not a
flash occurred.
Method BFinite (or Actual) Flash Point^A specimen of a
sample is introduced into the cup of the selected apparatus
that is maintained at the expected flash point. After a specified time a test flame is applied and the observation made
whether or not a flash occurred. The specimen is removed
from the cup, the cup cleaned, and the cup temperature adjusted 5C (9F) lower or higher depending on whether or
not a flash occurred previously. A fresh specimen is introduced and tested. This procedure is repeated until the flash
point is established within 5C (9F). The procedure is then
repeated at 1C (2F) intervals until the flash point is determined to the nearest 1C (2F). If improved accuracy is
desired the procedure is repeated at 0.5C (1F) intervals
until the flash point is determined to the nearest 0.5C
(1F).
ASTM D 6450, Standard Test Method for Flash Point by Continuously Closed Cup (CCCFP) TesterThe lid of the test
chamber is regulated to a temperature at least 18C below
the expected flash point. A 1 mL test specimen of a sample
is introduced into the sample cup, ensuring that both specimen and cup are at a temperature at least 18C below the
expected flash point, cooling if necessary. The cup is then
raised and pressed onto the lid of specified dimensions to
form the continuously closed but unsealed test chamber
with an overall volume of 4.0 0.2 mL. After closing the
test chamber, the temperatures of the test specimen and
the regulated lid are edlowed to equilibrate to within 1C.
Then the lid is heated at a prescribed, constant rate. For the
flash tests, an arc of defined energy is discharged inside the
test chamber at regular intervals. After each ignition, 1.5
0.5 m L of air is introduced into the test chamber to provide
the necessary oxygen for the next flash test. The pressure
inside the continuously closed but unsealed test chamber
remains at ambient barometric pressure. The exceptions
are for the short time during the air introduction and at a
flash point. After each arc, the instantaneous pressure increase above the ambient barometric pressure inside the
test chamber is monitored. When the pressure increase exceeds a defined threshold, the temperature at that point is
recorded as the uncorrected flash point.
Each of these three test methods contains an introduction
that is similar to the following:
This flash point test method is a dynamic test method and
depends on definite rates of temperature increase to control
the precision of the test method. The rate of heating may
CHAPTER
not in all cases give the precision quoted in the test method
because of the low thermal conductivity of certain materials. To improve the prediction of flammability,
Test
Method D 3941, an equilibrium method was developed in
which the heating rate is slower. This allows the vapor
above the test specimen and the test specimen to be at
about the same temperature.
ASTM D 3941, Standard Test Method for Flash Point by the
Equilibrium Method with a Closed-Cup
ApparatusThis
method covers the determination of the flash point of hquids in which the specimen a n d the air/vapor mixture
above it are approximately in temperature equilibrium.
The test method is limited to a temperature range from
32-230F(0-110C).
Method D 3941 should b e used to measure Eind describe the
properties of material, products, or assemblies in response to
heat and flame u n d e r controlled laboratory conditions. It
should not be used to describe or appraise the fire hazard or
fire risk of materials, products or assemblies under actUcJ fire
conditions. However, results of this test may be used as elements of a fire risk assessment that takes into account all of
the factors that are pertinent to a n assessment of the fire hazard of a particular end use.
It is important to note that while D 3941 may be an acceptable alternative m e t h o d for some applications, the
method(s) listed in a given specification, such as D 975,
should not be replaced without prior knowledge and consent
of all interested parties. This is because the measured flash
point of a fuel is dependent not only on the composition of
the fuel but also on the apparatus used to make the measurement. ASTM Manual 9 describes many flash point test methods, both U.S. and international [41]. It also lists pertinent
specifications/standards worldwide.
Lubricity
Diesel fuel functions as a lubricant in certain items of fuel injection equipment such as rotary/distributor fuel p u m p s and
injectors. In limited cases, fuel with very specific properties
can have insufficient lubricating properties that can lead to a
reduction in the normal service life of fuel p u m p s or injectors. Two fuel chciracteristics that affect equipment wear are
low viscosity and lack of sufficient quantities of trace components, which have a n affinity for metal surfaces. If fuel viscosity meets the requirements of a particular engine, a fuel
film is maintained between the moving surfaces of the fuel
system components. This prevents excessive metal-to-metal
contact and avoids premature failure due to wear. Simileirly,
certain surface-active molecules in the fuel (such as acids and
heteroatomics) adhere to, or combine with, metallic surfaces
to produce a protective film that also can protect surfaces
against excessive wear. The concern about fuel lubricity is
limited to the use of fuels with viscosities lower than those
specified for a particulcir engine. Also of concern is the use of
fuels that have been processed in a manner that results in the
elimination of the trace levels of the surface-active species
that act as lubricating agents. Presently, the only fuels of the
latter type shown to have lubricity problems resulted from
sufficiently severe processing to reduce aromatics substantieJly below current levels. Research is in progress to identify
the chciracteristics of such fuels and where the use of a lu-
5: GAS TURBINE
FUELS
129
LOAD
. " ^ Q
P'O.
3 ^ ^ COtfTACT U>Ap
MEAW-OUTT
FNCUMATIC
PWTOM
S c h e m a t i c D i a g r a m of t h e Scuffing L o a d Ball-on-Cylinder
Lubricity Evaiuator (not including Instrumentation)
MANDREL ASSEMBLY
SCREWS W REQ'a
BUTTON HEAD
8-32
DRIVESHAFT ASSEMBLY
Fluid volume
50 1.0 mL
Fluid temperature
25 1C
Conditioned air^
50 1 % relative tiumidity at 25 1C
Fluid pretreatment: 0.50 U min air flowing through and 3.3 L/min air flowing
over the fluid for 15 min
Fluid test conditions: 3.8 L/min air flowing over the fluid
Cylinder rotational speed
525 1 rpm
Applied Load
Break-in period
500 g
Incremental-load test
500 to 5 000 g
Single-load test
user defined'
Test Duration
Break-in period
30 s
Wear tests
60s
*Fifty percent humidity should be achieved using equal volumes of dry and
saturated air. The SLBOCLE has a water column through which air passes and it
is assumed to be saturated when it exits this column.
"The applied load for the single test Is set at the pass/fail requirement for the fuel
being evaluated.
FIG. 1 0 T e s t e q u i p m e n t a n d t e s t c o n d i t i o n s f o r s c u f f i n g l o a d b a l l - o n cylinder lubricity e v a i u a t o r ( D 6 0 7 8 ) .
131
Test Plata
Loading
Aromatics
Relative humidity
Applied load
Test duration
Bath surface area
2 0.20 mL
1 0.02 mm
50 1 Hz
25 2C
or
60 2C
>30%
200 1 g
75 0.1 min
6 1 cm^
FIG. 11Test equipment and test conditions for high frequency reciprocating rig (D 6079).
Diesel fuel contains many types or classes of compounds including paraffins, naphthenes, olefins, and Eiromatics. Compounds that contain heteroatoms such as sulfur, nitrogen,
and oxygen are also present. Aromatics warrant discussion
because 1) they have an effect on the combustion quality of
the fuel, 2) typically, they are the only hydrocarbon type
listed in diesel fuel specifications (including D 975), and 3)
increased amounts of aromatics can have a negative impact
on vehicle emissions.
It is well known that an increase in the total aromatics content of a diesel fuel can (and usually does) have an adverse effect on the ignition quality, i.e., cetane number of the fuel.
Several methods are available for the measurement of aromatic content. They eire described below:
ASTM D1319, Standard Test Method for Hydrocarbon Types
in Liquid Petroleum Products by Fluorescent Indicator AdsorptionApproximately 0.75 mL of sample is introduced
into a special glass adsorption column packed with activated silica gel. A small layer of the silica gel contains a
mixture of fluorescent dyes. When the entire sample has
been adsorbed on the gel, alcohol is added to desorb the
sample down the column. The hydrocarbons are separated
in accordance with their adsorption affinities into aromatics, olefins, and saturates. The fluorescent dyes are also
separated selectively, with the hydrocarbon types, and
make the boundaries of the aromatic, olefin, and saturate
zones visible under ultraviolet light. The volume percentage of each hydrocarbon type is calculated from the length
of each zone in the column.
This test method was originally developed for the analysis
of gasoline (spark ignition engine fuel). It is for determining
hydrocarbon types over the concentration ranges from 5-99
volume % aromatics, 0.3-55 volume % olefins, and 1-95 volume % saturates in petroleum fractions that distill below
315C. The test method may apply to concentrations outside
these ranges, but the precision has not been determined.
Samples containing dark-colored components that interfere
in reading the chromatographic bands cannot be analyzed.
D 1319 was applied to and specified for diesel fuel usually
because no other suitable method was available. As suitable
methods became standardized they grew in use but have not
replaced D 1319 in D 975. This is because the requirement for
aromaticity currently included in D 975 comes from the requirement in 40 CFR Fart 80. Since federal law requires D
1319, it is the method listed in D 975. Method D 5186, described below, is more appropriate for diesel fuel and is often
used in place of D 1319. However, in case of dispute, D 1319,
by virtue of it's status as the legislated method, is considered
the referee method.
ASTM D 5186, Standard Test Method for Determination of
Aromatic Content and Polynuclear Aromatic Content of
Diesel Fuels and Aviation Turbine Fuels by Supercritical
Fluid ChromatographyA small aliquot of the fuel sample
is injected onto a packed silica adsorption column and
132
MANUAL
HANDBOOK
+s)] + 9.420s
where:
Q
d
X
y
5
Density,
g/cm^
Regular gasoline
Premium gasoline
Jet fuel
Diesel fuel
0.735
0.755
0.795
0.850
Net Heat of
Combustion,
Btu/lb
18
18
18
18
630
440
420
330
Net Heat of
Combustion,
Btu/gal
114
116
122
130
200
200
200
000
- (x+y
where:
Qp = net heat of combustion at constant pressure,
MJ/kg,
d = density at 15C, kg/m^,
X = mass fraction of water,
y = mass fraction of ash, and
s = mass fraction of sulfur.
This test method is useful for estimating, using a minimum
n u m b e r of tests, the heat of combustion of burner and diesel
fuels for which it is not usually critical to obtain very precise
heat determinations. This test method is purely empirical. It
is applicable only to liquid hydrocarbon fuels derived by normal refining processes from conventional crude oil. This test
method is valid for those fuels in the density range from 750
to 1000 kg/m^ and those that do not contain an unusually
high aromatic content. High aromatic content fuels will not
normally meet fuel specification criteria for this method.
This test method is not applicable to pure hydrocarbons. It is
not intended as a substitute for experimental measurements
of heat of combustion.
According to the m e t h o d the estimation of the heat of
combustion of a hydrocarbon fuel from its density, sulfur,
water, and ash content is justifiable only when the fuel belongs to well-defined classes for which a relationship between these quantities have been derived from accurate experimental measurements on representative samples of these
classes. Even in these classes, the possibility that the estimate
may be in error by large amounts for individual fuels should
be recognized. This test method has been tested for a limited
number of fuels from oil sand bitumen and shale oil origin
and has been found to be valid. The classes of fuels used to
establish the correlation presented in this test method are
represented by the following specifications:
1. D 396 Fuel Oils Grades 1, 2, 4 (light), 4, 5 (hght), 5 (heavy),
and 6
2. D 975 Diesel Grades 1-D, 2-D, and 4-D
3. D 1655 Aviation Turbine Jet A, Jet A-1, and Jet B
4. D 2880 Gas Turbine Grades 0-GT, 1-GT, 2-GT, 3-GT and 4GT
5. D 3699 Kerosine Grades 1-K and 2-K
ASTM D 4809, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method)This test method covers the determination of the heat of combustion of hydroccirbon fuels. It was
HANDBOOK
Total Sulfur
The test methods for measuring total sulfur in diesel fuel, as
prescribed in D 975 are:
ASTM D 2622, Standard Test Method for Sulfur in Petroleum
Products by Wavelength Dispersive X-ray Fluorescence SpectrometryD 2622 is prescribed for the measurement of total sulfur in Grades Low Sulfur No. 1-D and No. 2-D. This
test method covers the determination of total sulfur in liquid petroleum products and in solid petroleum products
that can be liquefied with moderate heating or dissolved in
a suitable organic solvent. The applicable concentration
range will vary to some extent with the instrumentation
used and the nature of the sample. Optimum conditions
will allow the direct determination of sulfur in essentially
paraffinic samples at concentrations exceeding 0.0010
mass%.
ASTM D 129, Standard Test Method for Sulfur in Petroleum
Products (General Bomb Method)The sample is oxidized
by combustion in a bomb containing oxygen under pressure. The sulfur, as sulfate in the bomb washings, is determined gravimetrically as barium sulfate.
D 129 is the prescribed method for the determination of total sulfur in Grades No. 1-D, No. 2-D, and No. 4-D. This test
Carbon Residue
Ash
136
MANUAL
HANDBOOK
100
80
60
40
30
20
i
s
s
t
CJ
Q_
i.r
^^.
*^
4
3
2
is
^5
li *o
eo
Q=
1.0
0.8
0.6
0.4
0.3
^
S
0.2
0.02 0.03
0.06
0.10
0.08
0.06
0.04
0.03
0.02
0.01
0.01
0.10
3 4
6 8 10
20
30 40 60 80 100
CHAPTER
pipeline following a shipnient of dyed fuel. In the cases
where the contaminated fuel has been aviation fuel, the result is usually the requirement to dispose of the contaminated fuel since most jet engines are not certified to operate on fuel with red dye.
Under the EPA regulations, kerosine used for home heating and other off-road applications must contain the red
dye. Since this fuel is not tcixed, the IRS does not require
the presence of the dye. Unfortunately, the evidence regarding the possible health effects of using red-dyed fuel in
un-vented kerosine heaters is minimal. Therefore, m a n y
users of these heaters are reluctcuit to use red-dyed kerosine. However, if the user wants un-dyed kerosine, they
must pay the tax so that it will not have to be dyed u n d e r
the IRS regulations. Understandably, m a n y kerosine
heater users are upset about having to pay the tcix. The laws
do allow a refund of the tax, however, and many users (and
in some cases, suppliers) are taking the necessary steps to
reclaim those monies. There is also work underway to develop information on the potential health effects of burning the dyed fuel in un-vented heaters. Users are encouraged to check with their fuel suppliers for additional
information.
Seal swell and elastomer compatibility problems brought
about by the reductions in ciromatic content in low sulfur
fuels. This is discussed in the section on aromatics.
It should be noted that the reductions in allowable sulfur
have also had some positive effects. Aside from the obvious
improvements in engine emissions, the hydrotreating required to remove the sulfur often means that the fuel has
significantly better stability characteristics (through the removal of precursors). The concomitant removal of aromatics can also bring some improvement to the ignition quality of the fuel.
The requirement to reduce sulfur levels in diesel fuel is now
a "fact-of-life" throughout the world. At the time of this writing, the EPA is proposing legislation to reduce the maximum
allowable sulfur level to I S p p m b y J u n e 1, 2006 [47]. The primary impetus for this continued reduction in sulfur is the
need to protect exhaust-treatment devices installed on diesel
engines, many of which are poisoned by sulfur.
World Wide Fuel Charter
The World-Wide Fuel Charter was jointly developed by the
E u r o p e a n Automobile Manufacturers Association (ACEA),
the Allieuice of Automobile Manufacturers, the Engine Mcinufacturers Association (EMA), the Japan Automobile Manufacturers Association (JAMA), and numerous associate mem-
5: GAS TURBINE
FUELS
137
Category 1
Category 2
Category 3
Category 4
48
45
0.50
400
No Requirement
No Requirement
53
50
0.030
400
24
25
55
52
0.003
400
24
15
55
52
Sulfur-free
400
24
15
HANDBOOK
D240
D613
D 2500 or
D4539
D6468
138 700
47.0
2C maximum
above the D 975
tenth percentile
minimum
ambient air
temperature
80%
L-10 Injector
6.0
10.0
definition of premium diesel. An NCWM task force composed of representatives from the oil industry, additive manufacturers, independent labs, and government agencies, with
the assistance of ASTM, prepared a set of requirements to define premium diesel. In late 1997, the NCWM task force recommended that a fuel must meet any two of the five criteria
listed in Table 8 before it can be labeled "premium diesel."
The NCWM adopted the plan at its 84th conference in 1999
[49]. The definition became a model law and was automatically adopted by some states; elsewhere, it will only become
effective if a state specifically adopts it.
The EMA issued a Recommended Guideline (FQP-IA) for
a premium diesel fuel. The proposed values are listed in
Table 9. From the EMA consensus position:
This diesel fuel is considered to be "premium" insofar as it
may assist in improving the performance and durability of
engines currently in use and those to be produced prior to
2004. It is not intended to enable diesel engines to meet any
emissions standard or, in general, to improve engine exhaust emissions... It is intended as a "living document" in
that, as other needs or test procedures are identified, the
recommendation will be upgraded [50].
The most significant aspects of this Consensus Position are
its requirements for a minimum fuel lubricity, increased
cetane number, improved cold weather performance, detergency, thermal stability, minimum energy content, and specifications regarding overall fuel "cleanliness."
Alternative Fuels
As in the early 1980s, research with alternative fuels is again
on the increase. Whereas the earlier work centered on the
suitability of alternative fuels to power diesel engines; most
of the current work is evaluating the potential these fuels offer to reduce engine emissions [51]. Fischer-Tropsch Liquids
and Biodiesel are the fuels that seem to show up the most in
the current literature and reports.
Fischer-Tropsch Synthesis is the process whereby natural
gas or coal is converted into hydrocarbons. The product hydrocarbons are usually upgraded to middle distillate products such as kerosine and diesel fuel. Typically Fischer-Tropsch diesel fuels have high cetane numbers, often greater than
70 cetane, no aromatic compounds, no sulfur, and a density
of around 0.78 kg/L [52]. The Fischer-Tropsch liquids have
Test Method
D93
D2709
D 1744
D 2276 or
D5452
D86
D445
D482
D2622
D 130
D613
D4737
D524
D287
D 6078(1)
D2274
L-10 Injector
D 2500 or
D4539
Requirements
52
0.05
200
10
332
355
1.9^.1
0.01
0.05
3b
50
45
0.15
39
3100
15
slO.O
s6.0
(2)
OH
O
JL
\ ^ ^
J.
+
"^^lalyst
HO
3(GH30H)
3(RCOOCH3) +
OH
O.^ ^ O
Triglyceride
3 iVIetlianol
"^^*^'^'
3 methyi-estiiers +
Glycerol
Flash point
(closed cup)
Water and
sediment
Kinematic
viscosity, 40C
Sulfated ash
Sulfur^
Copper strip
corrosion
Cetane number
Cloud point
Carbon residue"
Acid number
Free glycerin'^
Total glycerin^
Test
Method''
Limits
Units
D93
100.0
minC
D2709
0.050
max % volume
D445
1.9-6.0"
mm 2/s
D874
D2622
D 130
0.020
0.05
No. 3
max % mass
max % mass
max
D613
D2500
40
Report to
customer
0.050
0.80
0.020
0.240
min
C
D4530
D664
max % mass
max mg KOH/g
% mass
%mass
HANDBOOK
TABLE 11Detailed requirements for gas turbine fuel oils at time and place of custody transfer to user.'
ASTM
Test Method"
Property
Graded''
No. 0-GT
f
0.05
No. l-GT'^
No. 2-Gr
No. 3-GT
No. 4-GT
38 (100)
38 (100)
55(130)
Flash point C (F) min
D93
66 (150)
0.05
0.05
Water and sediment
D2709
1.0
% vol max
D1796
1.0
Distillation Temperature C (F)
D86
90 % volume recovered
282
min
max
288
338
Kinematic viscosity 2 mm/s^
D445
At40C(104F)
f
1.3
1.9
5.5
min
5.5
max
2.4
4.1
50.0
At 100C (212F) max
50.0
Ramsbottom
0.15
0.35
Carbon residue on 10% distillation
D524
0.15
Residue % mass, max
0.01
0.01
D482
0.01
0.03
Ash % mass, max
Density at 15C k g W
D 1298
max
850
876
-18
D97
-6
Pour pointC (F) max
"To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer.
''Gas turbines with waste heat recovery equipment may require fuel sulfur limits to prevent cold end corrosion. Environmental limits may also apply to fuel sulfur in selected areas in the United States and in other countries.
"The test methods indicated are the approved referee methods. Other acceptable methods are indicated in 6.1.
''No. 0-GT includes naphtha, Jet B fuel and other volatile hydrocarbon liquids. No. 1-GT corresponds in general to specification D 396 Grade No. 1 fuel and D
975 Grade 1-D diesel fuel in physical properties. No. 2-GT corresponds in general to Specification D 396 No. 2 fuel and D 975 Grade 2-D diesel fuel in physical
properties. No. 3-GT and No. 4-GT viscosity range brackets specification D 396 Grades No. 4, No. 5 (light). No. 5 (heavy), and No. 6, and D 975 Grade No. 4-D diesel
fuel in physical properties.
"Under United States regulations. Grades No. 1-GT and No. 2-GT are required by 40 CFR Part 80 to contain a sufficient amount of dye Solvent Red 164 so its
presence is visually apparent. At or beyond terminal storage taniks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid dye standard Solvent Red 26.
'when the flash point is below 38C (100F) or when kinematic viscosity is below 1.3 mm^/s at 40''C (104F) or when both conditions exist, the turbine manufacturer should be consulted with respect to safe handling and fuel system design.
*For cold weather operation, the pour point should be specified 6C below the ambient temperature at which the turbine is to be operated except where fuel
heating facilities are provided. When a pour point less than 18C is specified for Grade No. 2-GT, the minimum viscosity shall be 1.7 mm^/s and the minimum
90% recovered temperature shall be waived.
D396
D975
D 2069
D 2880
D 3699
Flash point
Water & sediment
Distillation
Viscosity
Carbon residue
Ash
Copper strip corrosion
Density
Pour point
Sulfur
Cetane #
Cloud pt.
Freezing point
Burning quality
Saybolt color
NOTE: An asterisk indicates the property is included in the specification.
components: compressor, combustor, and turbine. The purpose of the compressor is to raise the pressure of the operating fluid usually a ratio of 10 to 20 to 1. It is desirable to accomplish this pressure increase as efficiently as possible to
maximize the available thrust or horsepower, because the efficiency determines how much horsepower is required for
the compression. The purpose of the combustor is to raise the
temperature of the operating fluid. The combustor inlet temperature depends on the pressure ratio and efficiency of the
compressor. In more complicated cycles some of the heat in
the exhaust is recovered and used to increase the combustor
inlet temperature, which reduces the required temperature
rise across the combustor and thus the amount of fuel required. Current combustor outlet temperatures are in the
1093-1482C (2000-2700F) ranges. The combustor must accomplish this temperature rise efficiently. Current combustion efficiencies are in the 99%-f range at most operating
conditions. Additionally the outlet temperature profiles have
specific requirements.
A gas turbine combustor operates at fuel-air ratios less
than stoichiometric and below the lower flammability level.
Figure 14 is a simplified diagram of how the air is introduced
in a conventional combustor i.e., not a low emission combustor. The figure shows the distribution of air for a combustor with an overall air to fuel ratio of 70 to 1. About four
parts of air per part of fuel are introduced in the swirler to
help stabilize the flame zone. Then, in the primary zone, 12
parts of air per part of fuel are introduced to provide enough
141
46
Parts
Air
OVERALL
AIR-FUEL
RATIO = 70
P = PRIMARY
S = SECONDARY
D = DILUTION OR TERTIARY
SW = SWIRLER
F = FUEL
142
MANUAL
HANDBOOK
Vanadium
0.5
0.5
0.5
0.5
Sodium plus
Potassium
Calcium
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
(Consult turbine manufacturers)
Lead
0.5
0.5
0.5
0.5
and can combine with sulfur in the fuel to yield sulfates with
melting points in the operating range of the gas turbine.
These compounds produce severe corrosion, and for turbines
operating at gas inlet temperatures above 650C, additives
that control such corrosion are not yet in general use. Accordingly, the sodium-plus-potassium level must be limited,
but each element is measured separately. Some gas turbine
installations incorporate systems for washing oil with water
to reduce the sodium-plus-potassium level. In installations
where the fuel is moved by sea transport, the sodium-pluspotassium level should be checked prior to use to ensure that
the oil has not become contaminated with sea salt. For gas
turbines operating at turbine inlet gas temperatures below
650C (1200F), the corrosion due to sodium compounds is
of minor importance and can be further reduced by siliconbase additives. A high sodium content is even beneficial in
these turbines because it increases the water-solubility of the
deposits and thereby increases the ease with which gas turbines can be water-washed to obtain recovery of the operating performance.
Calcium is not harmful from a corrosion standpoint; in
fact, it serves to inhibit the corrosive action of vanadium.
However, calcium can lead to hard-bonded deposits that are
not self-spalling when the gas turbine is shut down, and that
are not readily removed by water washing of the turbine. The
fuel washing systems used at some gas turbine installations
to reduce the sodium and potassium level will also significantly lower the calcium content of fuel oil.
Vanadium can form low melting compounds such as veinadium pentoxide that melts at 691C, and causes severe corrosive attack on all of the high temperature alloys used for gas
turbine blades. If there is sufficient magnesium in the fuel, it
will combine with the vanadium to form compounds with
higher melting points and thus reduce the corrosion rate to
an acceptable level. The resulting ash will form deposits in
the turbine and will require appropriate cleaning procedures.
When vanadium is present in more than trace amounts either
in excess of 0.5 mg/kg or a level recommended by the turbine
manufacturer, it is necessary to maintain a weight ratio of
magnesium to vanadium in the fuel of not less than 3.0 in order to control corrosion. An upper limit of 3.5 is suggested
since larger ratios will lead to unnecessarily high rates of ash
deposition. In most cases, the required magnesium-to-vanadium ratio will be obtained by additions of magnesium-containing compounds to the fuel oil. The special requirements
covering the addition of and type of magnesium-containing
additive, or equivalent, shall be specified by mutual agreement between the various interested parties. The additive will
ASTM STANDARDS
No.
D 56
D 86
D 93
D 97
D 129
D 189
D 240
D 445
D 482
D 524
D 613
D 976
D 1266
D 1298
D 1319
D 1552
D 2068
D 2274
D 2425
D 2500
D 2622
D 2709
Title
Test Method for Flash Point by Tag Closed Tester
Test Method for Distillation of Petroleum Products
Test Methods for Flash Point by Pensky-Martens
Closed Cup Tester
Test Method for Pour Point of Petroleum Products
Test Method for Sulfur in Petroleum Products
(General Bomb Method)
Test Method for Conradson Carbon Residue of
Petroleum Products
Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by B o m b Calorimeter
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Test Method for Ash from Petroleum Products
Test Method for Ramsbottom Ceirbon Residue of
Petroleum Products
Test Method for Ignition Quality of Diesel Fuels by
the Cetane Method
Test Method for Calculated Cetane Index of Distillate Fuels
Test Method for Sulfur in Petroleum Products
(Lamp Method)
Test Method for Density, Relative Density (Specific
Gravity), or API Gravity of Crude Petroleum and
Liquid Petroleum Products by Hydrometer Method
Test Method for H y d r o c a r b o n Tjrpes in Liquid
Petroleum Products by Fluorescent Indicator Adsorption
Test Method for Sulfur in Petroleum Products
(High-Temperature Method)
Test Method for Filter Plugging Tendency of Distillate Fuel Oils
Test Method for Oxidation Stability of Distillate
Fuel Oil (Accelerated Method)
Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry
Test Method for Cloud Point of Petroleum Products
Test Method for Sulfur in Petroleum Products by
Wavelength Dispersive X-ray Fluorescence Spectrometry
Test Method for Water and Sediment in Middle Distillate Fuels by Centrifuge
CHAPTER
D2887
D 6426
D 6450
D 6591
5: GAS TURBINE
FUELS
143
REFERENCES
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[9] "Diesel Fuels: Performance and Characteristics," SAE SP-675,
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[14] Westbrook, S. R., et. al., "Fuel System Design Considerations for
Diesel and Gas Turbine Engine Powered Military Vehicles," Proceedings of the Second International Conference on Long-Term
Storage Stabilities of Liquid Fuels, Southwest Research Institute,
San Antonio, TX, 1986, pp. 416-425.
[15] "Diesel Fuel Low-Temperature Operability Field Test," Coordinating Research Council Report No. 528, Coordinating Research Council, Inc., Atlanta, GA.
[16] Chandler, J. E., "Comparison of All-Weather Chassis Dynamometer Low-Temperature Operability Limits for Heavyand Light-Duty Trucks with Standard Laboratory Methods,"
SAE Report No. 962197, Society of Automotive Engineers, Warrendale, PA, 1999.
[17] Chandler, J. E., "Evaluation of Faster LTFT and SFPP for Protection of Low Temperature Operability in North American
Heavy Duty Diesel Trucks," SAE Report No.932769, Society of
Automotive Engineers, Warrendale, PA, 1993.
[18] Chandler, J. E. and Zechman, I. A., "Low-Temperature Operability Limits of Late Model Heavy-Duty Diesel Trucks and the
Effect Operability Additives and Changes to the Fuels Delivery
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
MNL37-EB/Jun. 2003
Introduction to Marine
Petroieum Fuels
Matthew F. Winkler^
century, although small quantities of petroleum were obtained as early as the 14th century. In Pennsylvania, Edwin
Drzike drilled the first oil well in 1859, striking oil at a depth
of 21 m. Drake's oil well was generally accepted as the start of
the petroleum industry. Kerosine or lamp oil was the object
of the early refining industry. The simple distillation process
was conducted to obtain as m u c h lamp oil as possible from
the Pennsylvania crude oil.
In 1870, the S.S. Constantine was the first of many sea vessels converted from coal to fuel oil. While trading in t h e
Caspian Sea, the vessel burned the residue from refined Russian crude oil. Early oil burners were primitive a n d ineiBcient, b u t the crude oil was plentiful a n d n o attempt was
m a d e to b u m the fuel oil economiccJly.
In the early years of oil firing, t h e marine industry a n d
Lloyd's Register considered oil-fired instcJlations as experimental, with the vast majority of vessels still powered by coal
at t h e end of the 19th century.
Early 20th century fuel oils were used to a greater extent
in steam boilers and the marine industry experimented with
oil-fired diesel engines in the M/T Vulcanus in 1910 and the
MA'^ Seletndia in 1911. Then, during the period u p to the
outbreak of the first World War, fuel oil was used increasingly in Marine Merchant vessels, predominantly in steam
boilers.
In the early 1920s, zJmost all motor ships r a n on a distillate
fuel CcJled "diesel oil" while the oil-fired steam ships burned
a residual fuel called "boiler fuel." The quality difference between the diesel oil and the boiler fuel was considerable.
In t h e mid-1920s, some m o t o r ships h a d experimented
with burning boiler fuel in the m a i n a n d auxiliary engines.
However, there was no commercial benefit in burning boiler
fuel, since the smedl price differential between diesel fuel cind
boiler fuel was offset by the increased mainteneince costs (resulting from burning boiler fuel).
By the beginning of World W a r II, about half of the world
marine fleet was oil fired. Of those ships, half were steam a n d
half were diesel powered.
As society increased the usage of distillate fuels for automotive, truck, railroad, and aircrzift, the increasing demand
for distillate fuels increased the cost differential between distillate fuels and residuals. This economic incentive prompted
the Mcirine Industry to improve t h e technical feasibility of
burning residual fuels (boiler fuels) in marine diesel engines.
' Vice President, Seaworthy Systems, Inc., P.O. Box 965, Essex, CT
06426.
In the late 1940s and throughout the 1950s, motor ship fuel
systems a n d marine diesel engines struggled to operate on
residual fuels a n d to control reliability a n d m a i n t e n a n c e
costs. The successful combination of modified diesel engines,
improved fuel handling, a n d purification systems, together
with, new, reformulated cylinder lube oils led to the economic use of residual fuels in motor ships.
By the mid-1960s, about half of the world merchant fleet
tonnage was powered by diesel engines. Then, the distillate
and residual fuel costs were jolted sharply upward in 1973
and again in 1979 by t h e Middle Eastern oil suppliers restricting oil supplies and raising crude oil prices. This caused
the metrine fuel expenditure to become a significemt factor in
the ship owner's operating costs, and caused overeJl propulsive efficiency to take on renewed significance. The result
was the rapidly declining popularity of steam-powered vessels. The m u c h m o r e thermally efficient a n d economical
diesel engine led to the dominant position in merchant vessels that it still enjoys today.
The goal of m o d e m m a r i n e diesel engines is to operate
with fuel efficiency a n d reability on cracked a n d heavier
residual fuels. Marine residual fuels provide the main source
of energy that is used to transport the world's sea trade. More
ton-miles are moved by ship than by all other transportation
means combined. Therefore, marine fuels have become even
more importcint today to world trade.
145
Copyright'
2003 by A S I M International
www.astm.org
HANDBOOK
Distillation
Fractional or atmospheric distillation is the oldest and most
basic refining process. The heated crude is charged to the
tower under pressure and a portion flashes to vapor while the
rest stays in the tower as a liquid residue. It consists of boiling
the crude oil in a pipe-still at atmospheric pressure up to
371F. Then the hydrocarbon vapors are directed to a fractionating tower, as shown in Fig. 1. As the various lighter hydrocarbons of the crude oil vaporize at different rates, the
lighter, more volatile vapors rise high in the tower before condensing and being drawn off. The heavier, less volatile vapors
condense and are collected lower in the tower. The residual
fraction is drawn off at the bottom. The fractions drawn from
the tower are called straight-run or virgin products.
In the 1950s, '60s, and early '70s, straight-run fuels produced from atmospheric distillation were the main residual
fuels used in marine diesel engines. Straight-run fuels provided good ignition quality, clean combustion, ease of fuel
handling, ease of water separation, storage stability, and
solid compatibility. Since the density was usually below 985
Kg/m^, the shipboard settling tanks and old style centrifugal
purifiers provided adequate treatment to remove water and
sediment from the fuel.
At complex refineries, the next refining process is vacuum
distillation of the heavy bottoms from the atmospheric distillation unit. This process is a modified atmospheric process
where the pressure in the fractionating tower is reduced below atmospheric to a partial vacuum, as in Fig. 2. The atmospheric tower residual is the feed stock for the vacuum distillation process to yield additional heavy distillates, and will
further concentrate the metals and carbon content into the
vacuum bottoms. The vacuum bottom residuals are generally
used as feed stocks for other refinery processes. They are generally not available as marine fuels due to the very high viscosity. The vacuum bottoms can be further refined by using
GASEOUS
FRACTIONING
TOWER
GASOLINE
NAPHTHA
KEROSENE
CRUDE
HEATER
NO. 2
DISTILLATE
REDUCED CRUDE
NO. 5 - 6 RESIDUE
_.CRUDE
OIL
CHAPTER 6: INTRODUCTION
147
VACUUM
DISTILLATION
CHARGE
HEATER
HEAVY
^
DISTILLATE
REDUCED
- CRUDE
OIL
VACUUM BOTTOMS
GASOLINE
"A,^
VISBREAKER
BLENDED WITH
CUTTING STOCKSNO. 6 EUEL OIL
DISTILLATE-
"^y"
RESIDUUM
FIG. 2Vacuum distillation.
coated and fall to the bottom of the reactor. The carbon coating is removed in the regenerator, since the catalyst is expensive. Once cleaned, the regenerated catalyst returns to the incoming hydrocarbon feed stock to start the cycle over.
During the FCC process, a small amount of slurry oil is produced that contains small particles of catalyst known as cat
fines. The slurry oil is normally decanted to reduce the concentration of "cat fines" and then the slurry oil is blended into
the residual fuel stream. A number of cases have been documented where catalyst fines have been delivered to ship owners in large quantities. These catalyst particles Eire very heird
and abrasive and have caused rapid and severe wear to fuel
injection pumps, fuel injectors, cylinder liners, piston rings,
piston grooves, and stuffing box seals. This is most evident
where conventional centrifugation and filtration have been
ineffective. Effective five to seven micron filtration of the
residual fuels has proven to control damages from cat fines.
Hydrocracking is a process that uses high pressures and
the addition of hydrogen to crack refinery residues and to upgrade the resulting products through the addition of hydrogen. Lighter hydrocarbon products exhibit lower viscosities
and lower sulfur levels because of hydrocracking. Since hydrogen is added during the process, this process is more expensive than thermal or catalytic cracking.
Refinery Blending and Storage
Marine fuel oils are blends of products from several different
processes. Combustion characteristics, handling properties,
stability characteristics, and storage stability are all affected
FRACTIONING
TOWER
GASOLINE
REACTOR
NO 2
DISTILLATE
- -e-ATALYST-
HEAVY
GAS OIL
by the composition of the blend. The blending processes begin at the refinery. Heavy products produced at the refinery
cire expected to be in the residual fuel blend to varying degrees. The blending process allows lower quality residuEils to
be converted into more suitable fuel oils by the addition of
small qucintities of lighter cutter stock, such as light or heavy
distillates, or by adding cycle oils. When distillate/residual
blends eire made, the solubility of the different components in
each other is important. When components Eire completely
soluble, the blend is considered compatible. Whenever a
blend is contemplated, the compatibility of the resulting
blend must be eveduated beforehand to prevent incompatibility problems that can cause excessive sludge accumulation
in storage, centrifugation, and filtration, and stratification in
the storage tanks.
As the refinery processes improve, and as crude oil distillate yields improve, a continuing decrease in the overall quality of cracked residuals used to produce blends for marine fuels can be expected.
In many refineries in the United States, all residual products are directed to the petroleum cokers, which convert the
residual products into light distillates and solid hydrocarbon
coke. At these refineries, n o residual fuels are sold or made
for the marine fuel industry. In the future, marine fuels could
compete with "cokers" for their feed stock requirements. Ano t h e r use for residual fuel for U.S. a n d E u r o p e a n power
plants is decreasing due to environmental restrictions,
thereby decreasing overall availability of residual fuel.
A large percentage of fuel contamination can be traced to
the hydrocarbon storage and transportation process. Water
and debris (solids and fibers) are frequently introduced into
the marine fuel originating from barge and tanker transport,
pipe line transport, and shore side tank storage. A more de-
(D-445)
CHAPTER
6: INTRODUCTION
(D
1298)
The density of a fuel is the mass-per-unit volume and is expressed as grams-per-milliliter (g/mL) for liquid fuels. In reality, density and specific gravity have very similar values
and, for approximate purposes, could be considered the
same. Originally, specific gravity at 60F was predominantly
used but, currently, meuine fuels will specify density at 15C
superceding specific gravity as the common usage. In 1977,
the Worldwide Marine Industry officially adopted SI units,
although it has tciken many years for the Marine Bunker Industry to adjust to the SI units.
Since all liquid hydrocarbon fuels expand their volume
when heated, their weight-per-unit volume decreases. Therefore, the density (and specific gravity) must be reported at a
standard temperature even though another temperature may
have been used in the test method. ASTM D 1550 contains
volume correction tables for reference.
The significance of fuel density revolves around the waterfuel separating technology, such as centrifugal separators or
settling tanks that operate on the difference of the densities
between the water and the fuel. Older centrifugal sepeirators
(purifiers) were limited to fuels at or below 991 density at
50C to control water removal efficiencies. The removal of
free water and salt water are important to control damage,
corrosion, and deposits in fuel injection systems; turbo
chargers and boilers in diesel; and gas turbine engines. The
more m o d e m centrifugal separators can efficiently remove
water u p to a fluid density of 1.012 at 50C.
TO MARINE
PETROLEUM
FUELS
149
Value (D
4868)
Heating value is the quantity of heat produced by the combustion of a unit of marine fuel under specified conditions.
The gross heating value is the sum of the heat produced by
the total combustion of the fuel and the heat released by the
condensation of the water and SOx gases formed during combustion. This is primjuily applicable to a steam boiler power
plant. The net heating value is the gross heating value minus
the heat released by the condensation of the water (vapor)
produced during combustion and the sulfur and metals con-
800
820
HANDBOOK
^800
810
840
-820
860
830
-3
880
-840
900
-850
920
940
860
960
870
980
880
1000
890
1020
-900
1040
910
-920
5000
930
20000
50000
-950
Ash (D 482)
Ash from the marine fuels includes the inorganic metallic
content, other non-combustibles, and miscellaneous contamination. Metallics can contain a mixture of aluminum, calcium, potassium, iron, vanadium, nickel, silicon, and
sodium. Ash deposits can cause localized overheating and
corrosion to the metal surfaces where they adhere, especially
to the exhaust valves. Excessive ash can cause abrasive wear
of the cylinder liners, piston rings, injection pumps, fuel
valves, and injection tips. Catalyst fines can result in just such
abrasive damage.
In marine fuels, some of the dispersed and insoluble metallic compounds can be removed onboard by settling, centrifugation, and filtration. However, fuel soluble metallics cannot
be reduced by shipboard fuel handling equipment [7-9].
Cat Fines (ISO 10478)
Catalyst (CAT) fines are small particles of aluminum silicate
used as a fluidic catalyst in the catalytic cracking units at
modem refineries. Cat fines can be carried over from the catalytic cracker and can be found in marine fuels. Cat fines are
very hard and abrasive and can cause excessive wear of engine components, particularly fuel pumps, cylinder liners,
piston rings, and piston ring grooves.
To prevent severe abrasive damage, cat fines must be limited by fuel specification restrictions or by shipboard removal settlement, centrifugation, or fine filtration of five to
seven micron control. Cat fine control can be monitored by
testing the treated fuel for aluminum/silicon levels [10,11].
CHAPTER
Water (D 95) (D
6: INTRODUCTION
4176)
Water is a contaminant that enters mEuine fuels during transport, usually when taken by tanker or barge over water. Salt
water can cause greater problems in marine fuels then fresh
water. Salt water has been considered the greatest single
cause of fouling, deposits, and corrosion, especially in the
higher temperature regions of the power plant. The presence
of water can initiate microbial growth in marine fuels. These
simple organisms must live in the water at the tank bottom
and feed on the marine fuel at the water/fuel interface.
Water in the marine fuels can cause large volumes of centrifuge sludge as a result of water-sludge emulsification during centrifugal separation.
Because of upcoming IMO and EPA exhaust gas emission
regulations, diesel engines may start using water in fuel
emulsions (made with potable water) to reduce oxidizes in
nitrogen (NOx), particulates and smoke. These water-in-fuel
emulsions can consist of u p to 50% additional potable water
and must be intentionally-made emulsions with a tightly controlled water droplet size and a control on all larger size
droplets. Lastly, whenever the diesel engine is shut down, all
emulsion must be purged out of the fuel system such that the
shut down diesel fuel injection system contains no water-infuel emulsion [12].
TO MARINE
PETROLEUM
FUELS
151
360
340
320
1500 P S I ,
900 P S I x
300
I1
300 F*SI
280
260
OPSI^
Fuel PropertiesChemical
Sulfur
(D
240
4294)
(D 524)
220
0
Sulfur [%]
FIG. 5Acid dew point for diesel engine fuels. Reprinted with
the permission of the Society of Naval Architects and Marine
Engineers (SNAME). Material originally appearing in SNAME
publications cannot be reprinted without written permission
from the Society, 601 Pavonia Ave., Jersey City, NJ 07306.
HANDBOOK
100
VA
ITO
55
'
B5
'
3D
~2!r
CHAPTER 6: INTRODUCTION
153
1600
1500
/
3Na20*V205
1400
o
1300
vp^
Q.
NA20*V 2O/5V2O
O)
1200
N a j O-V^Os
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2Na20*V205
1100
5Na zO-V^O/ 11V 2 0 \
1000
900
0
10
20
PRACTICAL FO ULING
ZONE
30
P
40
50
60
70
80
90
can damage high-pressure fuel injection pumps and fuel injectors. Sediment can be removed by gravity settling, filtration, and by centrifugal separators.
Fuel Additives
A fuel additive can be any material that, when added to a marine fuel, changes its properties, characteristics or performance. As secondary refinery processing cracks fuels more
severely, the resultant meirine fuel quality becomes more difficult to handle, store, and combust efficiently. The increased
amounts of metallic components, ash levels, and carbon contents adversely affect the performance of the fuel treatment
system and the power plant itself. Fouling and corrosion of
engine components and increased tank, centrifuge, and filter
sludge levels can present costly challenges for the ship's engineers. As fuel cracking intensifies, the fuel density increases
and it can make the centrifugal removal of free and emulsified water more difficult.
In addition to the conventional methods of settlement, centrifugation, and filtration, a chemical (additive) approach
Cin sometimes offer a solution to a particular problem. The
chemical additives that have been the most effective are the
stabilizers and dispersants, ash modifiers, biocides, demulsifiers, and emulsifiers [14].
Stabilizers and Dispersants
Stabilizers and dispersants tend to control the formation of
new sludge and to aid in the dispersion of existing sludge. By
limiting sludge, more of the hydrocarbon content of the
sludge can be burned and there is less sludge to incinerate or
to offload in the next port. Asphaltenes can significantly contribute to sludge production. By dispersing the asphaltenes
into very small particles with dispersant additives, sludge can
be reduced. Some additives work by using surfactants to facilitate a surface film formation at the fuel/asphaltene interface to stabilize the asphaltenes. The additional surface tension reduction tends to break the asphaltenes into minute
particles and stabilizes the fuel.
Additive additions are typically known as "tank treatments." Usually, when this additive is first used, it dissolves/disperses existing sludge and organic sediment and it
places a heavy burden upon the centrifugal separators and
filters as it begins to clean up tanks, piping, etc.
154
MANUAL
Ash
Modifiers
HANDBOOK
These ash modifying materials can react with corrosive elements of the fuel during combustion to raise the melting temperatures above the critical temperatures, thereby avoiding
high temperature corrosion. Magnesium compounds represent one of the more popular ash modifiers since they are
available in many forms and are relatively inexpensive. Prior
to combustion, these chemicals are added so that the magnesium combines with the vanadium (from the fuel) to form
harmless, high-melting compounds that no longer adhere to
and corrode the exhaust valves and seats, piston crowns and
turbo charger nozzles in diesel engines and the superheater
tubes in boilers. It is preferred to know the vanadium-plusnickel content of the fuel to determine the proper additive usage. Overdosing of ash modifiers could produce h a r d deposits within the cylinder of a diesel engine, which can lead
to abrasive wear of the piston rings and cylinder liners.
Demulsifiers
These chemical additives cause small water droplets to coalesce and separate more readily from the marine fuel. They
are typically added to the fuel storage tank before bunkering
fuel. They allow better water settling in storage, in the settling tank, and in the centrifugal purifier. These demulsifiers
are most effective when the water in the fuel exists as a fine
dispersion or as an emulsion.
Biocides
These chemicals are toxic to microbiological growth in marine fuels, tanks, and piping. This growth typically lives in the
water at the bottom of a fuel tank and feeds on the fuel at the
interface between the fuel and the water. Since this growth
must live in water, the goal of good housekeeping practices is
to keep the tank bottoms drained of water. This is a challenge
since fuel transport is usually by barge or tanker over seawater. A small quantity of biocide will keep the overall fuel system free of microbiological growth. Biocides should be selected carefully since some are fuel soluble a n d some are
water soluble.
F u e l Oil I m p a c t o n E x h a u s t E m i s s i o n s
There are several marine fuel properties that can impact exhaust gas emissions. Sulfur is the first fuel property to be regulated by international and domestic rules. The International
Maritime Organization (IMO) has limited sulfur to a maxim u m of 4.5%. Some localized regions, such as the Baltic Sea,
have imposed even lower sulfur levels.
The next emission to be regulated will be Oxides of Nitrogen (NOx). The IMO will restrict new marine diesels installed
after 2000 to NOx limits based upon the rotational speed of
the engines. Slow speed engines have the highest limits,
medium speed next, and high speeds have the lowest limits.
The nitrogen content of marine fuels does contribute to NOx
emissions, b u t to date, no organization has attempted to limit
fuel nitrogen.
Ignition quality, cetane for distillate fuels and CCAI for
residual fuels, has an impact on NOx produced in a diesel engine. Usually, the lower the ignition quality of the fuel, the
higher the NOx exhaust emissions.
CHAPTER
6: INTRODUCTION
Summer quality
Cloud point, C
Carbon residue on 10% bttns,
Ramsbottom, % mass
Carbon residue, Ramsbottom, % mass
Ash, % mass
Sediment by extraction, % mass
Water, % vol
Cetane number
Visual inspection
Sulfiir, % mass
Vanadium, mg/kg
TO MARINE
PETROLEUM
FUELS
155
duced a document called Annex VI of MARPOL 73/78, the regulations for the prevention of air pollution from ships, which
caps the sulfur level in marine fuels at 4.5 wt. percent and has
a provision that will restrict the NOx production from marine
diesel engines after Jan 1, 2000. As time moves forward, the
IMO will continue to regulate and restrict air pollution from
marine diesel engines. In some cases, as in the SOx emissions,
the air pollution control will be regulated by restricting fuel
properties. Therefore, although the IMO MARPOL regulations are not strictly fuel specifications, they will achieve
some of their regulation by restricting marine fuel properties,
as has already been done with a fuel sulfur cap.
ASTM Marine Fuel Specifications
The ASTM D 2069-98 Fuel Specifications are similar to the
ISO 8217 standard in many ways. Figure 8 shows the ASTM
detailed requirements for marine distillate fuels, and Fig. 9
shows the ASTM requirements for marine residual fuels.
Military F u e l Specifications
Military marine fuels consist of all distillate fuels that meet
an individual country's fuel specifications but most also conform to North Atlantic Treaty Organization (NATO) fuel
specifications as well. Military fuels place additional restrictions u p o n these distillate fuels to support the unique, multipurpose military requirements, as well as to provide for extended storage times. In the U.S. Mihtary, the MIL-F-16884
fuel specification requires a clean, stable distillate, somewhat
similar to marine gas oil, with additional properties and testing required before acceptance. Therefore, MIL-F-16884,
Diesel Fuel Marine (DFM), and NATO F-76 are the same fuel
that requires dedicated clean handling to prevent transport
contamination, which can cause the fuel to tail out of specification.
Limit
max.
min.
max.
min.
max.
max.
max.
max.
max.
max.
max.
max.
min.
max.
max.
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5.50
43
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1.50
6.00
60
DMB
900.0
DMC
920.0
11.0
60
14.0
60
-6
0
0
6
0
6
0.25
0.01
0.07
0.30
35
2.50
0.05
2.0
2.0
100
-16"
0.20
0.20
0.01
0.01
45
40
1.0
1.5
0.30
HANDBOOK
The U.S. Navy uses a ciistillate fuel, JP-5, for aircraft gas
turbine engines anci selected high speed diesel engines. This
fuel is lighter than MIL-F-16884. It differs from other aircraft
fuel primarily by its higher flash point requirements (60C vs.
38C). JP-5 fuel must be handled and stored clean.
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Fuel Sampling
Fuel sampling is the critical first step in obtaining knowledge
about the newly bunkered marine fuel. For a fuel test and
analysis to be meaningful, it is critical that a representative
sample be taken during the delivery of the fuel. A representative sample requires continuous sampling throughout the entire bunkering operation, since marine fuels can stratify or
can vary the blending ratios during the delivery period. Most
marine fuel testing services provide detailed directions and
equipment to take a continuous, representative sample. Also,
ASTM D 4057 can provide detailed instructions on taking a
representative sample. The old practice of taking a "spot or
grab" sample is no longer acceptable.
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CHAPTER 6: INTRODUCTION
On Board Testing
Since the shore side testing can take 24-72 h, some operators
prefer to supplement the shore side testing with quick, simple on board tests that are helpful in the short term. These
quick on board tests provide the immediate results often
needed to support decisions on fuel treatment system alignments, adjustments, and operations. The alignments and adjustments of the centrifugal separators can be effected by fuel
density, water content, compatibility, abrasive content, etc.
Typical on board tests include those for viscosity, density,
water, compatibility, and particle content.
157
quently inspect and maintain the condition of the flame arrester screens on the fuel tank vent lines, and careful and safe
use of the ullage equipment is imperative.
In a steam propulsion plant system, a duplex heater set
heats the fuel to the atomizing viscosity prior to the fuel
reaching the boiler fire front.
In a diesel engine propulsion system, the settling tank delivers heated residual fuel to the purifier heater set prior to
the centrifugal separator(s). It is important that the residual
fuel temperature to the separator stably remain at 98-99C to
maintain high separator efficiency and to prevent boiling of
the water (in the fuel) within the separator.
Service tanks or day tanks provide an additional opportunity to further settle water and solids from the heated residual fuel. The service tank can be filled by the centrifugal separators and provides additional time for deaeration.
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CHAPTER 6: INTRODUCTION
The marine diesel fuel storage (see Fig. 11) provides a separate fuel supply for cold boiler start up and for the emergency diesel generator. A small diesel fuel service tank is used
to provide clean fuel for emergency operation when neither
steam nor electricity is available. This diesel service tank is
located high in the machinery space so that gravity will supply enough fuel pressure to start the boilers and diesel generators in an emergency.
161
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CHAPTER
6: INTROD
UCTION
TO MARINE
PETROLEUM
FUELS
163
164
MANUAL
HANDBOOK
function of a homogenizer is to disperse the sludge and asphaltenes in the residual fuel to prevent the removal of these
hydrocarbons while passing through the fine filter. Therefore, the homogenizer can greatly increase the life of the filter elements as well as reduce the total quantity of sludge removed from the residual fuel. The reduction in sludge burden
reduces the problems and expense of sludge removal and decreases the wasted heating value of the lost sludge.
Some fine filters have the ability to remove trace quantities
of free water missed by the purifiers. Even though trace water removal might seem insignificant, shipboard testing has
shown a 100% increase in injection p u m p life after the addition of fine filters to remove the trace water from the marine
residual fuel. It is critical that the water sumps in fine filters
are drained daily to prevent water from rising above the
sump level and wetting the filter elements.
Self-cleaning or auto-flushing filters contain metallic
screens that automatically or periodiccdly back flush to clean
sections of the screen to allow for continuous operation. The
sludge and debris back flushed must be treated and finally
discarded. A problem can arise when filtering even a mildly
incompatible fuel since the increased sludge volume can require the filter to back flush u p to 400 times a day. This can
cause increased wear on back flushing components and on
the screen, as well as produce a Icirge volume of sludge for
disposal.
There are two t3rpes of replaceable, cjirtridge-type fuel filters: the surface type a n d the depth type. Surface elements
are similar to metal screens that have a limited thickness.
They can be made from cellulose, fiberglass, felt, or metal.
Surface filter elements are frequently pleated to increase the
filtration surface area within a given space and to increase
the element's life. A problem with surface filters is that organic sludge and/or asphtdtenes, together with solids, cEin accumulate on the surface of the filter and seal the surface. This
results in rapidly increasing pressure across the filter, which,
in turn, limits the useful filter life.
A depth filter is designed so that the entire depth of the element works as a progressive filter. This allows the contaminants to be controlled throughout the element's depth Eind reduces the buildup of contaminants on the surface that can
reduce filter life. This feature is especially important for fuels
with residual components that can cause problems for surface filtration.
CHAPTER 6: INTRODUCTION
sure of 350 kPa will be needed for high viscosity residucil fuel
that requires a high preheat for proper injection viscosity.
Homogenizer
As residual fuels become more dense with a higher viscosity
and higher carbon and asphaltene contents, homogenizers
will become more important to aid in the preparation of the
fuel for injection, complete combustion, and the reduction of
exhaust peirticulates cmd opacity (smoke). Very simply, a homogenizer disperses insoluble hydrocarbon clusters in the
residual fuel, completely disperses all free water and cem produce a stable, water-in-fuel emulsion (when potable water is
added to the fuel prior to the homogenizer). The homogenizer breaks up the insoluble hydrocarbon materials and
sludges into very fine particles that aid ignition and burnout
of the high boiling range, high molecular weight materials.
There are several different types of homogenizers available,
but the most effective operate on cavitation and shear principles, and require significant power to operate. Other units
operate on some ultrasoniccJly. As fuels become more heavily cracked, the use of homogenizers will increase. When
used regularly, homogenizers can reduce the unbumed fuel
particles that cause waste heat boiler fires (from unbumed
fuel particles).
165
Emulsifiers
Emulsifiers are units that produce a controlled, stable, waterin-fuel emulsion of residucd fuel. Emulsifiers can be homogenizers with the addition of potable water. The IMO has considered water-in-fuel emulsions as the most cost-effective
method to reduce NOx exhaust emissions for existing marine
diesel engines. If marine diesel NOx reductions ever mandate
the control of NOx on existing ships, water emulsion retrofits
will be the primary technology utilized.
Waste Heat Economizers
As diesel engines become more efficient and slower ship
speeds result in reduced diesel engine loads, the heavily
cracked fuels are not completely burned out in the diesel engines. The residue of unbumed cylinder lube oil added to the
organic fuel residue causes the waste heat economizer to experience a greater rate of tube fouling, soot fires, and major
economizer (iron or hydrogen) fires. Since the mid 1980s, the
incidence of economizer fires has steadily increased. The homogenizer Ccm minimize the unbumed residual fuel residues
and, if potable water is added to produce water in fuel emulsions, the economizer can be maintained in a cleaner condition. Chemical additives used in the residucd fuel can also
benefit the cleanliness of the economizer.
As a minimal precaution, waste heat boilers should instcJl
cind monitor the economizer exit temperature and the pressure drop across the unit to warn the engineers about an impending fire.
Tankage
The fuel treatment system actually begins with the fuel tamks,
since the initial settlement for free water and solids occurs in
storage. Gas turbine fuel tanks should be fitted with floating
suctions and fill line diffusers. The floating suctions draw the
cleanest fuel from the top of the tank continuously, allowing
more time for the settlement of contaminants in the mid and
lower regions of the tanks. A fill line diffuser reduces the velocity of the fuel and redirects it during tank filling to prevent
reentrainment of tank bottom settlement. Also, it all but eliminates currents in the tank that hinder settling.
Since metallic contamincmts are to be minimized, coating
the inside tank surfaces with an inert, non-metallic coating,
such as an epoxy, is recommended. Under no circumstances
should a zinc type coating be considered.
Fuel Treatment
As with all marine fuel treatment systems, the centrifugal
separator is the foundation and keystone of the system. But,
with gas turbine systems, this separator system becomes
much more comprehensive and complicated [18]. A modem
residual fuel or crude oil burning gas turbine usually requires
two stages of water washing, centrifuging at reduced flow
rates, the use of demulsifying chemical additives, and the use
of metallic neutralizing fuel additives (see Fig. 14). Demulsifying chemicals reduce the tendency of residual fuels to readily emulsify with water. Since these emulsions are difficult to
break in the sepjirator, the use of a demulsifier is recommended to prevent a problem during water washing of the
gas turbine fuel.
Figure 14 shows a typical two-stage water washing gas turbine system using a demulsifying additive. The staged water
cr
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In a typical gas turbine treatment system, iron-based materials, steel, and stainless steel are all valid material choices. It
is important that no copper, copper alloys, zinc or any of its
alloys (such as galvanized) be allowed to come into direct
contact with the fuel. Copper and zinc alloys or coating must
never be used in tubes or coils within heaters nor in any coating or cladding for fuel storage tanks. It is essential to avoid
the use of any galvanized piping or tank plating, as well as the
CHAPTER
6: INTRODUCTION
TO MARINE
D396
D2880
(also see D 4418)
PETROLEUM
FUELS
167
Conclusions
The supply of marine residual fuels will experience pressure
from three eireas. Refineries will receive heavier crude oils,
which will result in higher density, higher carbon content
marine residual fuels. Then as refineries upgrade, there is
more pressure to increase the intensity of cracking that will
result in fuels with more ignition problems and higher carb o n contents. Lastly, the shore side (and to a lesser extent
marine) environmental regulations will require cleaner burning fuels with less sulfur and less aromatics. This will divert
more difficult, heavier fuels into the marine market. The net
result will be that more difficult fuels will increase in the marine market.
Then, from the engine manufacturers, come new diesel engines with higher Brake Mean Effective Pressure (BMEP),
higher fuel injection pressures, that are more demanding of
ignition quality and are more sensitive to fuel contaminants.
The combustion of the residual fuel supply quality and the
trend in m o d e m diesel engine design will demand larger,
more efficient fuel treatment equipment to be assembled into
more comprehensive fuel treatment systems to preclude operating problems and schedule interruptions. Older diesel
ships should upgrade fuel treatment systems to prevent problems caused when older fuel treatment equipment/systems
try to cope with m o d e m cracked fuels.
As gas turbine engines continue to grow in the military marine and in cruise ships, their fuel treatment systems must
maintain the highest fuel quality and least contamination of
any marine engine. Since gas turbine engines use only 100%
distillate fuels, the problems are initially easier, but one load
of contaminated fuel can cause severe hot corrosion damage,
so continued vigilance is needed to prevent fuel related problems.
ASTM STANDARDS
No.
D 445
D 1298
D 613 for Distillates
D 4868
D 93
D
D
D
D
97
482
95
4176
D 4294
D 524
D 2069-98
Title
Kinematic Viscosity of Transparent &
Opaque Liquids
Density by Hydrometer
Cetane N u m b e r of Diesel Fuels
Estimation of Net and Gross Heat of
Combustion of Petroleum Fuels
Flash Point by Pensky-Martens Closed
Cup
Pour Point of Petroleum Products
Ash from Petroleum Products
Water by Distillation
Free Water and Particulate Contamination in Distillate Fuels
Sulfur in Petroleum Products by Energy-Dispersive X-ray Fluorescence
Spectroscopy
Carbon Residue, Conradson,
of Petroleum Fuels
Marine Fuel Specifications
OTHER STANDARDS
ISO
ISO 8217, Annex B for Residuals: Calculated Carbon Aromaticity Index Calculation
ISO10478, Cat Fines: Digestion & Analysis of Catalyst Particles
ISO 10307-2, Compatibility: Total Sediment Potential of
Petroleum Fuels
ISO 14597,Vanadium and Nickel: Determination of Vanadium and Nickel in Liquid Fuels^Wavelength Dispersive
X-Ray Fluorescence Spectrometry
ISO 10478, Sodium: Sodium Content of Petroleum Fuels
ISO 3735, Storage Oxidation: Storage Oxidation of
Petroleum Fuels
ISO 3735/10307-1, Sediment: Total Sediment Existent of
Petroleum Fuels
ISO 8217, Petroleum ProductsFuels (Class F): Specifications of Marine Fuels
Military F u e l Specifications
MIL-F-16844: All Purpose Marine Distillate Fuel
REFERENCES
[1] Winkler, M. F., Residual Fuel Oil User's Guidebook, Volume 4,
Diesels; and Volume 3, Gas Turbines; Southwest Research Institute for Electric Power Research Institute, May 1988. EPRIAP-5826.
[2] Leigh-Jones, C, A Practical Guide to Marine Fuel Oil Handling,
The Institute of Marine Engineers, London, 1998.
[3] Winkler, M. F., The Influence of Fuel Quality on the Performance,
Operation, and Maintenance of Diesel Propulsion Engines, Maritime Administration, U.S. Dept. of Commerce, March 1979.
[4] Winkler, M. F., Relationship of Fuel Quality to Marine Boilers and
Diesel Engine Performance, The Society for Marine Port Engineers, NY, January 1978.
[5] Barnes, G. K., Liddy, J. P., and Marshall, E. G., "The Ignition
Quality of Residual Fuels," CIMAC Paper 25, International
Council of Combustion Engines, 1 Birdcage Walk, Westminster,
London SW1H911, UK, June 1987.
[6] The Flammability Hazards Associated with the Handling, Storage
and Carriage of Residual Fuel Oil, Oil Companies International
Marine Forum (OCIMF), 27 Queen Anne's Gate, London,
SWIH, 9BU, December 1989.
[7] Winkler, M. F., "Coping with Today's FuelsDistillate and
ResidualDiesel and Steam," Society of Naval Architects and
Marine Engineers, Jersey City, NJ. Presented at the SNAME
Chesapeake Marine Engineering Symposium, Washington,
D.C., January 1984; Society of Marine Port Engineers, NY,
March 1982; National Maritime Show, Baltimore, March 1982.
[8] Winkler, M. F., "Fuel Management: Coping With Future Fuels,"
Marine Engineering/Log Magazine, March 1983.
[9] Newbery, P. J., Davies, T. A. C, and Chomske, K. M., "Heavier
Residual Fuels for Marine Diesel Engines," MotorShip Magazine,
West Sussex RH16 3DH, UK. Presented at the 6th International
Motorship Conference, London, March 1984.
MNL37-EB/Jun. 2003
chemistry:
provide a brief overview of the base oil market and identify
emerging trends,
outline the refinery processing scenzirios typical of current
base oil production in the United States,
review the chromatographic and spectroscopic techniques
most commonly used to characterize base oil composition,
provide a comparison of hydrocarbon tjrpe distributions
for base oils obtained by several different refinery processes, including re-refined oils,
review important chemical mechanisms leading to the oxidation and degradation of base oils,
outline composition/performance relationships for base oils
in various automotive and industrial lubricant applications.
of engine oils, industrial lubricants, greases, and other products, are composed of a broad spectrum of molecular species
including aromatic, paraffinic, a n d cycloparaffinic (naphthenic) molecules [1-4]. Over the past severeil decades, new
separation methods and analytical techniques have made it
possible t o accurately characterize and quantify the hydrocarbon t5^es that exist in base oil while relating these compositional pEirameters to crude oil source and refining conditions. F o r example, ASTM test m e t h o d D 2549 exploits
column chromatography to separate a base oil into saturate
and aromatic fractions while D 2786 and D 3239, mass spectrometry techniques, further sub-divide each fraction into a
group of molecular types. As a result, the physical and chemical properties of base fluids are now m u c h better understood
and, in some cases, it has become possible to predict the performance of a formulated lubricant directly from base oil
composition using statistical m e t h o d s o r neural network
modeling [3-8].
LUBRICANT B A S E OIL M A R K E T
Refining Capacity i n the United States
Copyright'
2003 by A S I M International
www.astm.org
HANDBOOK
Location
Baton Rouge, LA
and Baytown, TX
Deer Park, TX,
Martinez, CA and
Wood River, IL'
Tulsa, OK and
Yabucoa, PR
Port Arthur, TX
Westlake, LA
Richmond, CA
Rouseville, PA and
Shreveport, LA
Beaumont, TX
Paulsboro, NJ
Lake Charles, LA
Catlettsburg, KY
Capacity
(mm GallonsA'ear)
577
298
271
269
269
214
199
180
176
146
130
Location
Newark, CA
East Chicago, IL
Calgary, Alberta
N. Vancouver, BC
Breslau, Ontario
Total
Capacity
(mm GallonsATear)
12.3
50.6
3.1
6.1
23.0
95.0
gional refinery supply/demand issues, Table 3 provides a general reflection of base oil prices in early 1999, when crude oil
averaged less than $20/bbl compared to 2000 when crude
cost climbed above $25/bbl [12 A,B]. Table 3 also illustrates
that base oil prices generally increase with increasing viscosity grade due to several factors including: the "natural"
molecular weight range of the crude sources used for lubricant manufacture and the extra refining required for heavier
distillate streams, since they are t3rpically richer in aromatics
and sulfur-containing molecules. Based on an average price
of $1.00 per gallon, domestic base oil refiners generate revenues in excess of $3.5 billion annually.
Future Refining Trends
Although basestock demand is growing only modestly in
North America at less than 3% per year [9], other regions of
the world are expanding more quickly [10]. Specifically, certain South and Central American and Asian countries are experiencing lubricant growth demand in excess of 5% per
year. In all cases, an evolution to higher quality base stocks,
such as Group II and III oils, defined below, is evident on a
worldwide basis [13]. As a result of extreme competition to
produce and utilize Group II base stocks and an overall reduction in demand for naphthenic stocks, the base oil refin-
ing capacity in North America has decreased by approximately 8% from 1980 to 1995 [10].
Average Cost
('99/'00)
Range of Prices
('99/'00)
Low (90-150iV)
Medium (200-250yV)
Heavy (500-600A^)
Bright Stock (Very Heavy)
0.85/1.17
0.86/1.18
1.00/1.27
1.19/1.52
0.79-1.04/1.07-1.23
0.80-1.04/1.07-1.27
0.94-1.17/1.20-1.37
1.16-1.31/1.41-1.53
CC
40C
100C
150C
75
100
125
150
192
155
117
92
21.0
19.5
17.7
16.3
4
4
4
4
1.87
1.91
1.97
2.03
CHAPTER 7: HYDROCARBON
171
Distillation
Two distillation units are typically required to effectively
fractionate crude oil for use in lubricants [10]. First, an atmospheric still is employed to selectively remove gases and
other light products such as gasoline and naphtha from the
lube distillate stream. Secondly, the remaining stock is distilled under reduced pressure in a vacuum distillation unit
yielding a number of viscosity fractions appropriate for various applications. Typical boiling points for each crude oil
fraction are shown in Table 5. The distillation cut corresponding to lubricating oils typically consists of molecules
that range in size from 20-40 carbon atoms per molecule.
Most refineries fractionate the distillate into 3-5 distinct viscosity grades, historically called "neutrals," for which 100C
kinematic viscosity values range from 3-5 cSt for so-called
"light neutral oils," 6-9 cSt for "medium neutrals" and > 10
cSt for "heavy neutrals." In commercial practice, the viscosity grade designation for base oils, such as 100 Neutral
(lOON), was based on the Saybolt Universal Second (SUS)
system of measuring viscosity that is no longer widely utilized. Table 6 illustrates the relationship between "historic"
SUS viscosity grades and kinematic viscosities obtained from
ASTM D 445.
Propane Deasphalting
Hydrogen Refining/Hydrocracking
Although solvent refining is effective in improving the quality of distillates in the manufacture of base oils, a significant
yield loss is normally associated with the extraction process.
This loss can be economically unacceptable for distillates derived from relatively poor crude oils that contain high concentrations of heavy aromatic compounds. Fortunately, it is
also possible to improve the quality of a raffinate through
various catalytic processes in which high-pressure hydrogen
(1500 - 4000-1- psi) is employed to saturate aromatic
molecules while cracking other large molecules to smaller
compounds of molecular weight appropriate for base oils
[10]. Olefins as well as sulfur and nitrogen containing compounds are also reacted and removed by hydrogen processing. Because aromatics are converted to saturated compounds, hydrogen processing normally increases VI.
Solvent Refining
For basestocks of low to moderately high viscosity, solvent
refining has been employed extensively and on a worldwide
basis; this refining technology is probably the most popular
method. Solvent refining removes undesirable polar and
highly condensed aromatic molecules from the distillate and,
in doing so, significantly increases VI. In this process, distillate is mixed with an insoluble polar solvent that creates a
two-phase system. Ideally, desirable paraffinic and naphTABLE 5Distillation cuts of crude oil [14, 15].
Fraction
<0
to 150
150-205
to 180
205-260
205-290
260-315
315-425
>400
425-600
>600
Kinematic Viscosity
at 100C (cSt)
3
4
6
8
10
12
14
16
18
SUS Viscosity
at 100F
70
100
200
310
430
560
710
870
1000
Dewaxing
Essentially, all crude oil and base oil distillates contain a
small fraction of linear paraffins (wax) [14] that can crystallize at low temperatures. For engine oils, transmission fluids,
and other lubricants that must remain liquid and pumpable
to temperatures approaching -40C, it is necessary to remove as much wax as possible from the basestock. To accomplish this task, at least two techniques are commonly
used to remove wax: solvent dewaxing (SDW) and catalytic
dewaxing (CDW). For SDW, the base oil is first diluted in a
solvent (toluene, for example) and then the mixture is added
to a wax non-solvent (typically ketones such as methyl ethyl
ketone-MEK). The mixture is then chilled to low temperatures to precipitate wax as a solid and is then collected by filtration. SDW is a batch process. In the CDW procedure, a
shape selective catalyst is exploited to "crack" the paraffins
into smaller, volatile segments that can be fractionated by
distillation. CDW is a continuous process and, as a result, en-
172
MANUAL
HANDBOOK
B A S E OIL CHARACTERIZATION
Hydrocarbon Type Analysis
The chemiCcd composition of lubricant base oil is strongly
dependent o n a n u m b e r of factors. These include crude oil
source, molecular weight range (generally higher molecular
weight crudes are richer in multi-ring aromatics), the refining process (solvent vs. hydroprocessing), the degree of refining, and the effectiveness of the finishing process.
Determining the chemical compositional profile of base
oil is usually initiated with a chromatographic separation
procedure to isolate the aromatic and saturate fractions
of the sample. ASTM method D 2549 involves an open colu m n procedure using a bauxite column packing with polar
and non-polar organic solvents to elute the aromatic and saturate fractions, respectively. In this procedure a sample of
base oil is applied to the top of the column, which is then
flushed sequentially with solvents of increasing polarity. Saturated molecules, including both paraffins and naphthenic
molecules, bind to the column less strongly than ciromatic
compounds and, as a result, they elute from the column with
n-pentane (non-polar) while the aromatics require "stronger"
polar solvents (chloroform/ethyl alcohol) to be eluted. Typical aromatic and saturate levels determined by D2549 for a
series of base oils, refined by different methods, are given in
Table 7. It may generally be concluded that base oils contain
a preponderance of saturate compounds and that the level of
aromatics for a solvent refined base oil increases with viscosity grade largely because heavier distillates contain higher
% Saturates
% Aromatics
70-90
65-75
60-70
50-60
90-100
95-100
60-70
10-30
25-35
30-40
40-50
0-10
0-5
30^0
CHAPTER 7: HYDROCARBON
levels of aromatics. Further, hydroprocessing techniques,
specifically hydrocracking and hydroisomerization, drastically reduce aromatic level. In addition, base oils processed
from naphthenic crudes typically exhibit a high aromatic
content and a very low level of paraffins (<8%).
A related column chromatography method, ASTM D 2007,
is based on a clay-silica gel adsorption procedure that resolves a base oil sample into aromatic, saturate, and polar
fractions. In this procedure, the following solvents are used
to elute the hydrocarbon fractions: n-pentane (elutes saturates), toluene (elutes aromatics), and toluene/acetone
(elutes polars). ASTM D 2007 was chosen as the preferred
method for base oil characterization in the so-called
"Base Oil Interchangeability Guidelines" established by the
American Petroleum Institute (API) in API Publication
1509 - Engine Oil Licensing and Certification System (API
Address: 1220 L Street NW, Washington, DC 20005-4070,
www.api.org). In this publication, the API concludes
that "Not all base oils have similar physical or chemical
properties or provide equivalent engine performance in engine testing
The API Base Oil Guidelines were developed
to ensure that the performance of engine oil products is not
adversely affected when different base oils are used interchangeably by engine oil blenders" (API 1509). Under these
guidelines base oils are grouped into three categories according to composition, VI, and sulfur content as shown in Table
8. Group IV is reserved for polyalphaolefins and Group V includes other basestocks not included in Groups I-IV.
API Publication 1509 also defines which engine tests are
required when interchanging a base oil in an approved gasoline or diesel engine oil formulation using the base oil definitions above. Currently in the U.S., approximately 1.76 billion
gallons of annual production of paraffinic base oil is Group I
while 870 million gallons/year is Group II [11]. The ratio of
Group II to Group I has increased significantly since the early
1990s and most new base oil plants utilize refining technology that provides Group II stocks.
In reference to the ASTM D 2007 procedure, it should be
noted that a hydrocarbon analysis technique based on ThinLayer Chromatography with Flame-Ionization Detection has
TABLE 8 --API lubricant base stock categories
API Group
I
II
III
% Saturates
% Aromatics
VI (1)
% Sulfur (2)
<90
>90
>90
>10
<10
<10
<120
>80, <120
>120
>0.03
<0.03
<0.03
Group I
Group II
Group III
Paraffins
Monocycloparafflns
DlcyloparafHns
Tricycloparafflns
TetracycloparafHns
Pentacycloparafflns
Hexacycloparaffins
23.9
14.7
11.3
8.1
9.9
6.6
4.2
22.0
23.1
19.2
11.7
9.3
7.2
5.6
70.2
11.8
5.3
1.8
1.6
0.6
2.5
Total
78.7
98.0
93.7
173
Group I
Group II
Group III
Monoaromatics
Diaromatics
Triaromatics
Tetraaromatics
Pentaaromatics
Thiophenaromatics
Unidentified Aromatics
Total
11.7
3.1
1.1
0.8
0.4
1.6
2.7
21.4
0.9
0.6
0.2
0
0
0.1
0.2
2.0
4.0
0.9
0.2
0.1
0.1
0.4
0.6
6.3
Volume %
Monoaromatics
Total
13.2
Alkylbenzenes
Naphthenebenzenes
Dinaphthenebenzenes
Diaromatics
6.94
3.37
2.92
Naphthalenes
Acenaphthenes, dibenzofurans
Flourenes
Triaromatics
0.91
0.89
0.77
Phenanthrenes
Napthenephenanthrenes
Tetraaromatics
0.45
0.22
Pyrenes
Chrysenes
Pentaaromatics
0.08
0.17
Perylenes
Dibenzanthracenes
Thiophenoaromatics
0.06
0.03
Benzothiophenes
Dibenzothiophenes
Naphthobenzothiophenes
Unidentified Aromatics
0.23
0.50
0.0
2.6
0.7
0.3
0.1
0.7
Total Aromatics
1.5
19.0
HANDBOOK
papers by Sarpal [18,23] and Sahoo [24] demonstrate the potential of this method in characterizing base oil. Aromatic
carbon atoms exhibit resonances at chemiced shifts ranging
from 100-160 while saturated carbons (paraffins and naphthenes) provide shifts in the range of 10-60 ppm [24]. From
the information in Table 14, it is also possible to estimate the
average peiraffinic chain length of base oils by developing ratios of chain ends (-CH3 groups) to -CH2- groups well separated from chain ends.
A relatively new pulse protocol called DEPT expands the
utility of ^^C-NMR for base oils in that it provides individual
spectra for each carbon atom t3?pe CH where n = 0-3
thereby increasing resolution and the ability to quantify carbon species [23]. In using NMR to study base oils, care must
be taken, however. '^C-NMR is inherently non-quantitative
since each carbon atom relaxes at a rate depending on its surroundings and complete relaxation is required for integration data to be quantitative. Since carbon nuclei relaxation
times can be on the order of seconds, total relaxation between NMR pulses is not typically achieved. As a result, the
use of a so-called relaxation agent, such as chromium acetylacetonate, is essential with base oils to ensure complete relaxation enabling quantitative integration.
Mononaphthenes
Dinaphthenes
Trinaohthenes
Monoaromatics
Structures
\A/^/\
-0oCc;r
V^A^A^-JY^
^<y^
Indanes:
Aromatic / Naphthene "Hybrid"
Diaromatics
/lL^js*^j,,Jk^
CHAPTER 7: HYDROCARBON
175
Hydrocarbon
Types
Triaromatics
Tetraaromatics
Thiophene
-o^
0
Benzothiophene
CO
Dibenzothiophene
0:p
Napthobenzothiophene
s
Description (1)
Short Branch E n d
Long Branch E n d (a)
Adjacent to Long Chain E n d (p)
Near Chain End (7)
Adjacent to Long Chain CH2 (8)
Middle of Long Chain (e)
Typical Chemical
Shift (ppm)
11.4
14.1
22.7
32.0
30.1
29.7
B A S E OIL C H E M I S T R Y
Oxidation Reactions
Hydroccirbon oxidation chemistry is of great importance in
the ukimate appHcation of base oils and lubricants, since at
the high temperatures typical of most lubricating environments, oxidation can lead to undesirable oil thickening, the
formation of insoluble sludge and varnish deposits, and the
creation of potentially corrosive organoacid compounds. Although this subject has been extensively covered in many ex-
I*
I-I
R-H + !
Propagation:
I-H + R*
->
R02*
R02 + R-H
Termination:
ROOH + R*
R + R02 "
-> ROOR
2R02
-R-O4-R
R-O4-R
-p. O2 +Non-Radical
Products
FIG. 1Hydrocarbon oxidation by free radicals.
CeHs CH3
sec-alkyl-COO
1
R-CH3
1
(CH3)3CO.
Cj6^5^'l2^H3
9
R2CH2
12
C6H5CH-(CH3)2
14
R3CH
44
of secondary or tertiary hydrogen atoms. The rate of free radical propagation is Eilso very dependent on ring geometry and
adjacent function groups as shown in Table 16 for phenyl
radicals [33].
As oxidation proceeds, propagation reactions involving
peroxy radical addition to other hydrocarbon molecules typically result in the formation of polar compounds and higher
molecular weight species, which may ultimately increase the
viscosity of the oil. The combination of oligomeric and polymeric radicals during the termination phase of oxidation can
also cause a molecular weight increase and viscosity enhancement. Studies on the autoxidation of n- hexadecane
(linear CI8 paraffin) at temperatures of 160-180C have illustrated that Ccirboxylic acids, hydroperoxides, ketones, alcohols, and esters Eire all formed over a period of hours. It is
interesting to note, however, that this "model system" exhibited a significant increase in viscosity while only a "modest"
increase in molecular weight was observed [31].
A useful oxidation model for thin hydrocarbon films on
metal surfaces has been developed by Professor E.E. Klaus
a n d his co-workers at the Pennsylvania State University
[34-36]. They have shown that if Molecule A is oxidized it
forms Molecule B that initially has the same molecular
weight as A. At this stage, both A and B can volatilize to A'
I m p a c t o f S u l f u r C o m p o u n d s o n B a s e Oil
Chemistry
Throughout the evolution of base oil refining and processing
technology, sulfur content has been employed as an indicator
of product quality and a predictor of lubricant performance.
In this context, the t e r m "sulfur" relates to soluble,
organosulfur compounds that occur naturally in crude oil in
contrast to elemental, yellow sulfur. Current domestic base
oil sulfur concentrations typically range from <0.05 wt% to
0.4% for light base stocks and u p to 0.8-1.0% for heavier viscosity grades. In other regions of the world, it is not uncomm o n to observe sulfur levels in excess of 1.5-2.0%. From the
perspective of base oil chemistry, how the organosulfur content impacts lubricant performance is very complex and depends, to a large extent, on the ultimate application and the
nature of the additives used in the formulation. Although current manufacturing trends suggest that a very low sulfur content is most desirable for base oil, it has historically been
thought that higher sulfur levels directionally improve base
oil oxidation stability as well as friction a n d wear performance.
The pioneering work of Dennison and Conduit [37] in the
1940s concluded that "the oxidation stability of refined
petroleum lubricating oils is the result of small quantities of
natural sulfur compounds and not of any inherent stability of
the hydrocarbon fraction itself. In the absence of the natural
sulfur compounds the hydrocarbon fraction oxidizes rapidly
and, in the initial stages of the reaction, autocatalytically."
This work clearly illustrated that certain sulfur containing
compounds, specifically monothioethers containing at least
one aliphatic or cycloaliphatic group attached to the sulfur
atom (sulfides), were very potent antioxidants in lubricants.
These authors were successful in selectively removing the
sulfur compounds from a mineral oil while keeping other
CHAPTER
7: HYDROCARBON
BASE
OIL CHEMISTRY
177
CH3 - X X =
Phenyl*
Phenyl*
Phenyl*
Phenyl*
Alkyl
Phenyl
Benzothiophene
2-Thiophene
RCH2*
RCH2*
Phenyl
2-Thiophene
HD + Carbazole
HD + Phenanthridine
Effective Nitrogen
Concentration (ppm)
RBOT Lifetime
(min.)
10
5
2
9
4.5
2
11
6
0.2
10
10
596
216
248
296
306
324
405
501
516
578
576
440
Nitrogen C o m p o u n d Reactivity
Nitrogen containing molecules found in base oils can also accelerate oxidation and deteriorate the useful lifetime of lubricants. More specifically, "basic nitrogen" compounds (socalled proton acceptors) such as various pyridine derivatives,
can act at very low concentrations (below 10 p p m based on
N) in deteriorating oxidative stability [6,38,39]. Oxidation
lifetime for the straight chain paraffin hexadecane, a base oil
"model compound," in the presence of small quantities of
"basic nitrogen" are shown Table 19. The data clearly illustrate that such species can promote oxidation rate in the
ASTM D 2272 RBOT procedure. These results illustrate that
the molecular structure of the "basic nitrogen" compound influences the oxidation reaction. More specifically, Yoshida
et. al [38] have found that reducing the pKb of the nitrogen
group enhances the overall rate of oxidation.
In addition to these model compound studies, statistical
and neural network modeling methods have demonstrated
that RBOT lifetimes for prototype industrial oils (hydraulic
178
MANUAL
HANDBOOK
fluids and turbine oils) also decrease with increasing base oil
basic nitrogen content. Further, thermal sludge formation
and oxidation onset determined by a high pressure differential scanning calorimetry technique indicated a deterioration
with higher levels of basic nitrogen [6].
Olefins
Although crude oils Eire generally relatively low in olefin content [10], base oil processing techniques can introduce
olefins, especially at high temperatures, due to "cracking" reactions. In the presence of heat or UV light, olefins can polymerize to form higher molecular weight products that can
color the base oil or actually cause sediment. In general,
olefins can be removed during the process of hydrofinishing
or by clay treatment discussed above [10].
CHEMICAL COMPOSITION/LUBRICANT
PERFORMANCE CORRELATIONS
As previously discussed, base oils contain a broad spectrum of
paraffinic, cycloparaffinic, and aromatic molecules, the distribution of which varies with crude source and refinery processing. More importantly to the lubricant chemist and engineer, each of these hydrocarbon types can exert a different
effect on the ultimate physical and chemical properties of the
base oil and, ultimately, the lubricant from which it is formulated. Table 20 illustrates the relationship between hydrocarbon type and performance for several important properties.
B a s e Oil R h e o l o g y a n d C o m p o s i t i o n
The flow properties, or rheology, of a lubriccint strongly reflect the composition of the base oil used in its formulation.
Comparing hydrocarbons of similar molecular weight, paraffins (especially linear paraffins) provide the highest positive
contribution to base oil VI while aromatics and naphthenes,
particulcirly multi-ring structures, strongly decrease VI. Base
oils of high VI Eire generally preferred for lubricants because
they provide higher viscosity at high temperatures and lower
viscosities at low temperatures, provided they are properly
treated to inhibit wax crystallization. In the absence of effective pour point depression, higher VI oils containing elevated
levels of wax display poor low temperature fluidity as wax
crystals form network structures that Eire resistant to flow. In
most cases, polymeric pour point depressant additives eliminate wax crystallization and, u n d e r these circumstances,
base oils rich in paraffins can exhibit excellent rheological
properties at low temperatures.
ParaiBns
Naphthenes
Aromatics
Excellent
Poor
Excellent
Poor
Excellent
Poor
Poor-Good
Good
Good
Good
Poor-Good
Good
Poor
Good
Good
Excellent
Poor
Excellent
"Unadditized.
''Treated with a pour point depressant.
CHAPTER
Roby and co-workers were also successful in developing
statistical correlations between base oil composition and performance in the ASTM Sequence HID and VD gasoline engine tests [40]. For high temperature oxidation in the HID
procedure, it was learned that no single base oil parameter
provided a good correlation to viscosity increase but a regression equation including nitrogen content (ASTM D
4629), olefin n u m b e r (ASTM D 460), sulfur content (ASTM D
1552) and saturates (column gradient elution chromatography) provided an excellent fit (R-squared = 0.97) to the observed data. For oxidation control, high levels of saturates
and sulfur compounds were beneficial while elevated olefin
and nitrogen levels contributed to poor performance. In the
Sequence VD gasoline engine test, which eveJuates deposit
formation at relatively low levels of oil oxidation, the individual variables discussed above all showed good correlations
(R-squared values > 0.79) to varnish formation with higher
nitrogen, olefin, and sulfur content being detrimental. Average engine varnish ratings in the Sequence VD improved with
increasing base oil saturates content, however.
More recently, base oil effects in the Sequence HIE and VE
engine tests have been studied [3,4] using Partial Least
Squares (PLS) and neural network modeling methods. These
authors evaluated the engine test performance of a group of
different base oils (approx. 12 oils) formulated into engine
oils using similar additive technology. For the Sequence HIE
oxidation test, viscosity increase and piston skirt varnish ratings generally improved with paraffin content while reacting
negatively to high levels of multi-ring naphthenes, multi-ring
aromatics, and thioaromatics. Total sulfur content was found
to reduce viscosity increase and piston deposits in the Sequence HIE, consistent with its antioxidant effect discussed
earlier. For the Sequence VE test, total sulfur, thioaromatics,
and multi-ring aromatics all enhanced the formation of varnish deposits.
Using the PLS modeling protocol described in Ref 3, it is
possible to predict the engine test performance of lubricants,
assuming a c o m m o n passenger car engine oil additive technology, using base oil compositional features as input. In this
fashion, the potential Sequence VE varnish ratings for engine
oils formulated from a population of base oils representing
typical U.S. production were predicted. Ratings are based on
a visual examination of a n u m b e r of engine pairts where 10.0
corresponds to a totally clean part, 5.0 is the m i n i m u m "passing" rating, and <4.0 corresponds to a very poor engine oil
formulation. API Group I oils gave varnish values of 5.0 or
less. Group II oils exhibited improved varnish ratings in the
range of 5.5-5.8, while Group III and IV oils provided ratings
of 6-6.5.
In a separate study, a group of re-refined oils (RR) were
evaluated and, on average, predictions suggested that they
would perform at levels comparable to "virgin" oils (VO) assuming normeJ test-to-test vEiriability. These results are summarized in Table 2 1 .
Several generalizations can be made about the role of base
oil composition in heavy duty diesel engine oils where oil
thickening due to the accumulation of soot cind piston ringland deposits are important considerations in several industry standard tests. Base oils of comparatively high saturates
content have been found to perform better in the Mack T-8
engine test than oils of higher aromatic content. This test
7: HYDROCARBON
BASE
OIL CHEMISTRY
179
High
Result
(VO/RR)
Average
Result
(VO/RR)
Low
Result
(VO/RR)
9.21/9.34
8.92/8.95
8.63/8.7
283/219
192/163
73/65
5.45/5.51
4.93/5.08
4.32/4.8
B a s e Oil E f f e c t s i n I n d u s t r i a l L u b r i c a n t s
Although base oil composition can play an important role in
defining the performance of engine oils, additive chemistry
and concentration can largely overcome potential deficiencies of a pEirticular basestock. Typically a 10-15% treat level
of dispersant/inhibitor package is added to a motor oil to control oxidation, deposits, etc. In industrial lubricants, however, formulation economics dictate very low additive treat
levels, usually less than 2% for products such as hydraulic
fluids, turbine oils, quenching oils, and other process fluids.
As a result, product quality is linked more directly to base oil
composition.
The work of Murray cited above [1] also demonstrates that
industrial oil oxidation lifetimes in the D 943 oxidation test
a n d the D 2272 Rotary B o m b Oxidation Test (RBOT) increased with increasing saturate levels for 150 N oils containing an oxidation inhibitor. Sulfur content played a minor
role, however, presumably because the inhibitor effectively
controlled oxidation. For the D 943 test, Firmstone and coworkers [4] showed, using Partial Least Squares models, that
increases in base oil peiraffin content, sulfur concentration,
VI, and aniline point enhance oxidation lifetime, while cycloparafHns, multi-ring aromatics, and nitrogen content have
HANDBOOK
cal device from high friction and premature weeir is dependent on the high shear viscosity of the lubricant and its viscosity-pressure coefficient [45]. Thicker lubricant films are,
therefore, produced by fluids exhibiting a higher a value.
However, in the design of many fuel economy enhancing "energy conserving" lubricants, a less viscous film is desired
since mechanical energy can be wasted if the film is too robust. In these cases, lubricants of lower a are favored. In
other applications such as Continuously Variable Transmissions (CVTs), where the fluid must provide high levels of traction, a very high a is needed [46].
Based on the importance of a in the design and application
of lubricants, effort has been focused on determining the relationship between base oil structure and its response to high
pressure [44]. Figure 2 illustrates the magnitude of viscosity
increase that can be expected for typical lubricant base oils,
over pressure ranges not uncommon in certain mechanical
devices, plotted by API base oil groups. These data were
recorded using a falling body viscometer [47].
In general, Group IV (polyalphaolefin) fluids provide the
lowest increase in viscosity with increasing pressure, followed by Group III, Group I, Group II, and finally napthenic
base oils. In this specific example, a statistical analysis [48]
revealed that the Group III and IV oils provided the lowest a
values because these products were very high in paraffin content (>60%), while Group I and II products provided intermediate performance because they contained less paraffins
and higher levels of naphthenic ring compounds (>40%).
Since the cycloparaffin ring structure is sterically very bulky,
it is especially sensitive to applied forces and contributes significantly to increasing the viscosity-pressure coefficient for
base oils. Planar aromatic rings appear to pack with less difficulty. Under pressure, paraffins are easily compressed and
can actually be induced to crystallize if pressures are sufficiently high. In the design of CVT fluids, molecules are synthesized to optimize their steric bulkiness [46].
A number of other procedures are also available to calculate the viscosity-pressure coefficient for base oils from com-
100
200
300
400
500
600
Pressure (MPa)
FIG. 2Viscosity - pressure relationships for base oils at 100C (nominaiiy 4 est at
100C, 1 atmosphere pressure).
CHAPTER
positional data and/or other bulk fluid properties [44,49].
Roelands [44] has shown that the viscosity-pressure relationship for base oil can be predicted solely from atmospheric
viscosity (TJO) a n d a knowledge of the percentage of
carbon atoms in a aromatic ring structure (CA) and the percentage of naphthenic (cycloparaffinc) carbons (Cn). Johnston determined that the pressure-viscosity coefficient could
be calculated from ambient pressure fluid density and the
viscosity/temperature relationship (specifically viscosity at
two temperatures is needed) [49]. More recently, Spikes and
co-workers have shown that the thickness of a lubricant film
under conditions of elastohydrodynamic lubrication (EHD)
can be related to a by the following expression obtained from
a high-speed ultrathin film interferometry technique [45]:
7: HYDROCARBON
BASE
OIL CHEMISTRY
181
Biological P r o p e r t i e s of B a s e Oils
Since lubricants can come in direct contact with humans in
some applications, the biological toxicity of base oils is a concern especially for those products containing high concentrations of polycyclic aromatic hydrocarbons (PAHs). These
compounds have been found to be mutagenec and carcinogenic axid the International Agency for Research on Cancer
has classified 18 PAHs as cancer causing [50 and references
therein]. From a molecular structure perspective, these 18
molecules each have in common a 4-6 fused aromatic ring
system and a so-called 3-sided concave "bay region" similar
in structure to the geometries shown for triaromatic and tertaaromatic molecules shown in Table 13.
Probably the most well established method to assess the
potential mutagenicity/carcinogenicity of base oils is the IP
346 Method that uses dimethylsulfoxide (DMSO) extraction
to isolate PAHs. By correlation to mouse skin painting studies, it was determined that base oils exhibiting DMSO-extractable levels exceeding 3 wt % should be considered carcinogenic [50]. F u r t h e r work by Nessel a n d co-workers
indicated that a level of 5% IP 346 extractables might be a
more appropriate target [50]. This group also developed a
NMR-based method to characterize the concentration of hydrogen atoms in the so-called "bay region" of PAHs and they
have compared these data to IP 346 results and t u m o r incidence results obtained from skin painting studies as shown in
Table 22. Based on these results, Nessel proposes that a limit
of 1500 p p m of bay region hydrogen atoms be established as
a limit of carcinogenicity [50]. NMR enjoys the advantage of
being much faster and less expensive than other methods of
assessing the toxicological effects of base oils.
Unpublished results generated by the author indicate that
the IP 346 method correlates reasonably well to the multiring aromatic content obtained from ASTM D 3239 for relatively light to m e d i u m viscosity base oils (70-150N or 3-5 cSt
at 100C). However, it underestimates the aromatic content
of m e d i u m to heavy grades (320-850N). Presumably the
DMSO extraction procedure of IP 346 is not effective in solubilizing higher molecular weight aromatics. It was not established, however, if these heavier aromatics promoted a mutagenic or carcinogenic response in animal tests. It is
possible that their relatively large size restricts their molecular mobility and ability to be adsorbed into the tissue of animals.
182
MANUAL
HANDBOOK
IP 346 - % DMSO
Extractables
Tumor
Incidence - %
Up to 39
Up to 86
100-600
100-200
1500
1500-3200
3800-9000
3800-5600
<1.0
<1.4
2.5-6
5-6
5-6
5-12
12-15
16-43
0
0
0
0
36-54
20-60
60-90
4-40+
IP Test
Number
D 445-97
71
D 611-82
D 2270-93
2
226
D 4629-96
379
Method Description
Biodegradability
The ability of a lubricant to degrade naturally in the environment is becoming an increasingly important property that is
directly related to the composition and molecular weight of
the base oil employed in its formulation [52,53]. Currently,
several standcird experimental protocols are widely utilized
to evaluate the biodegradability of a lubricant: ASTM D 5864
(fully formulated lubricants), D 6006 (hydraulic fluids), and
the European method CEC-L-33-T-82. Voltz has shown that
hydraulic fluids based on hydrocarbon mineral oils only degrade to an extent of 40% after 25 days in the CEC test while
synthetic, ester-based fluids are degraded almost entirely
(>90%) [53]. Synthetic hydrocarbons and polyethylene glycols were found to display intermediate behavior with maxim u m degradation levels of 70% and 55%, respectively.
In addition to composition, the size of a base oil molecule
can influence its biodegradability. Weller has reported using
the CEC protocol, that 2 and 4 cSt PAOs degrade at reasonably high levels, 75% and 65% respectively, while 6, 10, and
100 cSt PAO samples degraded less than 20% [54]. Similar results have been reported for other types of base oil suggesting
a limiting molecular size exists above which an organism
cannot adsorb and biodegrade hydrocarbon molecules.
INTERNATIONAL STANDARDS
As shown in Table 23, many of the ASTM experimental test
procedures outlined in this chapter have analogs in the Institute of Petroleum (IP) Standard Test Methods published in
the UK. Several examples are given below where the ASTM
and IP organizations share a single test method: in m a n y
other cases, the ASTM and IP have developed methods to determine the same lubricant property (sulfur content, low
temperature viscosity, base oil aromatics, etc) through the
application of somewhat different procedures. Each organization maintains an web site with extensive capabilities of
searching for specific methods. The addresses for each site
CONCLUDING REMARKS
It was the objective of this chapter to demonstrate that hydrocarbon base oils are a complex collection of molecules
whose diverse individual properties combine to determine
the performance characteristics of a formulated lubricant.
Examples and references have been provided that support
this objective and serve to highlight the overall importance
and complexity of base oil technology as an integral part of
the lubricant industry.
In addition, an effort was made to highlight those anal34ical techniques and predictive modeling procedures that enable the chemical composition of a base oil to be determined
and then exploited to predict how it will behave in actual
product applications. Although further research and method
development is still needed, a future can be envisioned where
actual engine tests, bench oxidation tests, or biological assays
are not needed to confirm the quality/toxicology of a base oil
relying, instead, on predictive modeling.
STANDARDS
ASTM
No.
D 92-01
IP
No.
36
D 93-00
34
D
D
D
D
97-96a
189-01
297-92
445-97
15
D
D
D
D
D
D
D
D
482-00
524-00
611-82
892-01
943-99
1492-96
1500-98
2007-01
D 2008-91
71
2
146
157
Method Description
Flash and Fire Points by Cleveland
Open Cup
Flash Point by Pensky-Martens
Closed Cup Tester
Pour Point of Petroleum Products
Conradson Carbon Residue
API Gravity
Kinematic Viscosity and Cal'c of
Dynamic Viscosity
Ash in Petroleum Products
Ramsbottom Carbon Residue
Aniline Point Determination
Lubricant Foaming
Oxidation of Inhibited Oils
Bromine Index
ASTM Color
Aromatics, Saturates, Polars in
Base Oil
UV Absorbance of Petroleum
Products
226
D 2272-98
D 2500-99
D 2549-91
219
D 2622-98
D 2710-99
D 2786-91
D 2887-01
D 2983-01
D 3228-96
D 3239-91
D
D
D
D
D
3339-95
3829-93
4289-97
4530-00
4624-93
D 4629-96
D 4636-99
D 4683-96
379
D 4741-00
D 4742-96
D 4871-00
D 4927-96
D 5293-99
D 5480-95
D 5481 -96
D
D
D
D
D
5483-95
5776-99
5800-00
5864-00
5949-96
D 5950-96
D 5985-96
D 6006-97
D 6074-99
D 6082-00
D 6366-99
D 6616-01
E 1687-98
REFERENCES
[1] Murray, D. W., MacDonald, J. M., White, A. M., and Wright, P.
W., "The Effect of Basestock Composition on Lubricant Oxidation Performance," Petroleum Review, February 1982, pp. 36-40.
183
[2] "Base Oils for Automotive Lubricants," Special Publication SP526, Society of Automotive Engineers, Warrendale, PA, 1982
(and references therein).
[3] Stipanovic, A. J., Smith, M. P., Firmstone, G. P., and Patel, J. A.,
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Lubricant Base Oils: Correlations to Sequence VE and IIIE
Gasoline Engine Tests," SAE Publication 941978, Society of Automotive Engineers, Warrendale, PA, 1994.
[4] Firmstone, G. P., Smith, M. P., and Stipanovic, A. J., "A Comparison of Neural Network and Partial Least Squares Approaches in Correlating Base Oil Composition to Lubricant Performance in Gasoline and Industrial Oil Applications," SAE
Publication 952534, Society of Automotive Engineers, Warrendale, PA, 1995.
[5] Smith, M. P., Stipanovic, A. J., Firmstone, G. P., Cates, W. M.,
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for Bench and Engine Tests," Lubrication Engineering, Vol. 52,
No. 4, 1995, pp. 309-314.
[6] Yoshida, T., Igarashi, J., Stipanovic, A. J., Thiel, C. Y., and Firmstone, G. P., "The Impact of Basic Nitrogen on the Oxidative and
Thermal Stability of Base Oils in Automotive and Industrial Applications," SAE Publication 981405, Society of Automotive Engineers, Warrendale, PA, 1998.
[7] Stipanovic, A. J., Firmstone, G. P., and Smith, M. P., "Having
Fun with Base Oils: Predicting Properties Using Neural Networks," Preprints (ACS Division of Petroleum Chemistry, Inc.),
Vol. 42, No. 1, 1997, pp. 284-286.
[8] Patel, I. A., Smith, M. P., Powers, J. R., Whiteman, J. R., and
Prescott, G. P., "Composition and Performance of a Hydroisomerized Wax Base Oil, Preprints (ACS Division of Petroleum
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[9] "1997 Report on U.S. Lubricating Oil Sales," National
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[10] Sequeira, A., Jr., Lubricant Base Oil and Wax Processing, Marcel
Dekker, Inc., NY, 1994.
[11] "1999 Lubricating Oil and Wax Capacities of Refiners and ReRefiners in the Western Hemisphere," National Petroleum and
Refiners Association (NPRA), 1999.
[12] A) Lubricants World, March 1999, p. 8.; B) Lubricants World,
March 2000, p. 8.
[13] Comitius, T., "Basestock Market Outlook," Lubricants World,
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[14] Speight, J. G., The Chemistry and Technology of Petroleum, 2"^
Edition, Marcel Dekker, Inc., NY, 1991.
[15] BP Petroleum, "Petroleum Refinery Products and Processes,"
Our Petroleum Industry, 1911, p. 230.
[16] Lane, E. C. and Garton, E. L., "Base of a Crude Oil," U.S. Bureau
of Mines-Report of Investigation 3279, Washington, DC, 1935.
[17] Barman, B. N., "Hydrocarbon-Type Analysis of Base Oils and
Other Heavy Distillates by Thin-Layer Chromatography with
Flame-Ionization Detection and by the Clay-Gel Method," Journal of Chromatography Science, Vol. 34, 1996, pp. 219-225.
[18] Sarpal, A. S., Kapur, G. S., Mukherjee, S., and Jain, S. K., "Characterization by 13C-NMR Spectroscopy of Base Oils Produced
by Different Processes," FMS/, Vol. 76, No. 10, 1997, pp. 931-937.
[19] Adhvaryu, A., Pandey, D. C, and Singh, I. D., "Effect of Composition on the Degradation Behavior of Base Oil," Preprints (ACS
Division of Petroleum Chemistry, Inc.), Vol. 42, No. 1, 1997, pp.
225-228.
[20] Coates, J. P. and Setti, L. C, "Infrared Spectroscopic Methods
for the Study of Lubricant Oxidation Products," ASLE Transactions, Vol. 29, No. 3, 1985, pp. 394-401.
[21] Altgelt, K. H. and Gouw, T. H., Chromatography in Petroleum
Analysis, Marcel Dekker, NY, 1979.
[22] Altgelt, K. H. and Boduszynski, M. M. "Composition and Analysis of Heavy Petroleum Fractions," Marcel Dekker, Inc., NY,
1994.
[39] Mooken, R. T., Saxena, D., Base, B., Satapathy, S., Srivastava, S.
P., and Bhatnagar, A. K., "Dependence of Oxidation Stability on
Base Oil Composition," Lubrication Engineering, 1997, p p .
19-24.
[40] Roby, S. H., Supp, J. A., Barrer, D. E., and Hogue, C. H., "Base
Oil Effects in t h e Sequence HID and Sequence V-D Engine
Tests, SAE Publication 892108, Society of Automotive Engineers, Warrendale, PA, 1989.
[41] Cherrillo, R. A. and Huang, A., "The Increasing Significance of
Base Oils in the Evolution of Heavy-Duty Diesel Engine Oils,"
1999 National Petroleum Refiners Association (NPRA), LW-99130, Houston, TX, 1999.
[42] Kramer, D. C , Ziemer, J. N., Cheng, M. T., Fry, C. E., Reynolds,
R. N., Lok, B. K., et al., "Influence of Group II and III Base Oil
Composition on VI and Oxidation Stability," National Lubricating Grease Institute (NLGI), Paper 9907, Tucson, AZ, 1999.
[43] Fresco, G. P., Klaus, E. E., and Tewksbury, E. J., "Measurement
and Prediction of Viscosity-Pressure Characteristics of Liquids," Journal of Lubrication Technology (ASME
Transactions),
Paper No. 68-Lub-8, 1968, pp. 1-7.
[44] Roelands, C. J. A., Vlugter, J. C , and Waterman, H. I., "The Viscosity-Temperature-Pressure Relationship of Lubricating Oils
and Its Correlation with Chemical Constitution," Journal of Basic Engineering, December 1963, pp. 601-610.
[45] Guangteng, G. and Spikes, H. A., "Boundary Film Formation by
Lubricant Base Fluids," Society of Tribologists and Lubrication
Engineers, Presentation 95-MP-7D-3, Chicago, IL, 1995.
[46] Tsubouchi, T., Abe, K., and Hata, H., "Quantitative Correlation
Between Molecular Structure of Traction Fluids and Their Traction Properties (Part 2): Precise Investigation into Molecular
Stiffness," Japanese Journal of Tribology, Vol. 39, No. 3, 1994,
pp. 373-381.
[47] Bair, S., "An Experimental Verification of the Significance of
the Reciprocal Asymptotic Isoviscous Pressure," ASLE Tribology
Transactions, April, 1993.
[48] A. J. Stipanovic, Unpublished Results.
[49] Johnston, W. G., "A Method to Cedculate the Pressure-Viscosity
Coefficient from Bulk Properties of Lubricants," ASLE Transactions, Vol. 24, No. 2, 1980, pp. 232-238.
[50] Nessel, C. S., Coker, D. T., King, A. G., and Mumford, D. L., "Carcinogenic Assessment of Lubricant Base Oils by Proton NMR,"
Preprints (ACS Division of Petroleum Chemistry), Vol. 42, No. 1,
1997, pp. 251-254.
[51] Trauth, E. J., "Future Product Development Needs-Comprehensive Life-Cycle Analyses," Lubricants World, July 1998, pp. 20-25.
[52] Tocci, L., "Clean Hydraulic Fluids," Lubes'n'Greases, November
1998, pp. 4 2 ^ 4 .
[53] Voltz, M., "Biodegradability of Lubricant Base Stocks and Fully
Formulated Products," Proceedings, ACS Petroleum Division
Symposium, San Diego, CA, 1994.
[54] Weller, D. E., Perez, J. M., and Keay, R. E., "Biodegradable Gear
Oils," Preprints (ACS Division of Petroleum Chemistry), Vol. 42,
No. 1, 1997, p p . 242-245.
MNL37-EB/Jun. 2003
DISCUSSION
In this chapter, a brief overview of the most common industrieJ production methods of C2, C3, and C4 synthetic hydrocarbons is provided. Typical purity standards and comm o n classes of impurities are also discussed. The chapter
also includes various types of ASTM analytical procedures
and the separation principles involved.
2003 by A S I M International
Hydrocarbon
Production
185
Copyright'
for Synthetic
www.astm.org
Boiling Range
(F)
Liquid Feedstock
Ethylene
Naphtha
Full range
Light
Heavy
Kerosine
Atmospheric gas oil
Light
Heavy
Vacuum gas oil
Gas condensates
80-430
80-300
250-430
400-500
400-680
600-800
800-1100
80-530
Naptha
Kerosine
Gas Oil
Kuwait
North Sea
Kuwait,
North Sea
0.839
0.1
0.724
0.04
28
121
175
0.801
0.03
180
206
242
29.7
220
290
380
27.7
72.3
50.9
41.8
16.7
15.8
10.5
14.9
7.9
19.2
14.1
20.9
4.0
11.0
known using feed streams from coal, ethanol, coke oven gas
and other sources, but these are rarely used. Therefore, S5T1thetic hydrocarbon p r o d u c t i o n from these alternative
sources will not be discussed in detail here.
The value of BMCI shown in Table 2 refers to the Bureau
of Mines Correlation Index. BMCI is used to estimate the
amount of ethylene in feedstocks. Higher numbers indicate
m o r e aromatic character. BMCI is calculated from the
following equation:
BMCI = VABP +
48640
473.7(^.5)
456.8
Production
[1]
Where: VABP is the volume average boiling point (K) and dis
is the density in g/mL at 15C.
The BMCI value estimates the extent of naphthenic and aromatic content of a hydrocarbon feedstock emd is calibrated for
hexane to yield 0% and pure benzene to yield 100%.
Synthetic hydrocarbon feedstocks are typically low in sulfur content. High sulfur feedstocks may be used, but these
materials produce larger quantities of acid gases, which must
be removed from the resulting products. Low chloride feedstocks should be used as chlorides may cause irreparable
damage in the furnace tubes due to chloride stress cracking
and corrosion.
It is possible to obtain any of the synthetic hydrocarbons
from any feedstock by steam cracking. Higher paraffinic content materials yield higher conversion to short-chain olefins.
The choice of feedstock for a steam cracker is typically deter-
In the steam cracking process, steam is added to the hydrocarbon feed stream to:
1. Reduce the partial pressure of the hydrocarbon
2. Reduce the high-temperature residence time
3. Reduce coke formation in the reactor. (Carbon monoxide
and hydrogen are formed by reaction of steam with carbon
at the high temperatures encountered in the reactor. This
is the famous "water-gas" reaction.)
Ethylene product yield, like that of other synthetic hydrocarbons, correlates with the carbon/hydrogen ratio of the
components in the feedstock being steam cracked. Generally,
as the feedstock becomes heavier (which is typically accompanied by increasing amounts of naphthenes and aromatics
and a corresponding lowering of the C/H ratio), the reaction
products become heavier and more aromatic, while conversion yields to lighter olefins decrease.
E t h a n e m a y be produced by Ci chemistry by thermal
cracking of methane at 1000C as shown in Scheme 1 [4].
This is not the preferred commercial route to ethane, however, because the bond dissociation energy of a CH bond of
93.3 kcal/mol is considerably higher than a CC bond-dissociation process of 71.0 kcal/mol [9], making this an energy inefficient process.
CH4 - CHs*
2CH3* -^ CH3 - CH3
S c h e m e 1Formation of ethane from methane.
Ethylene m a y be produced by the dehydrogenation of
ethane as shown in Scheme 2. This reaction process, like all
thermal cracking processes, is accompanied by side reactions, which lead to the formation of aromatic and naphthenic hydrocarbon ring structures.
CH3 - CH3 ^ CH2 = CH2 + H2
S c h e m e 2Ethylene formation by dehydrogenation of
ethane.
TABLE 3Selected feedstocks for synthetic hydrocarbon
production.
Gases or Gas Liquid Products
Ethane
Propane
Butane
Refinery off-gases
Liquid Feedstock
Naphtha
Kerosine
Raffinates from extraction processes
Atmospheric gas oil
Vacuum gas oil
Natural gasoline
Gas condensates
COUNTRY
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
COMPANY
BPCHEM.
BP CHEM.
COND.VISTA
CPCHEM
CPCHEM
CPCHEM
CPCHEM
CPCHEM
CPCHEM
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DOW
DUPONT
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EQUISTAR
EXXONMO.CH
EXXONMO.CH
EXXONMO.CH
EXXONMO.CH
EXXONMO.CH
FORMOSA PL
FORMOSA PL
HUNTSMANC
HUNTSMANC
HUNTSMAN C
JAVELINAC
SHELL CHEM
SHELL CHEM
SHELL CHEM
SHELL CHEM
SHELL CHEM
SUNOCO CH.
SUNOCO CH.
TEXAS EAST
WESTLAKECA
WESTLAKEPC
WESTLAKEPC
WILLIAMS 0
SITE
AVJimx
ALVIN/TX
LAKECWLA
OEDAR BAYO
PORTAR/TX
SWEENY/TX
SWEENYm(
SWEENY/TX
SWEENY/TX
FREEPORT/T
FREEPORT/T
PLAQUEMINE
PUQUEMINE
SEADRIFT/TX
TAFT/U
TAFT/U
TEXAS CITY/rx
ORANGE/TX
CHANNELVIE
CHANNELVIE
CHOC.BAYOU
CLINTON/IA
CORPUS/TX
LfiPORJEfTX
LAKECH/LA
MORRIS/IL
BATON R/LA
BAYTOWN/TX
BAYTOWN/TX
BEAUMON/TX
HOUSTOWrX
POINT CX5MF/TX
POINT CMF/TX
ODESSAAJS
PORTAR/TX
PORTNECHE
CORPU^TX
DEER PA/rX
DEER PA/rX
NORCO/LA
NORCO/U
NORCO/LA
BRANDENBUR
CLAYMONT/D
LONGVIE/TX
CALVERT CI
LAKECHAA
LAKECHflJ^
GEISMAR/LA
ROUTE
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBOI
HYD-CARK)N
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARODN
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
RFRY-QAS
HYD-CARBON
RFRY-GAS
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
HYD-CARBON
TECHNOLOQY
STCRACKIN
ST CRACKIN
ST CRACKIN
STCRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
ST CRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
ST CRACKIN
ST CRACKIN
STCRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
ST CRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ETH RECOV
ST CRACKIN
N.A.
STCRACKIN
STCRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
STCRACKIN
STCRACKIN
ST CRACKIN
STCRACKIN
ST CRACKIN
LICENSOR START
NA.
1975
1977
BRAUN
N.A.
1^8
1977
LUMMUS
1970
LUMMUS
1957
N.A.
N.A.
1967
BRAUN
1978
BRAUN
1991
DOW
1972
1994
BRAUN
HA.
1972
DOW
1980
1957
N.A.
1967
LUMMUS
1978
LUMMUS
N.A.
1969
LUMMUS
1967
1976
UMIMUS
LUMMUS
1977
1980
N.A.
1^8
KELLOGG
S&W
1980
KELLOGG
1991
N.A.
1971
LUMMUS
1972
1972
LUMMUS
KELLOGG
1979
1997
EXXON
N.A.
1961
N.A.
1978
1994
KELLOGG
2001
KEUOGG
N.A.
1965
1979
S&W
N.A.
1978
N.A.
0
1978
KELLOGG
N.A.
0
KELLOGG
1975
1981
KELLOGG
N.A.
2000
1952
N.A.
1961
N.A.
1974
KELLOGG
BRAUN
1964
KELLOGG
1991
1997
LUMMUS
1968
LUMMUS
40%
C3H8 -^ C3H6 + H2
36%
10%
14%
n - C4H10 ^ H2 + 2C2H4
/ - C4H10 -^ H2 + i - C4H8
C3H7 ^ H + C3H6
>
r:
Acid Gas
Removal
Compression
Quench
* Pyrogasoline Product
Chilling
Train
Dryers
Secondary
Dryers
Acetylene
Reactors
H2. CH4.
Compression
Depropanizer
C-4+
Ethylene
Recovery
Demethanizer
(H2, CH4)
_w Off-Gas
Deethanizer
Ethylene
Refiigeration
Ethylene
" Product
C-2 Splitter
Propylene
Product
T}
Pyrogasoline
Product
prude C-4
Product
C3,C3=,MA, PD
Ethane
Recycle
Propane
Recycle
Propylene Production
Propylene is most often produced by either steam cracking or
cataljrtic cracking. Propylene is a major by-product from ethylene production when feedstocks heavier than ethane are
used. In steam cracking, generally, the heavier the feedstock,
the greater the a m o u n t of propylene produced relative to ethylene. It is not unusual for propylene production to amount to
40-70% of ethylene production [1]. It should be noted, however, propane and low boiling liquid feedstocks may not conform to this pattern if the cracking severity is low. This is why
such plants are more often called "olefin plants." Since ethylene and propylene are co-produced in the same units, propylene production will not be detailed separately here.
Table 7 provides a summary of typical product specifications for polymer grade propylene. The physical properties of
propylene are summarized in Table 6.
Butylene and Butadiene Production
Reaction Chemistry and MechanismButadiene
may be synthesized by dehydrogenation of n-butenes at 1100-1250F
(593-677C) over a metal catalyst as shown in Scheme 8 [21].
However, due to the relatively high temperatures required for
conversion, the reaction selectivity is often poor. Reaction
Component
Ethylene
Methane and ethane
Hydrogen
Acetylene
Propylene and propane
Oxygen
Carbon monoxide
Carbon dioxide
Water
Methanol
Total sulfur
C4H8 O C4H6 + H2
Scheme 8Butadiene synthesis by butene dehydrogenation.
temperatures may be reduced to 750-1100F (399-593C),
thus permitting improved selectivity, by introducing air
(steam + oxygen) into the reaction (oxidative dehydrogenation) as shown in Scheme 9. Catalysts that have been reported
to produce good yields include: bismuth molybdate, mixed ox-
Ethylene [1]
28.05
-169.19
0.11
3350
-103.71
13 540
20.27
67.4
1.61 X 10""
0.0164
42.84
Propylene
42.08
-185.26
9.54 X 10"^
3003
-47.6
18 420
14.47
1-Butene
Cis-2-Butene
Trans-2-Butene
1,3-Butadiene
56.11
56.11
56.11
54.09
-185.35
-138.91
-105.55
-108.92
3848
7309
9757
7980
1.92 X lO""*
.0167
62.49
-6.25
21 917
11.15
118
1.98 X lO"'*
.0160
88.49
3.72
23 349
11.43
127
1.73 X 10"''
.0156
76.89
91.8
4.62
5.52
0.2750
2.058
146.4
4.02
4.153
0.2760
2.719
0.88
22 757
11.17
1.79 X 10"^
.0160
86.00
-4.4
22 597
12.03
123.6
1.98 X 10"^
.0176
77.13
162.4
4.21
4.277
0.2720
2.712
155.5
4.10
4.207
0.2740
2.707
151.9
4.33
4.525
0.2700
2.541
1.6
10.0
385
1.6
9.7
325
1.6
9.7
324
2.0
11.5
420
297.1
213.7
234.1
281.1
Jmor^K"'
Critical point
Temperature, C
Pressure, MPa
Density, mol/dm^
Compressibility factor
Gross heat of combustion of the gas
(25X), MJ/mol
Limits of flammability of atmospheric
pressure at 25C
Lower limit in air, mol%
Upper limit in air, mol%
Autoignition temperature in air at
atmospheric pressure, "C
Vapor pressure at 25C, kPa
9.2
5.042
7.635
0.2813
1.411
2.7
36
490
7065
1.9
11.1
455
1156
Concentration
99.5 mol% min
0.4 inol% max
5 mol ppm max
100 mol ppm max
1 mol ppm max
5 mol ppm max
5 mol ppm max
5 mol ppm max
5 mol ppm max
5 mol ppm max
5 mol ppni max
2 mol ppm max
10 mass ppm max
1 mass ppm max
stream is quenched by cooling, washed in a wash tower to remove oxygenated bjrproducts, and finally scrubbed with an
oil to extract the organic products from nitrogen and carbon
dioxide. The hydrocarbons Eire removed by stripping them
from the oil a n d then using extractive distillation to recover
the butadiene.
Most of the butadiene production in the world today is obtained as a by-product of ethylene manufacture (see Table 8).
When there is excess capacity, butadiene may be selectively
hydrogenated to butenes. Alternatively, excess butadiene
n-BUTANE
n-BUTANE
BUTANE CATALYTIC
DEHYDROGENATION
(HOUDRY)
BUTANE CATALYTIC
DEHYDROGENATION
BUTANE
; BUTANE ONLY ;
'-in
BUTADIENE SEPARATION
1 BUTENES SEPARATION i
(FURFURAL EXT. DIST.)
BUTADIENE
I BUTENES i
BUTENE DEHYDROGENATION
K ( 0 ) + C4H8 -^ K(OC4H8)
CAT^kYTIC
r 'o)(YDiHYDROGENATibNi
j f STEAM
i.-i
191
BUTADIENE SEPARATION
(FURFURAL EXT. DIST)
AIR
*.
BUTENE
OXYDEHYDROGENATION
CATALYTIC
4 . . I BUTADIENE SEPARATION
K ( ) + O2 ^ K ( 0 2 ) + K ( ) ^ 2 K ( 0 )
S c h e m e 10Mechanism of butylenes synthesis by oxidative dehydrogenation.
The first reaction in Scheme 10 can act to isomerize 1butene into cis- and trans-2-butene [26]. The reactivity of the
butene isomers on an aluminum oxide catalyst decreases in
the following order: 1-butene > cis-2-butene > trans-2b u t e n e [27]. Unsaturated carbonyl c o m p o u n d s can b e
formed as byproducts. Adzhamov reports that these carbonyl
compounds inhibit the oxidative dehydrogenation process
and butene isomerization [28]. Other by-products that are
possible include furan, acetaldehyde, acetone, acrolein,
formaldehyde, methyl ethyl ketone, methyl vinyl ketone, and
other carbonyl compounds and carbon dioxide [27].
Commercial Butadiene Production Processes^Two industrial
processes for butadiene production by oxidative dehydrogenation are the Phillips Petroleum Company Process [24,25]
and the Petro-Tex Chemical Company Process [22]. These
two processes are illustrated schematically in Fig. 2 [30,31].
The butene feed stream is typiccJly mixed with steam and air
and passed through a fixed-bed reactor. The reaction product
BUTADIENE
Note: BROKEN LINES INDICATE AN ENLARGEMENT OF AN EXISTING
OPERATION OR THE ADDITION OF A NEW OPERATION.
Composition
0.1 mol% max
35-75 mol%
0.2-0.5 mol%
0.7-1.4 mol%
4-5 mol%
4.5-6.5 mol%
20-30 mol%
15-25 mol%
5-15 mol%
0.5-1 mol%
0.1 mol% max
5 mass ppm max
HANDBOOK
CHAPTER 8: HYDROCARBONS
these components may affect the commercial use of propylene concentrates.
In Test Method D 2712, a relatively large volume of sample
is charged to a gas partition chromatograph equipped with a
column that will separate trace hydrocarbon constituents
from the major components. Any column or combination of
columns may be used providing that they exhibit the necessary resolution. Various columns that have been used successfully are provided in Table 1 of Test Method 2712.
Determination of Trace Methanol in Propylene Concentrates
(Test Method D 4864)Methanol is a common impurity in
propylene. It can have a deleterious effect on various processes that use propylene as a feedstock. Test Method D 4864
determines methanol in propylene concentrates in the range
of 4 ^ 0 parts per million by weight.
For Test Method D 4864, a known weight of water is measured into a sample cylinder containing a known amount of
liquefied propylene. The contents in the cylinder are shaken
and the water/methanol phase is withdrawn. A reproducible
volume of the extract is then injected into a gas chromatograph equipped with either a thermal conductivity or a flame
ionization detector. The methanol concentration is calculated from the area of the methanol peak using calibration
and extraction factors obtained from synthetic blends of
known methanol content.
Determination of Trace Carbonyl Sulfide (COS) in Propylene
(Test Method D 5303)This test method measures traces of
COS in propylene in the range of 0.5-4.0 parts per million by
mass. In propylene producing processes, COS usually remains with the C3 and must be removed since it affects product quality. COS acts as a poison to commercial polymerization processes, resulting in deactivation and costly process
downtime. Accurate gas chromatographic determination of
trace COS in propylene involves unique analyticcJ problems
because of the nature of COS and idiosyncrasies of trace level
analyses. These problems result from the reactive and adsorptive nature of COS, the low concentrations being measured, the tj^e of detector needed, and interferences from the
propylene sample matrix. Test Method D 5303 addresses
these analytical problems and ways to properly handle them
to assure accurate and precise analysis.
Separation of the COS from propylene is accomplished by
gas chromatography. A relatively large volume of sample is
injected onto a gas chromatograph equipped with a single
packed column and flame photometric detector. The separation is achieved isothermally at 10-50C. Calibration data,
based on peaJi areas, are obtained using a known gas standard blend of COS in the range expected for the sample. The
COS peak area in the sample is measured and the concentration of COS is calculated.
C-4 Product Characterization
Guide for Analysis of 1,3-Butadiene (Standard Guide D
5274)Standard Guide D 5274 covers the analysis of I,3-butadiene products produced in North America. Standard
Guide D 5274 is intended to provide information on the likely
composition of 1,3-butadiene products and possible ways to
test them. Since there are currently no ASTM test methods
for determining all components of interest. Standard Guide
D 5274 provides information on other available test methods.
193
194
MANUAL
HANDBOOK
CHAPTER
8: HYDROCARBONS
AND SPECIALTY
USES
195
This is a complicated gas chromatography method. Molecular size is determined by using boiling point columns or
molecular sieve columns. Polar columns separate by polarity.
Hydrogenation is done on column using a platinum lined
column a n d hydrogen gas. In addition, t e m p e r a t u r e programming is used for separation.
Determination of Boiling Range (Test Methods D 2892 and D
2887)Test Method D 2892 details procedures for the production of a liquefied gas, distillate fractions, and residuum
of' standardized quality o n which analytical data can be obtained, and the determination of yields of the above fractions by b o t h mass and volume. From the above information, a graph of temperature versus mass-percent distilled
can be produced. This distillation curve corresponds to a
laboratory technique, which is defined at 15/5 (15 theoretical plate column, 5:1 reflux ratio) or TBP (true boiling
point). This test m e t h o d can also be applied to any
petroleum mixture except liquefied petroleum gases, very
light naphthas and fractions having initial boiling points
above 400C.
Alternatively, the boiling range distribution of petroleum
fractions may be determined by gas chromatography using
Test Method D 2887. This test m e t h o d is applicable to
petroleum products and fractions having a final boiling point
of 538C (1000F) or lower at atmospheric pressure and is
limited to samples having a boiling range greater than 55C
(100F) and having a vapor pressure sufficiently low enough
to p e r m i t sampling at a m b i e n t t e m p e r a t u r e . For m o r e
volatile p e t r o l e u m fractions, including oxygenated compounds. Test Method D 3710 should b e used.
ASTM STANDARDS
No.
D 1018
D 1025
D 1157
D 1550
D 2163
D 2384
D 2426
D 2504
D 2505
TABLE 9ASTM D 4808 test procedures available for
different petroleum products.
Approximate Boiling Range
"C (-F)
Petroleum Products
Test Method
A
Light distillates
15-260(60-500)
B
Middle distillates
200-370 (400-700)
B
Gas oil
370-510(700-950)
C
Residual
510+ (950+)
FOR CHEMICAL
D 2593
D 2712
D 2887
Title
Standard Test Method for Hydrogen in Petroleum
Fractions
Test Method for Nonvolatile Residue of Polymerization Grade Butadiene
Test Method for Total Inhibitor Content (TBC) of
Light Hydrocarbons
ASTM Butadiene Measurement Tables
Test Method for Liquefied Petroleum (LP) Gases
and Propylene Concentrates by Gas Chromatography
Test Methods for Traces of Volatile Chlorides in
Butane-Butene Mixtures
Test Method for Butadiene Dimer and Styrene in
Butadiene Concentrates by Gas Chromatography
Test Method for Noncondensahle Gases in C2 and
Lighter H y d r o c a r b o n Products by Gas Chromatography
Test Method for Ethylene, Other Hydrocarbons,
and Carbon Dioxide in High-Purity Ethylene by
Gas Chromatography
Test Method for Butadiene Purity a n d Hydrocarbon Impurities by Gas Chromatography
Test Method for Hydrocarbon Traces in Propylene Concentrates by Gas Chromatography
Test Method for Boiling Range Distribution of
Petroleum Fractions by Gas Chromatography
196
MANUAL
D 2892
D 3246
D 3710
D 4423
D 4424
D4808
D 4864
D
D
D
D
5234
5273
5274
5303
D5443
D 5799
D 6159
HANDBOOK
OTHER STANDARDS
D e u t s c h e s I n s t i t u t fur N o r m u n g ( D I N )
ISO 6684:1982
ISO 6792:1982
150 7381:1986
ISO 7382:1986
ISO 8174:1986
ISO 8175:1986
ISO 8176:1986
ISO 6378:1981
ISO 6379:1981
ISO 6380:1981
ISO 6381:1981
UOP
UOP 212-77
UOP 344-87
UOP 496-63T
UOP 542-88
UOP 569-79
UOP 603-88
UOP 772-77
UOP 791-94
UOP 834-82
UOP 845-90
[17] Fair, J. R. and Rase, H. F., "Process Design of Light Hydrocarbon Cracking Units," Chemical Engineering Progress, 1954, Vol.
50, No. 8, pp. 415-420.
[18] Schutt, H. C , "Optimum Temperature Profile for Endothermic
Conversions in Tubular Reactors," Zeitschrift fuer Elektrochemie. Vol. 65, 1961, pp. 245-255.
[19] Buell, C. K. and Weber, L. J., "Ethylene Production by Cracking
of Ethylene-Propylene Mixtures," Petroleum Processing, Vol. 5,
March 1950, pp. 266-272.
[20] Kamptner, H. K., Krause, W. R., and Shilken, H. P., "High-Temperature Cracking," Chemical Engineering, Feb. 28 1966, pp.
93-98.
[21] Schutt, H. C. and Zdonik, S. B., "Processing Scheme-Pyrolysis
Methods," Oiland Gas Journal, Vol. 54,2 April 1956, pp. 99-103.
[22] Haddeland, G. E., "Butadiene," Process Economics Program,
Report No. 35, Stanford Research Institute, Menlo Park, CA,
March 1968.
[23] Anonymous, "New Plants and Facilities, CE Construction
Alert," Chemical Engineering, April 5 1971, pp. 111-116.
[24] Nolan G. J., Hogan R. J., and Farba F., Jr., "2-Butene Dehydrogenation Catalyst," U.S. Patent 3,501,547, 17 March 1970.
[25] Friedman, L., Womeldorph, D. E., a n d Stevenson, D. H.,
"Houdry Dehydrogenation for Olefin Production," Proceedings
of the American Petroleum Institute, Sect. Ill, Vol. 38, 1958, pp.
203-212.
[26] Shchukin, V. P., Ven'yaminov, S. A., and Boreskov, G. K. "IronAntimony Oxide Catalysts of Partial Oxidation. III. Kinetics and
Mechanism of the Oxidative Dehydrogenation of Butylenes,"
Kinetika I Kataliz, Vol. 11, No. 5, 1970, p p . 1236-1242.
[27] Echigoya, E., Watanabe, T., and Sano, H., "Studies on Oxidative
Dehydrogenation of Butylenes over Bismuth Molybdate Catalyst," Journal of the Chemical Society of Japan, Industrial Chemistry Section, Vol. 73, No. 5, 1970, pp. 933-937.
[28] Skarchenko, V. K., "Oxidative Dehydrogenation of Hydrocarbons," International Chemical Engineering, Vol. 9, No.l, 1969,
pp. 1-23.
[29] Adzhamov, K. Y., Alkhazov, T. G., Belen'kii, M. S., and Lisovskii,
A. E., "Effect of Carbonyl Compounds on the Oxidative Dehydrogenation of Butenes," Kinetika i Kataliz, Vol. 9, No. 6, 1968,
pp. 1279-1284.
[30] Newman, F. C , "Process for Butadiene Manufacture by Oxydehydrogenation of Butenes," Industrial and Engineering Chemistry, Vol. 62, No. 5, 1970, p p . 42-47.
[31] Husen, P. C , Deel, K. R., and Peters, W. D., "Phillips Butadiene
Process is Success," Oil and Gas Journal, 2 Aug 1971, pp. 60-61.
[32] Reis, T., "Compare Butadiene Recovery Methods Processes, Solvents and Economics," Petro/Chem Engineer, August 1969, pp.
12-22.
[33] Reis, T., "Butadiene Extraction," Chemical and Process Engineering, March 1970, pp. 65-69, 72-76.
[34] Baron, T., "Precise Separations and Selective Extractions are
Keys to Petrochemicals," Oil and Gas Journal, 1971, July 5, Vol.
67, No. 27, p p . 100-102.
MNL37-EB/Jun. 2003
base oils and synthetic basestocks, do not possess the properties necessary to perform effectively in today's demanding
lubricating environments. To function in such environments
properly, base fluids need the help of chemicals called additives. Additives improve the lubricating ability of base oils, either by enhancing the desirable properties already present or
by adding n e w properties. Such properties include suitable
viscosity, slipperiness, high film-strength, low corrosivity,
low pour point, good cleansing and dispersing ability, low
toxicity and low flammability [1]. Most of today's lubricants
are formulated lubricants, and additives are their integral
part. The 1998 world consumption of lubricant additives is
estimated at 2.588 million metric tons, of which North America a n d Western Europe consumed 67%. This estimate is
based on 1995 SRI data [2] and the estimated growth rate.
LUBRICANT COMPOSITION
A formulated lubricant comprises a base fluid and a performance package, and in the case of multigrade oils, an additional viscosity modifier. The performance package contains
a n u m b e r of additives, the quantity of which is a function of
their quality (the ability to deliver the necessary performance), the quality of the base fluid (governed by its physical
and chemical properties), and the lubricant's intended use.
The performance package can make u p to 30%, and sometimes even higher, of the total lubricant composition, depending upon the desired performance level and the severity
of the end-use requirements [3]. In general, poor-quality base
fluids need better additives a n d in larger amounts than base
fluids of good quality. Likewise, applications such as engine
oils a n d automotive gear oils, which place a higher demand
on the lubricant, require superior additives than those that
are less demanding. Engine oils account for the largest shaire
of the additive use.
LUBRICANT BASESTOCKS
Lubricants perform a variety of functions to prolong the life
of the equipment. These include lubrication (reduction of
friction and wear), dissipation of heat, corrosion control, prevention of excessive deposit formation, dispersion of use-gen' Research and Development Manager, Lubricant Additives Division, King Industries, Inc., Science Road, Norwalk, CT 06852.
199
Copyright'
2003 by A S I M International
www.astm.org
200
MANUAL
HANDBOOK
PERFORMANCE PACKAGE
Lubricant additives are usually supplied as performance
packages that are blended in basestocks to yield formulated
lubricants. This is not the case in some applications, such as
metalworking fluids, where the end user may purchase the
individual additives and blend them in base oil prior to use.
In the U.S., foixaulated lubricants are expected to meet performance requirements generally established by the Society
of Automotive Engineers (SAE), American Petroleum Institute (API), U.S. Military, Original Equipment Manufacturers
POLAR MOIETY
Surface Active Group
NON-POLAR MOIETY
Oleophilic Group
Consistsof a hydrocaibon
chain
POLAR GROUP
Surface-active
NONPOLAR GROUP
Oil-solubllizing
H H H H H . H H
H3C' X X X W
HH
H H
HH
H!
HHHHHH|!,,!,HHHHHH
;o
Oleic Acid
FIG. 1A general representation of a typical additive
molecule.
201
that make up the lubricant. The reaction sites, in order of decreasing ease of attack, are benzylic, allylic, tertiary alkyl, secondary alkyl, cind primary alkyl hydrogens. The result is the
formation of hydroperoxides and peroxy or other radicals.
The rate of oxidation of hydrocarbons in addition depends
upon the amount of oxygen, presence or absence of nitrogen
oxides (NOx, a general term used for NO and NO2), ambient
temperature, and the presence or absence of metal ions.
Hydrocarbon oxidation is a three-step process, and comprises initiation, propagation, emd termination (Fig. 2). Initiation involves the attack of atmospheric oxygen or of nitrogen
oxides (NOx) on hydrocarbon molecules. The result is the formation of hydroperoxides (ROOH) and alkyl (R*) and peroxy
(ROO') radicals. During the propagation stage, hydroperoxides decompose either on their own or in the presence of metal
ions to alkoxy (RO') and peroxy radicals. These react with the
lubricant hydrocarbons to form a variety of additional radicals and oxygen containing compounds, such as alcohols,
aldehydes, ketones, and carboxylic acids [see the chapter on
Oxidation]. Aldehydes and ketones are highly reactive and can
form polymers in the presence of acids, such as nitric and sulfuric acids. These acids result from the interaction of nitrogen
oxides and sulfur oxides, products of combustion, with water.
Carboxylic acids attack iron, copper, and lead, present in the
mechanical equipment, to form metal carboxylates that further increase the rate of oxidation. During the termination
stage, the radicals either self-terminate or terminate by reacting with oxidation inhibitors [8]. Oxidation inhibitors (InH)
circumvent the radical chain mechanism by promoting deRH
O2
ROOH
RH
O2
ROO-+H
RH
+-NO,
'
Initiation
R- + HNOx
ROOH
>v
RO- + OH-
ROOH + Fe+2
-*-
ROOH + Fe*'
-*
ROO- + Fe*^ + H*
ROO - RH
-*
ROOH R-
ROO-
-*-
R- O2
RO - ! RH
-*
R O H -I- R-
OH- + RH
*-
H2O
ROO- + ROO-
*-
RR + 2O2
ROO- + InH
*-
ROOH + In-
RO- + InH
-^
ROH + In-
R- + InH
-*
R H I n -
> Propagation
R-
>-
Termination
RH = Hydrocarbon
ROOH = Hydroperoxide
R - = Alkyl Radical
InH = Inhibitor
202
MANUAL
HANDBOOK
1. Hydroperoxide Decomposers
R-S-(S)rS-R
DialkyI polysulfide
RQ.,,S
(R0)2R,
H
:>-c'
Zn
RO'%
CHo
R
DialkyI hydrogen
phosphite
Alkylphenol
Zinc dialkyi
dithlophosphate
2. Radical Scavengers
Methylene coupled
dlthlocarbamate
3. lUletal Deactivators
2,6-DI-f-butyl-4-methylphenol
Alkylated diphenylamine
203
Hydroperoxide
RCH2CH(CH3)2 + O2
CH3
_,OH
R<hr^=S:,^~.
O2
'^"-X^-^*^^
Hydroperoxide
*-
RCH2CH(CH3)2 +
Alkene
RCH2CH(CH3)2 + N O ,
HNO,
o-
R ^ ^ C H 3
R^^N^CHj
. OH
CH3
CH3
Hydroperoxide
O
Alltoxy radlcai
.OH
O+ NO,
R ^ x k , ^ ^
MONO
Allyloxy radical
Hydroperoxide
o-
ONO
/
RCH2CH(CH3)2
I
RCH2CH(CH3)2
Nitrite Ester
RCH2CH(CHi)2 + NO2
RCHiCHCCHjlj-
RCH=CH(CH3)2
NO2
NItroalkane
ONO2
+ NO2 *
Aliyioxy radical
^<!x^;^^^/^
Nitrate Ester
Dispersants
Dispersants are additives that suspend oil-insoluble resinous
oxidation products and particulate contaminants in the bulk
oil. By doing so, they minimize sludge formation, particulaterelated abrasive wear, viscosity increase, and oxidationrelated deposit formation. Dispersants perform these functions by:
solubilizing polar contaminants in their micelles.
stabilizing colloidal dispersions in order to prevent aggregation of their particles and their separation out of oil.
suspending such products, if they form, in the bulk lubricant.
modifying soot to minimize its aggregation and oil thickening.
lowering surface/interfacial energy of dirt to decrease its
tendency to adhere to surfaces.
Dirt is a generic term that describes undesirable materials
that result from oxidative degradation of the lubricant, the
reaction of chemically reactive species (such as carboxylic
acids) with the metal surfaces in the engine, or the decomposition of thermally unstable lubricant additives, such as extreme pressure agents.
HANDBOOK
Fuel
JNOx
Liquid Nitrated and Oxygenated lUlonomers
Lubricant
Carbon
Water
\
Solids
/
Varnish
Resin
-Sludge
-" Varnish
Accumulate as
deposits in areas
of low oti velocity
Resin-coated
Soot Particles
Resin + Soot
Soot-coated
Resin Particles
Resin + Soot + Oil + Water
-*-
Lacquer
Sludge
^
A
Soot
Resin
o-
Additive
Separation
Distance
FiG. 7iVIeclianism of steric stabiiization.
c : ^ ^
Particle ) ^
cAi,
c^^
205
with like charges, which minimizes agglomeration. The development of charged particles in a low-dielectric medium,
such as oil, can be explained in two ways [18]. According to
the first explanation, the dispersant is already ionized and
through adsorption imparts a chcirge to the particle (depicted
by mechanism A in Fig. 8). According to the second explanation, the non-ionized dispersant adsorbs onto the surface of
the particle, an acid-base reaction involving the transfer of a
proton or another ion occurs, and the counter-ion desorbs resulting in the formation of a charged particle. Particles with
like charges repel one another, thereby preventing agglomeration. This is shown in part B of the exhibit. Neutral and high
soap detergents, discussed in next section, are believed to
perform via this mechanism. It is important to note that for
certain classes of dispersants, both mechanisms might be operating simultaneously.
Interestingly, empirical data suggest that the ionic mechanism, although it seems unlikely due to the organic nature of
the lubricant medium, does operate [18].
The essential performance features in a dispersant are its
thermal and oxidative stability, its low-temperature properties, and above all its ability to disperse soot, deposits, and
deposit precursors. Poor thermeJ stability can impair a dispersant's ability to disperse polar oxidation and decomposition products in the bulk lubricant. Poor oxidative stability
can make a dispersant contribute towzirds deposit formation.
Low temperature properties of the modem lubricants are
gaining importance. The use of light base oils to meet low
temperature requirements in finished lubricants is no longer
possible because of the volatility specifications (ASTM D
5480 and D 5800). The use of pour point depressants for
paraffinic oils has limited utility because it only affects some
low temperature properties, such as pour point, but not others, such as cold cranking. Base oil manufacturers therefore
use a number of strategies to develop base oils with good low
temperature properties. These include isomerization via hydrocracking and use of special synthetic oils as additives. Because dispersant is a major component in engine oil formulations, its structure can antagonize low-temperature
properties of these oils. And of course soot and deposit control, or dispersancy, are the primary functions of a dispersant. If a dispersant does not possess these properties, it is
not effective as an additive.
A dispersant contains three structural features: a hydrocarbon group, a polar group, and a group that connects the two
together, the connecting group or a link. These are depicted
in Fig. 9 by a graphic representation of a disperscuit molecule.
While each structured feature affects a different property or
properties in a dispersant, all three are essential to a dispersant's oversdl performance. The nature of the hydrocarbon
Connecting Group
Nitrogen or o)^gen _
Derived Functionality
206
HANDBOOK
group impacts all key properties, namely, thermal and oxidative stability, low-temperature performance, and dispersancy. Its structure can influence a dispersant's thermal and
oxidative stability and low-temperature properties. Its degree
of branching can improve or hurt the low temperature properties and compatibility with the additive package. Its molecular weight can affect dispersancy. The hydrocarbon radical
in dispersants is oligomeric or polymeric and is usually
aliphatic in nature. It contains 70 to 200 or more carbon
atoms to ensure good oil solubility. A polyisobutenyl alkyl
group is the most commonly used hydrocarbon group. In
some dispersants, the hydrocarbon moiety is derived from a
high molecular weight polymer, such as olefin copolymer,
polyacrylate, polymethacrylate, or styrene-ester polymer.
Such dispersants can also function as viscosity modifiers and
are appropriately called dispersant viscosity modifiers.
The link is the weakest portion of the dispersant molecule
because of its chemical structure. It can fall apart thermally
or chemically, making a dispersant ineffective. The most
commonly used polar groups are alcohol and amine derived.
They can oxidize, hydrolyze, and or thermally degrade and
make dispersant molecule lose its structural integrity. The
size and the nature of the polar group (whether it is oxygen
or nitrogen-based) determine dispersancy.
Chemical classes suitable for use as dispersants include
cilkenylsuccinimides, alkenylsuccinate esters, high molecular
weight amines, Mannich bases, and phosphonic acid derivatives. Polyisobutenylsuccinic acid derivatives (succinimides
and succinate esters) are commercially the most commonly
used dispersant types.
Both succinimides and succinate esters are prepared from
alkenylsuccinic anhydrides. Polyisobutylene (the most com-
PIB
<"
Polyisobutylene
PIB
Polyisobutenyl
Succinic Anhydride
Maleic Anhydride
""'^ ~ |
H2NCH2CH2NHCH2CH2N
,NCH2CH2NHCH2CH2l<^
\
Alkylenepolyamlne
Polyisobutenylsucclnlmlde
Polyisobutenyl
Succinic Anhydride
H2
R'
,C
PIB
PIB
HOH2C-CCH2OH
R
Polyisobutenyl
Succinic Anhydride
Polyol
V
o
R'
/
Y~CH20
R
<j^^CH20R
Polylsobutenylsuccinate Ester
FIG. 10Synthesis of alkenylsuccinimides and alkenylsuccinates.
207
MANNICH DISPERSANTS
?"
Js.,.CH2NCH2CH2NHCH2CH2Nv
CH2O + H2NCH2CH2NHCH2CH2N
R'
'^
Alkylenepolyamine
Polyaminomethylalkylphenol
Alkylphenol
R=Polyisobutyl Group
PHOSPHONIC ACID DISPERSANTS
PIB
Polylsobutylene
P2S5
Adduct
PIBP-OH
Phosphorus
Pentasulfide
or
OH
PIBP-OH
OH
Polyisobutylenethiophosphonic Acids
S
11
PIBP-OH
I
OH
Alkenylphosphonic
Acid
Pro
Propylene Oxide
S
II
CH3
I
PIBPOCH2CH O H
I
OCH2CH O H
Bis-hydroxypropyl
Alkenylthiophosphonate
I
CH,
Alkylene or Pdyalkyleneamine
Derived Bridging Group
Hydrocarbon
Groups
low. The excess base per equivalent of acid in metal hydroxide-containing detergents is generally lower t h a n t h a t in
metal carbonate-containing detergents. Detergents are described chemically in terms of their metal ratio, soap content,
sulfated ash (ASTM D 874), degree of overbasing or conversion, and total base n u m b e r (TBN) [5].
Let us represent a detergent, for example a basic calcium
sulfonate, by the general formula (RS03)vCaw(C03)a:(OH)y ,
where v, w, x, and y denote the n u m b e r of sulfonate groups,
the n u m b e r of calcium atoms, the n u m b e r of carbonate
groups, and the n u m b e r of hydroxyl groups, respectively. The
metal ratio is defined as the total equivalents of metaJ per
equivEdent of acid. Since calcium is a divalent metal, each
atom of calcium represents two equivedents. Hence, the metal
ratio can be Ccilculated by the equation.
Metal Ratio =
2\v
N u m b e r of equivalents of base ^ .
Number of equivalents of acid
2w
X 100
In other words, conversion is the metal ratio times 100. Neutral detergents have a conversion of 100 because the ratio of
equivalents of base to the equivalents of acid is 1. Soap content refers to the a m o u n t of neutral organic acid salt and reflects a detergent's cleansing ability, or detergency, and dirt
suspending ability. The soap content can be determined by
the use of the following formula.
Percent soap
(2w - v) X 56100
Effective formula weight
SO,
!<
R
Alkylbenzenesulfonic
Acid
Alkylbenzene
COOK
Olefin
Plienol
R=Alkyl Group
Sulfur CoupledAlkylphenol
or Phenol sulfide
PIB
Polyisobutylene
Methylene Coupled
Alkylphenol
H,0
P,S
2*5
Adduct
Phosphorus
Pentasulfide
209
RIBP-OH
I
OH
Polyisobutenylphosphonic
Acid
X = O or S
FIG. 13Detergent substrates.
210
MANUAL
HANDBOOK
with these compounds and keep t h e m in solution. The mechanism by which detergents perform is analogous to that of
dispersants, which is shown in Figs. 7 and 8. Depending upon
the lubricant's end-use, insoluble by-products may be soot,
acidic decomposition products, or deposit-forming resinous
species [14,16]. Detergents control the buildup of these undesirable contaminants by keeping equipment surfaces clean
and neutralizing acidic products from lubricant oxidation
and decomposition. They keep surfaces clean by forming a
protective film via adsorption and by suspending depositforming species in the bulk oil through association [7].
Detergents can also act as oxidation inhibitors, depending
u p o n the n a t u r e of their functional group. For example,
phenates, sulfurized phenates, and salicylates possess oxidation-inhibiting properties, primarily due to the presence of
the phenolic functional group.
-*-
Neutral Salt
stoichiometric Amount
^ ^ Basic or Overbased
Salt
No CO,
Stoicliiometnc Excess
n 1 or 2
0)xlWI
^?\.S03)xM
0)xlWI
R
R
Metal Salicylate
Metal Sulfonate
or
s
RP-O
I
I
O-IW
r. n
RP-O
'
'
Metal
Phosphonate
Metal
Thiophosphonate
0-iw
II
II
R_p_s-p-R
I I
o^ .o
X = 1 or 2
Y = S or CHa
lUI = Na, lUlg, Ca
M
Metal
Thiopyrophosphonate
211
O
II
-s-o
'6 \
II
-s-o
II
Sulfonate
Head Group
Hydrocarbon
Group
Additive It/lolecule
Metal Surface
Mack T-6, T-7, T-8/E, T-9, and T-10). Detergents have additionEil use in automatic transmission fluids and tractor hydraulic fluids. However, their use in these applications is not
to control deposits but to modify the fluid's frictional properties.
Film-Forming Agents
Physisorption
Cliemisorption
o o o o o o
o o o o o o
Chemical Reaction
FIG. 17Modes of additive - surface interactions.
Detergents have major use in crankcase lubricants. Gasoline and diesel engine oils account for over 75% of the total
detergent consumption. Detergent treatment levels in engine
lubricant formulations are fairly high, with marine diesel engine lubricants containing the highest detergent concentrations. Marine engines use high-sulfur fuel, which leads to
acidic combustion products (sulfuric acid). Therefore, lubricants for these engines need the base reserve of the "basic"
detergents for neutralization.
Detergency in diesel engine oils is evaluated by using both
single cylinder engine tests (Caterpillar IK, IM, IN, IP, and
IR) and multicylinder engine tests (GM 6.2L and 6.5L; and
HANDBOOK
Cohesion or Association
with Lubncant
\ ^
Ifl
\!*
"
"
^ ^ ^
^ H
HtOT fVSft<
HHZH" H^^HH ^ ^ H ^
QH^H
H-4HQ H ^
^
Hfi^
(A) Physisorption
(B) Chemisorption
FIG. 18Adsorption of polar additives on the metal surface.
213
0.16
LFW-1 Machine
Coefficient of Friction
0.057
0.054
0.055
0.052
Coefficient of Friction
20
30
40
50
60
LVFA Machine
Static
Dynamic
0.070
0.050
0.052
0.042
0.052
0.043
0.062
0.050
110
modifiers. Graphite presents problems when used in conventional lubricants; hence, at present, its use is limited to
greases.
The effectiveness of friction modifiers and antisquawk
agents is judged by the lubricant's performance in LVFA and
SAE # 2 tests. Their load-carrying capacity is determined by
the film strength tests, such as the Timken test.
Antiwear and Extreme Pressure Agents
Wear occurs in all equipment that has moving parts in contact. Three conditions that can lead to wear are surface-tosurface contact, surface contact with foreign matter, and erosion due to corrosive materials. Wear resulting from
surface-to-surface contact is frictional or adhesive wear,
from contact with foreign matter is abrasive wear, and from
contact with corrosive materials is corrosive wear. Fatigue
wear is an additional tjrpe of wear that is common in equipment where surfaces are not only in contact but also experience repeated stresses for prolonged periods. Abrasive wear
can be prevented by installing an efficient filtration mechanism to remove the offending debris. Corrosive wear can be
controlled by using additives that neutralize the reactive
species that attack the metal surfaces. The control of adhesive wear requires the use of additives called antiwear and extreme pressure (EP) agents.
214
MANUAL
HANDBOOK
Under normal conditions of speed and load, two metal surfaces are effectively separated by a lubricant film; a condition
identified as hydrodynamic lubrication. An increase in load or
a decrease in speed promotes metal-to-metal contact. This
causes a temperature rise in the contact zone due to frictional
heat, which results in the loss of lubricant viscosity a n d
hence its film-forming ability. With a progressive increase in
load and/or a decrease in viscosity, the nature of lubrication
changes from hydrodynamic to mixed-film to boundary lubrication. Antiwear additives and EP agents offer protection under mixed-film andboundary lubrication conditions [26]. This
is shown in Fig. 22, Part B [27].
Antiwear and EP additives both provide protection by a
similar mechanism, except that EP additives typically require
higher activation temperatures and load than the antiwear
additives. Simply stated, antiwear additives perform under
mild conditions and EP additives perform under severe conditions. The severity of conditions is determined by the "load
factor" experienced by the additive and the temperature at
which the additive functions. Load is a function of equipment speed and service. Heavy loading requires the use of extreme pressure agents and mild loading requires the use of
antiwear agents. Thus, it is important to consider both the
load and the temperatures that the equipment is likely to experience before selecting these additives.
Antiwear agents are commonly used in engine oils, automatic
transmission fluids, power steering fluids, and tractor hydraulic
fluids. Extreme pressure agents are used in other power-transmitting fluids, gear oils, shock-absorber fluids, and metalwork-
ing fluids. For GF-2 and API SH and SJ quality engine oils, ASTM
Sequence IIIE and VE engine tests are used to determine the effectiveness of antiwear agents. However, for API SL and ILSAC
GF-3 categories (approved in 2001), ASTM Sequence IIIF, IVA,
and VG engine tests are used. To determine the performance of
EP agents in gear oils, the CRC L-37 and CRC L-42 axle tests are
used. The general effectiveness of these additives in metalworking fluids is determined by Timken, Four-Ball, and Falex tests.
Extreme pressure additives are usually supplemented with antiwear additives to make the formulations effective at lower temperatures and under milder loading conditions as well.
Most antiwear and extreme pressure agents contain sulfur,
chlorine, phosphorus, boron, or combinations thereof. The
classes of compounds that inhibit adhesive wear include alkyl
and aryl disulfides and polysulfides, dithiocarbamates, chlorinated hydrocarbons, and phosphorus compounds such as
alkyl phosphites, phosphates, dithiophosphates, and
alkenylphosphonates.
Both antiwear and extreme pressure additives function by
thermal decomposition and by forming products that react
with the metal surface to form a solid protective layer. This
solid metal film fills the surface cavities (asperities) and facilitates effective film formation, thereby reducing friction
and preventing welding and surface wear. The meted films
consist of iron halides, sulfides, or phosphates, depending
upon the antiwear and EP agents used. Friction modifiers
differ from antiwear and extreme pressure agents in that they
form the protective film via physical Eind chemical adsorption instead of chemical reaction.
LubricantFilm
FLUID-FILM LUBRICATION
Surfaces well separated by
the bulk lubricant film
.. * J
c
Lubricant
Film
1 Boundary Lubrication
MIXED-FILM LUBRICATION
Both the bulk lubricant and
the boundary film play a
role
! \ / - ^ Mixed-film Lubrication
u.
"5
c
a>
8
o
Fluid-film Lubrication
.ZN.
P
(A) RELATIONSHIP OF VISCOSITY (2),
SPEED (AO, AND LOAD (P) TO
FRICTION AND FILM THICKNESS
BOUNDARY LUBRICATION
Performance essentially
depends upon the quality of
the boundary film
4R0H
+ P2S5
.^'
(R0)2P,
215
+ H2S
SH
DialkyI Dtttiiophosphoric
Acid
2 (RO)2P.
.^'
(R0)2P\ .
ZnO
SH
DiaikyI Dithjophosphoric
Acid
Activated
Olefin
Zn
H2O
Zinc DialkyI
Dithioptiosphate
2 CH2=CH<
OR
i^l<
2 (ROhP,
Zn
J2
5 Cn2 CH2
Zinc Diaryl
Oithiophosptiate
C.
OR
DialkyI Ditliiophosphate
Ester
THERMAL STABILITY:
216
MANUAL
HANDBOOK
dent of the nature of the alkyl group, but their antiwear action is not. Aliphatic zinc dialkyl dithiophosphates have better antiwear performance t h a n a r o m a t i c derivatives. And
among ahphatics, the secondary alcohol derived are better
than those that are primary alcohol derived.
Extreme Pressure Agents^Alkyl and aryl disulfides and polysulfides, dithiocarbamates, chlorinated hydrocarbons, dialkyl hydrogen phosphites, a n d salts of alkyl p h o s p h o r i c
acids are the c o m m o n extreme pressure (EP) agents.
Polysulfides are synthesized from olefins either by reacting
with sulfur or sulfur halides, followed by dehydrohalogenation. Sulfurization of olefins with elemental sulfur, or sulfur
and hydrogen sulfide, yields organic sulfides and polysulfides
[28,30]. Dialkyldithiocarbamates are prepared either by neutralizing dithiocarbamic acid (resulting from the low-temperature reaction of a dialkylamine and carbon disulfide)
with bases, such as zinc oxide or antimony oxide, or by its addition to activated olefins, such as alkyl acrylates [31]. The
synthesis of these materials is described in Fig. 24 and Fig.
25, respectively.
Alkyl and aryl phosphites are obtained by reacting an alcohol or a phenol with phosphorus trichloride or by a transesterification reaction [32]. Alcohols a n d phenols react with
phosphorus pentoxide to yield a mixture of an alkyl (aryl)
phosphoric acid and a dialkyl (diaryl) phosphoric acid [33].
These acids, when treated with bases, form salts. Alkyl phosphates can also be prepared by the oxidation of phosphites.
The preparation of eJkyl phosphites is outlined in Fig. 26 a n d
of alkyl phosphates is outlined in Fig. 27.
The extent of EP protection in equipment depends upon
the conjunction temperature of the two metal surfaces in
contact [34]. Figure 28 shows a direct correlation between
the conjunction temperature and the degree of EP protection
needed. The equipment that operates at low speeds and high
loads generally requires more EP protection than equipment
that operates at high speeds and low loads. This is because
RCHaCH=CH2
Olefin
Sg
I
Heat
RCH=CHCHa
RCH=CHCHz
RCHz
Sx
I
+
Sa
I
R-CH2-CH-CH3
RCH2CHCH2
RCH
Organic Poiysutfides
+
R
Dithiolethione
FIG. 24Olefin sulfurization.
RCH2CHCH3
RjNH
RzN ct
CSj
Oialkylamine
217
SH
Carbon
Disulfide
Ditliiocarbamic
Acid
lUletai Oxide
or IHydroxidey
CH2=CHCOOR
Activated
Olefin
//
M = Zn or Sb
X = 2 or 3
R2N C '
R2NC
SCH2CH5-COOR
Metal Dithiocarbamate
Dithiocarbamate Ester
PCI,
3 HCI
Triaryl Phosphite
.^
(R0)2P.
PCI3
3 ROH
Alcohol
{PhO)3P
2 H C I + RCI
DialkyI Hydrogen
Phosphite
2 ROH
H2O
^
(R0)2P.
DialkyI Hydrogen
Phosphite
Triphenyl
Phosphite
(CH30)2P^
2 ROH
H
Dimethyl Hydrogen
Phosphite
(RO)2p^
3PhOH
Phenol
2CH3OH
Diallcyl Hydrogen
Phosphite
Methanol
218
HANDBOOK
3R0H
Alcohol
P2O5
II
ROPOH +
Phosphorus
Pentoxide
OR
II
ROPOH
I
OH
R'NHa
Metai Base
/
Metal Salts
Amine Salts
P=0
Triaryl Phosphite
Triaryi Phosphate
O
S^35fl|
52
3
(B
a> 30C
Q.
ffi
I-
I 25q
lilHPI^a
u
c
5*200
o
u
[ZESSIS
15a-
Some additives in a formulation can diminish the effectiveness of EP/AW agents. These include surface-active additives,
such as certain friction modifiers, oxidation inhibitors, rust
inhibitors, metal deactivators, detergents, and dispersants.
These components either irreversibly adsorb on the surface
and interfere with the EP mechanism, or they form complexes
with EP agents, thereby rendering them inactive [40,41]. The
same is true of some highly polar basestocks. This type of antagonism is quite common for some lubricants, such as gear
oils, where EP agents form the core of the formulation.
Antiseize additives are a separate class of antiwear additives, which perform independently of temperature. They improve boundary lubrication by forming the protective film
through deposition. Molybdenum disulfide and graphite,
common additives of this type, are generally used in greases,
some industrial oils, and various break-in lubricants.
RO.
RO
K
RO.
FeO Fe
OFe Fe
FeO Fe
OFe Fe
fFeO Fe
sii OFe Fe
FeO Fe
OFe Fe
FeO Fe
\^''''' OFe Fe
FeO Fe
S>>ii
RS
-Olefin
OR
I
S=PSZrw
I
O
EP Film
containing
Sulfur and
Phosphorus
Compounds
K
s=psziw-X
Fe
Fe
or
Fe203
RO
POLYMER
Adsorption
Fe
or
Fe203
Reaction
Original Profile
Worn Profile
FIG. 31Controlled wear of asperities to produce submicron
debris.
200
300
220
MANUAL
HANDBOOK
The rate of electrochemical corrosion depends upon the nature of the metal oxide film, the presence or absence of a polar solvent such as water, the presence or absence of an electrolyte (salts, acids, or bases), and the temperature.
Chemical corrosion, on the other hand, does not need an
electrolyte and can occur both in aqueous and organic media.
It involves the attack of corrosive species, such as acids,
bases, and sulfur, on metals. The damage occurs when the resulting compounds are removed.
Factors that affect corrosion include internal factors and
external factors [42]. Internal factors are directly related to
the metal itself, and include its composition, structure, surface condition, oxidation potential, a n d the presence of
stresses. External factors pertain to the environment and include the nature of the oxide film, acidity, alkalinity, the presence of electrolytes, the presence and reactivity of the aggressive species, and the temperature. While the role of these
factors is considered elsewhere [42], we are especially interested in the oxidation potential of various metals.
Oxidation potentials of the elements that make u p the metallurgy of m o d e m mechanical equipment are provided in Fig.
33. The elements that are primarily used to fabricate metal
parts are shown by bold italic symbols. The potentials reported in the table are relative to hydrogen with a value equal
to 0. Positive values indicate ease of oxidation and negative
values indicate resistance to oxidation. Because of hydrogen
being the reference point, we can directly compare these values to assess the relative oxidative tendency of various metals. The higher the oxidation potential, the easier it is for the
metal to oxidize. Metals in the left column of the table with
smaller values are therefore less susceptible to oxidation, and
corrosion, than those in the right column. The values with
slash indicate a metal's first and second oxidation potentials.
For example, for iron, 0.44 represents the oxidation potential
of the Fe to Fe"^^ transition and 0.04 represents the oxidation
potential of the Fe to Fe^^ transition. The same is true for
copper. Of the metals of interest, aluminum is the easiest to
oxidize, followed by iron and lead. Copper with negative values is the most resistant of the metals listed in the table.
Of the external factors listed above, acidity, alkalinity, the
presence of the reactive species, and the temperature have
the largest impact. The presence of acids and bases can accelerate corrosion. In lubricant applications, acids result
from the oxidation of the fuel sulfur and the basestock. Lubricant contains additive derived bases, both organic and inorganic, which are usually weak a n d therefore pose little
problem by themselves. However, the reaction between the
acidic and the basic species results in salts, which can promote corrosion because they are electrolytes. The lubricant
also contains additives that can lead to acidic decomposition
products. Some of these additives are sulfur and phosphorus
compounds that are added to the lubricant to improve its oxidative stability and antiwear performance. These can corrode metals either directly or by forming aggressive chemical
species via decomposition. Higher temperatures, which are
typically encountered in the internal combustion engines,
can accelerate corrosion as well.
Metallurgy in automotive equipment commonly contains
iron (Fe), copper (Cu), lead (Pb), chromium (Cr), manganese
(Mn), antimony (Sb), a l u m i n u m (Al), vanadium (V), zinc
(Zn), nickel (Ni), and tin (Sn). Protecting four of these elements against corrosion is of primary interest: iron, which is
the principal metal used to forge the engine and the auxiliary
equipment; copper, which is present in bearings and seals;
lead, which is also present in bearings; and aluminum that is
used in newer cars and trucks to make them lighter for better
fuel economy.
Protection against corrosion is necessary because it can
lead to a loss of metal thereby lowering the integrity of the
equipment and resulting in its malfunction. In addition, corrosion exposes fresh metal that can wear at an accelerated
rate and result in metal ions that can act as oxidation promoters.
Corrosion of iron and its alloys, sometimes referred to as
ferrous corrosion or rust, is primarily electrochemical in nature. It can occur b o t h in liquid and vapor phase and needs
water, electrolyte, and oxygen. In an internal combustion engine, water results from fuel combustion, oxygen comes from
the air, and electrol3?tes are metal salts that form by the reaction of metals and certain additives with combustion and oxidation acids. This type of corrosion mainly occurs in engines
that are run in short cycles (stop-and-go driving). Rust initiates when water sets u p a localized electrochemical reaction
between the surface iron and the iron oxide layer. Nascent
iron acts as the anode, and the iron oxide layer acts as the cathode. Iron emits electrons and forms ferrous ions that are re-
Electrode Reaction
M
Metal
M"* +
Lithium = Eo of +3.05
Hydrogen = Eg of 0.00
nQ
Eo Volts
Metal
Eo Volts
Lead(Pb)
0.13
Zinc (Zn)
Tin (Sn)
0.14
Chromium (Cr)
0.86/0.74
0.25
Manganese (Mn)
1.18/0.283
Nickel (Ni)
Iron (Fe)
Copper (Cu)
0.76
0.44/0.04
Vanadium (V)
1.18
-0.S2l-O.34
Aluminum (Al)
1.66
221
PROBLEM
>- Lubricant
Part A
Rust
^ 40H"
Fe^* + 2e
SOLUTION
y Lubricant
Parte
Protective
Layer
Iron
' Metal
PROBLEM
S S S S
S S S S S
ss s s
sss s
Corrosive
Materials
>- Lubricant
Part A
mmxm
SOLUTION
s s s s
SSSSS
Corrosive
Materials
^^ s
^SSs
Parte
Deactivator
Film
s '^ss <. , s ^ \
. Copper
Metal
Ss s s
sss s
^s^
"* Lubricant
www^
. Copper
Metal
N-N
>-Lubricant
"SSR
Cu O Cu O Cu O Cu O Cu O Cu OCu O Cu O Cu O Cu O Cu O Cu
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O
Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O
Oxide
l^yer
(a)
vProtective
'^Film
Nc. JJ-R
KyN-fl
N>yN-R
KyN-R
1
<
~Cu 0"Cu 0"Cu b'Cu <5 Cu'd Cii'dCu O'Cu'CJCu O Cu D Cii O Cu"
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O
Oxide
Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu
L^yer
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O
(b)
FiG. 36Copper passivators and mode of thieir action.
LCT^I
^^\.0(CH2CH20)xCH2CH20H
Ca
Polyethoxyiated Ptienol
Lpr-]
II
RCH C - O H
CHCOH
Ca. xCaCOs
2
II
Alltenylsuccinic Acid
II
) - - P - O H . R'N
.CH2CH2OH
RN
Aiitylammonlum
Phosphates
OR
\H2CH2OH
R O P - O H . R'NHa^
Diethanolamine
OH
RSS^^^S
\\
//
N-N
SSR
RS
SH
N
N-N
Dimercaptothiadiazole Derivatives
FIG. 37Corrosion iniiibitors.
X
Alicylbenzotriazole
CHAPTER
adsorbed films. For many applications such as gear oils, rust,
and corrosion, inhibitor systems are required to provide both
vapor-phase and liquid-phase protection, i.e., for surfaces
above and below the lubricant level.
Corrosion inhibitors have major uses in engine oils, gear
oils, metalworking fluids, and greases. Thiadiazole and triazole derivatives are especially useful in protecting against
nonferrous or yellow metal corrosion.
Metal corrosion is measured by a variety of tests, depending upon the application. For GF-2 and API SH and SJ quality oils, CRC L-38 Test (copper/lead), the ASTM Sequence
IID Rust Test (ASTM D 5844), and Cummins Bench Corrosion Test (copper/lead/tin) are used. For GF-3 and API SL
quality oils, ASTM Sequence VIII (unleaded L-38 Test;
ASTM D 6709) and Ball Rust Test (ASTM D 6557) are used.
For gear oils, CRC L-13, L-21, and L-33 Tests are used for
rust and the ASTM D 130 Test is used for copper. For industrial products, the ASTM D 665 Test is used for rust and
the ASTM D 130 Test is used for copper. For hydraulic and
metalworking fluids, a n u m b e r of ASTM specified tests are
utilized [3].
Polymeric Additives
Materials with polymeric structures are the key components
in high-performance lubricants. They can be used as lubricant basestocks (see synthetic lubricants) or to enhance a lubricant's inherent properties, such as viscosity and p o u r
point. They can also be used as starting materials to prepare
certain classes of additives, such as dispersants and detergents. The materials used for this p u r p o s e are m o r e oligomeric than polymeric, i.e., their molecular weight is relatively lower. Polymeric additives used in lubricants comprise
viscosity modifiers, p o u r point depressants, emulsifiers and
demulsifiers, and foam inhibitors.
Most polymeric materials are compositions that consist of
polymer chains of varying sizes. The bulk properties of these
compositions depend upon the average molecular weight of
the polymer chains. The molecular weights of poljoneric materials are expressed as n u m b e r average, weight average,
z-average, (z-l-1) average, and viscosity average molecular
weights [43,44]. Of these, number-average (Mn), weight-average (Mw), and z-average (Mz) molecular weights are most
often used to describe polymer compositions. The numberaverage molecular weight (Mn) represents chemical stoichiometry cind is useful in carrying out chemical reactions involving polymers. The weight-average molecular weight
(Mw) cortelates with mechanical properties, such as tensile
strength and modulus in plastics, films, and fibers, and the
viscosity-improving behavior of the polymers. The z-average
molecular weight (Mz) largely influences the polymer's viscoelastic properties, such as melt elasticity. While average
molecular weight information is important, it is the molecular weight distribution that is more useful in understanding
the polymer properties. The molecular weight distribution is
m e a s u r e d by polydispersity
index or heterogeneity
index,
which is the ratio of the weight-average molecular weight to
the number-average molecular weight, or Mw/Mn. For
monodisperse polymers, which contain molecules of essentially the same chain length, the value of this index is close to
1. For polydisperse samples, it is greater than 1 because of
9: ADDITIVES
AND ADDITIVE
CHEMISTRY
223
the greater contribution of the higher molecular weight fractions in the molecular weight-determining process.
The polydispersity index is a function of the polymerization
method. It is closer to 1 for polymers derived from anionic
polymerization, 1.5-2.0 for polymers derived from step
growth polymerization, between 2 and 5 for polymers derived from radical polymerization, and above 5 for polymers
derived from polymerization using coordination catalysts.
Viscosity
Modifiers
Mineral oils, which are effective lubricants at low temperatures, become less effective at high temperatures. At these
t e m p e r a t u r e s , their film-forming ability (in the hydrodynamic lubrication regime) diminishes due to a drop in viscosity. Prior to the use of viscosity modifiers, this problem
was partly overcome through seasonal oil changes. In winter,
low-viscosity oils were used and in s u m m e r high-viscosity
oils were used. The invention of viscosity modifiers led to the
introduction of multigrade oils thereby relieving the owner
from seasonal oil changes.
The principal function of a viscosity modifier is to minimize viscosity variations with temperature. Previously, viscosity index was used as a measure of an oil's response to
temperature changes. Viscosity index (VI), which is derived
from the viscosity of the oil at 40C and 100C, is no longer
meaningful. This is because most m o d e m equipment operates at extreme temperatures ( - 4 0 to +150). At these temperatures, the viscosities do not conform to those predicted
by the viscosity index [4b,45].
Viscosity modifiers are polymers with average molecular
weights of 10000 to 150000; but those with molecular
weights between 10000 and 20000 are used most often. These
chemicals are added to low-viscosity oils to improve their
high-temperature lubricating characteristics. Viscosity modifiers minimize viscosity change with a change in temperature. This is a practical m e a n s of extending the operating
range of mineral oils to higher temperatures, without adversely affecting their low-temperature fluidity.
Viscosity modifiers cause an increase in oil's viscosity at cJl
temperatures, except that thickening at lower temperatures
is less than that at higher temperatures. At low temperatures,
the polymer molecules occupy a small volume and therefore
have a m i n i m u m association with the bulk oil, or a small hydrodynamic volume. Hydrodynamic volume is the volume of
the polymer and the associated oil. The effect is a marginal
viscosity increase. At high temperatures, however, the situation is reversed because the polymer chains extend or expand
as a consequence of the added thermal energy. This increases
polymer's association with the bulk oil due to an increase in
its surface area [7]. The result is an effective increase in viscosity. Another way to describe this phenomenon is that at
higher t e m p e r a t u r e s the polymer becomes more soluble,
thereby causing viscosity to increase. The effect of a polymer
on the viscosity-temperature (VT) properties of an oil is depicted in Fig. 38. Note that the VT line for the viscosity-modified oil has a lower (shallower) slope than that for the base
oil, thereby indicating a lower drop in viscosity with increasing temperature. Figure 39 illustrates the mechanism of oilthickening by viscosity modifiers.
Variable thickening of oil by viscosity modifiers at low and
high temperatures allows the formulation of mutigrade oils.
HANDBOOK
The multigrade oils are designed to provide adequate viscosity at high temperatures for engine protection and low viscosity at low temperatures for easy startability. Figure 40 shows
the VT characteristics of single grade and multigrade oils.
It is technically inaccurate to assess low-temperature viscosities of the Vl-improved oils by linearly extrapolating the
VI (or VT) curves based on 40 and 100C viscosities. This is
because such oils can show an inflection at low temperatures
thereby leading to erroneous viscosity estimates [4a]. The
low-temperature viscosities of the Vl-improved oils should be
determined experimentally. It is also important to note that
superior viscosity-temperature relationship of the multigrade
oils, as expressed by the viscosity index, is not solely due to a
greater preferential swelling of the polymer at higher temperatures. The use of low-viscosity oils with good viscositytemperature behavior to prepare these oils makes a substantial contribution towards the overall effect [46]. In addition
to affecting the VT relationship, viscosity modifiers affect a
lubricant's other properties. These include pour point, dis-
Viscosity-modified Oil
Base Oil
Temperature
FIG. 38The effect of viscosity modifier on VT relationship
of an oil.
Polymers
Oil Associated
with Polymer
Poor-4^
Low ' ^
SOLUBILITY
TEMPERATURE
Good
High
SAE30
SAE 10W-30
-20
0
20
Temperature (C)-
120
Styrene-diene polymers (STDs) can be of the diblock or random-block type and are produced by anionic polymerization
of stjrene and butadiene or isoprene. This type of poljrmerization produces polymers with a narrower molecular weight
distribution than those obtained by the use of Ziegler-Natta
and Friedel-Crafts catalysts or the free radical initiators. That
is, their Mw/Mn is closer to 1. Because of the narrow molecular weight distribution, these polymers possess the best thickening power of the types discussed so far. However, the presence of the aromatic rings and the double bonds makes these
polymers more susceptible to oxidation. This problem is
somewhat overcome by catalytically hydrogenating the double bonds. Figure 41 schematically presents the synthesis of
these types of polymers. Recently, a different type of polymer,
labeled a "star" polymer, also called radial isoprene, has become commercially available. It has thickening power similar
to that of the styrene-diene type, but has better shear stability.
A clustered polyanion prepared from divinylbenzene and
styrene forms the center of the star, and the rays are made up
of the polymerized diene monomer units. Commercial olefinbased polymers include Exxon's Paratone series, Texaco's
TLA products, and Shell's Shell Vis polymers.
Ester Polymers
These include polymethacrylates and styrene-ester polymers.
Polymethacrylates (PMAs) are produced by free radical polymerization of alkyl methacrylate. Since free radical polymerization produces polymers with relatively broad molecular
weight distribution, such polymers have low thickening efficiency. Because of this, polymethacrylates have only moderate viscosity-improving ability. However, the alkyl group in
the ester portion of the polymer can be altered to obtain products that have the best oil solubility and optimum viscosityimproving properties. In addition, these polymers have good
225
1. Polyolefin
'^3^N
C=CH2
H3C
CH3
Acid
-=SS.
-CH2-C
CH3 J n
Polyisobutylene
Isobutylene
2. Olefin Copolymer
CH3
Ziegler
m CH2=CH2
CH3CH=CH2
Ethylene
~f~ CH2
\
Natta cat.
Propylene
CH2'~i CHCH2'm
3. Styrene-Diene Poilymers
CH3
-CHCH2-
CH=CH2
CHCH=CCH2-
CH,
+
n CH9CH
Styrene
Anionic
^1
Initiator
C-CHo
Isoprene
Styrene-dlene Polymer
CHa
CH3
Radical
Initiator
H2C=cCOOR
Alkyl Methacrylate
-CH,0I
COOR
Alkyl Methacrylate Polymer
He=CH2
-CH-CHjCHCHRadical
Initiator
Styrene
%
Maleic
Anhydride
'I
o^ "o" ^o
Styrene-maleic
anhydride Polymer
-CH-CH2CHCH0=C
I
NH
II
R'
1. ROH
/
2. H2NCH2(CH2)xNI
C=0
I
OR
R'
CHAPTER
bearings a n d cylinder walls that have intermediate shear
rates falls in between.
The viscosity loss can be temporary or permanent. If the
viscosity bounces back to the original viscosity when the
stress is removed, it is termed as temporary viscosity loss.
This t j ^ e of loss is due to the reversible deformation of the
polymer u n d e r the influence of shear forces, which minimizes the association between the polymer and the lubricant.
Temporary viscosity loss, shown in Fig. 45, is desired in lubricants because it decreases the viscous drag at low temperatures and therefore could contribute towards fuel economy
[47].
The viscosity loss is considered p e r m a n e n t if after the
shear forces are removed, the viscosity does not revert to its
prior value [47]. Permanent viscosity loss occurs when the
polymer in the viscosity-modified oil breaks down to the
lower molecular weight fragments u n d e r the influence of
shear [48]. This type of viscosity loss is not desired because a
formulated lubricant will not stay in its viscosity grade.
Whether temporary or p e r m a n e n t , viscosity loss depends
upon the shear stability of the polymeric viscosity modifier
used, which is a function of its molecular weight. More
9: ADDITIVES
AND ADDITIVE
nii-mf
X 100
mi-mo
m;
227
specifically, it is the function of the size of the polymer backbone. This relationship, which holds within a polymer type,
is shown in Fig. 46.
High molecular weight polymers generally lose viscosity at
a higher rate u n d e r shear than low molecular weight polymers. Hence, the lubricants thickened with low molecular
weight polymers are more likely to maintain their viscosity in
the desired viscosity range than the lubricants thickened with
high molecular weight polymers. Figures 47 and 48, respectively, depict the temporary and the permEinent viscosity loss
in oils containing viscosity modifiers of two different molecular weights [47]. As can be seen, in both cases the lower
molecular weight polymer experiences a lower viscosity loss.
The problem of viscosity loss due to shear can be alleviated
by pre-shearing the high molecular weight polymer prior to
blending, or by choosing a more shear-stable polymer. Shear
stability, which can be defined as the ability of a lubricant to
resist viscosity loss under the influence of shear, primarily relates to the permanent viscosity loss. Shear stability of a polym e r is inversely related to its molecular weight: the lower the
molecular weight, the higher the shear stability. The percent
loss of viscosity in polymer-thickened oils is expressed in
terms of their shear stability index, SSI, which can be represented as follows.
SSIr^
Molecular Weight -
CHEMISTRY
228
MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
Viscosity
Modifiers
A n u m b e r of tests are available to measure the viscosity improving properties and the shear stability of polymers in lubricants. The shear stability of a lubricant is measured by the
CRC L-38 Test, FZG Shear Test, Sonic Shear Test (ASTM D
2603), Orbahn Shear Test, Bosch Injector Test, and the Tapered Bearing Simulator Test (ASTM D 4683, D 4741, and D
6616). In terms of severity, the Tapered Bearing Test is the
most severe, followed by the FZG Test, Orbahn Test, and the
CRC L-38 Test.
Viscosity Loss Due to Polymer DegradationIn addition to mechanical breakdown (shear), polymers can undergo thermeJ
and oxidative degradation. Thermal degradation occurs when
the polymerization process is reversed under the influence of
heat. Polymers break down via chain scission to form lower
molecular-weight fragments. The consequence is a loss in viscosity. This type of degradation, which is more prevalent in
aromatic polymers due to their ability to form more stable allylic and benzylic radicals, is shown in Fig. 51. Oxidative
degradation occurs when weak carbon hydrogen bonds in the
Molecutar Weight
>
Vjvelogt^
f ^ OH mm
^ ~ "
Polvmer-containina
Oil
N. [Temporary
\ w Shear Loss
^
Base
Oil
lU
102
10*
10
106
to*
Shear Rate,-=(3-1)
1 .
107
108
'
\Mn=20,000
Mn=40,000\
2"
u
>
Base Oil
1
io3
^&^
io5
10^
Shear Rate (s-i)
io7
lo^
/
/
'
^=40,000
229
^
^
Mn=20,000
1
10
1
20
lOOT
30
80
Gear Oil
Tractor
Transmission
Fluids
|40|
to
Hydraulic
Fluids
Automatic
Trimsmissiori
Fluids
20
Engine
Oils '
0.1
04
1
3
Weight Average Molecular Weight (IMWxIO-^
230
MANUAL
HANDBOOK
i2or
0.01
0.05
0.10
0.15
0.20
0.25
>
FIG. 50The effect of specific viscosity on oil viscosity and shear stability.
Pour Point
Depressants
231
[-H-]
CH3
O2
.0-
Bond Cleavage
Other Oxidation Products
(Tliese include Carboxyiic Acids and Esters)
IHeat, Oj, and
Cataiysts
Varnish a n d C o k e Deposits
FIG. 52Mechanism of oxidative degradation of polymers.
CH3
CH,
CH2=CCOCH2CH2N ^
II
'
"
/
\
CH,
R
1-Vinyl-2-pyrrolidinone
or N-Vinylpyrrolidinone
Dimethylaminoethyl
Methacrylate
R'
Alkylnaphthalene
Alkylphenol
R, R' = Waxy Alkyl Groups
0\
CH3
A-A
CH2=CCOCH2CH2N
2- or 4-Vinylpyridlne
Morpholinoethyl
Methacrylate
CH3
CH,
CH-CH2OHOH-
i r
Styrene Ester
CH3
-OH,0
COOR
Alkyl Methacrylate
Polymer
CH2=CC0(CH2CH20|-[-CH2CHO-]R
O
Polyether Ester of
Methacryllc Acid
FIG. 53Monomers used in synthesizing dispersant viscosity modifiers.
232
HANDBOOK
CHAPTER
Foam
9: ADDITIVES
AND ADDITIVE
CHEMISTRY
233
OIL
Inhibitors
Foam forms when a large a m o u n t of gas is entrained in a liquid. While foaming is desirable in certain applications, such
as flotation, washing, and cleaning, it is undesirable in others,
such as distillation and pumping of fluids. In lubricant-related
applications, foam can act as an impediment and must be controlled. Almost every lubricant application involves some kind
of agitation that encourages foam formation through air entrainment. Excessive foaming will result in ineffective lubrication and, over time, will cause oxidative degradation of the
lubricant. The viscosity and the surface tension of a lubricant
determine the stability of the foam. Low-viscosity oils produce foams with large bubbles, which tend to break quickly.
High-viscosity oils, on the other hand, generate stable foams
that contain fine bubbles and are difficult to break. The presence of surface-active materials, such as dispersants and detergents, further increases the lubricant's tendency to foam.
^^(OCW^A
OIL
(a)
H2O
v^0
O^^^
H2O
Other Additives
In addition to the major classes of additives described above,
lubricants contain a n u m b e r of other additives. These include
seal-swell agents, dyes, biocides, and couplers. Seals are used
in m o d e m machinery for a variety of reasons. In lubrication
systems, their functions are to:
Isolate various lubrication environments from harmful elements.
H2O
Non-ionic
CH2CH2OH
RN
RO{CH2CH20)xCH2CH20H
NH(CH2CH20)xH
N-Hydroxyalkylamide
CH2CH2OH
Poiyethoxylated Alcohol
(HydroxyalkyI Ether)
DIettianolamlne
R"
RC
^CpNa
1
1
R"
Sodium
Carboxylate
Anionic
(b)
Trialkylammonium
Salt
R'
RNCH2CH2 C,
1
1
R"
Tetraalkylammonium
Carboxylate
Cationic
FIG. 56Emulsifiers and demulsifiers.
Amplioteric
CH,
- 0 - S I - OSI0--SI
I
CH,
CH,
CHa
DImethylslloxane
Polymer
CH3
CH,
-CH2-
-C
I
COOR
Alkyl Methacrylate
Polymer
MULTIFUNCTIONAL NATURE OF
ADDITIVES
A number of additives perform more than one function. Zinc
dialkyl dithiophosphates, known mainly for their antiwear
action, are also potent oxidation and corrosion inhibitors.
Polyacrylates and styrene-ester polymers can act as viscosity
modifiers, dispersants, and pour point depressants. Basic
sulfonates, in addition to acting as detergents, perform as
rust and corrosion inhibitors. They do so by forming protective surface films and by neutralizing acids that arise from
fuel combustion, lubricant oxidation, and additive degradation.
CHAPTER
PERFORMANCE TESTING
Reliable lubricant performance is a function of the quality of
its components. This implies both the base oil quality and
that of the performance package. Because most additives are
reactive components, their quality is assessed both individually as well as in an additive package, which comprises a collection of additives.
9: ADDITIVES
AND ADDITIVE
CHEMISTRY
235
236
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
Physical tests, commonly used for finished lubricants, include those relating to density (ASTM D 1298), viscosity
(ASTM D 445), viscosity index (ASTM D 2270), shear stability (ASTM D 1298, D 4624, D 5481, D 5133, D 2603, D 4683,
Additive
Gasoline
Engine Oils
Diesel Engine
Oils
Dispersant
Detergent
Antiwear/EP Agent
Oxidation Inhibitor
Corrosion Inhibitor/Metal Deactivator
Friction Modifier
Pour Point Depressant
Foam Inhibitor
Viscosity Modifier
Other'
Stationary Gas
Engine Oils
Two-stroke
Cycle Engine
Oils
Aviation
Engine Oils
Additive
Dispersant
Detergent
Antiwear/EP Agent
Oxidation Inhibitor
Corrosion Inhibitor/
Metal Deactivator
Friction Modifier
Pour Point Depressant
Foam Inhibitor
Viscosity Modifier
Other^
Automatic
Transmission
Fluids
Gear Oils
Automotive
Industrial
Gear Oils
Gear Oils
Hydraulic Fluids
Tractor
Hydraulic Fluids
Industrial
Hydraulic Fluids
Metalworking
Fluids
Greases
CHAPTER
Viscosity Tests
Viscosity plays a crucial role in forming effective lubricating
films, which makes it one of the most important properties of
a fluid [57]. Viscosity, defined as a fluid's resistance to flow,
is mainly a consequence of the internal friction of the fluid
[4]. Viscosity requirements or specifications are therefore
prescribed for almost all lubricants. Meeting these is absolutely critical for automotive lubricants, such as engine oils,
transmission fluids, and tractor hydraulic fluids.
For automotive engine oils, viscosity requirements are described in the SAE Standards J300 [58] and J1536 [59]. The
SAE Standard J300 deals with the viscosity of lubricants for
four-stroke cycle engines, of both compression ignition (CI)
and spark ignition (SI) types, and two-stroke cycle CI engines.
The SAE Standard J1536, on the other hand, specifies viscosity of oils for two-stroke cycle SI engines only. The SAE Standard J1536 describes the miscibility and fluidity grades for
two-stroke cycle engine oils. The basic viscosity grade categories for engine oils are determined by the Crankcase Classification System devised by the SAE, which uses test methods
approved by the ASTM. For transmission fluids and tractor
hydraulic fluids, the SAE grades are the same as those used
for engine oils. However, for automotive gear oils, these are
different and are described in the SAE Standard J306 [60].
Viscosity of non-automotive lubricants, such as industrial
gear lubricants and industrial oils, is described by the American Gear Manufacturers Association (AGMA) and International Standardization Organization (ISO) Standards, respectively.
ACEA uses SAE viscosity classification system, described
in SAE J300. However, it has additional requirements relating to shear stability, evaporation loss, elastomer compatibility, sulfated ash, foaming tendency, and changes in viscosity
due to high shear and high temperature. Special laboratory
test procedures are used to determine if a lubricant meets the
desired performance requirements in these areas. These procedures are described in the SAE J2227 report [61].
The ASTM D 445 method is used to determine kinematic
viscosity of a lubricant at 40C and 100C. This procedure employs a capillary viscometer. The ASTM methods D 2602,
D2983, D 3829, D 4684, and D5293 are used to determine low
temperature viscosity of lubricants. ASTM D 2602 uses cold
cranking simulator to determine apparent viscosity at 0 to
- 4 0 C range. The ASTM D 3829 and D 4684 procedures use
mini-rotary viscometer and are used to measure borderline
pumping temperature (BPT) and apparent yield stress and apparent viscosity, respectively. ASTM D 5133 is scanning
Brookfield technique that is used to measure gellation point,
point at which sample viscosity reaches 30,000 cP. ASTM D
2983 is also a Brookfield procedure that is used primarily for
low temperature properties of automotive gear oils, automatic transmission fluids, torque and tractor fluids, and hydraulic fluids. The measurement is carried out at a constant
temperature in the range of 0 to 40C. The ASTM procedures
D 5624, D 4683, D 4741, and D 5481 are used to measure high
temperature/high shear viscosity (HTHS). The ASTM D 5624
procedure uses a capillary viscometer where force is applied
to a lubricant that is at 150C to generate a high shear rate (10
s"'). The ASTM D 1092 procedure, used to measure viscosity
of greases, also uses pressure [57b]. The ASTM D 4683 and
9: ADDITIVES
AND ADDITIVE
CHEMISTRY
237
D 6616 methods, on the other hand, use tapered bearing simulator to determine HTHS viscosity. Two procedures that are
used to measure grease viscosity are ASTM D 1092 and ASTM
D 4693. The first measures apparent viscosity and the second
measures pumpability. The procedures ASTM D 2270 and D
2161 do not directly measure viscosity but are used for conversion purposes. ASTM D 2270 or D 39 B is used to calculate
viscosity index (VI) from 40C and 100C kinematic viscosities
and ASTM D 2161 is used to convert viscosities measured in
now obsolete units of Saybolt Universal Seconds (SUS) and
Saybolt Furol Seconds (SFS) into centistokes (cSt).
For two-stroke cycle SI engine oils, viscosity grades are
based on miscibility with fuel and fluidity. This is to ensure
that the lubricant is miscible with fuel and that the blend
meets the low-temperature viscosity requirements. The rationale behind these requirements is that two-stroke cycle SI engines usually do not have an oil sump, and the lubricant is
mixed with the fuel in the fuel tank. The testing involves mixing lubricant with fuel and determining its pour point (ASTM
D 4682). The performance of the new oil is compared with
that of the reference oils to assign a viscosity grade. Transmission and tractor hydraulic fluids, like engine oils, have
low t e m p e r a t u r e and high t e m p e r a t u r e viscosity requirements. Low temperature requirements are base upon ASTM
D 2983 (Brookfield test) and ASTM D 445 is the basis for 40C
and 100C kinematic viscosities.
Performance Tests
As mentioned earlier, each tjrpe of lubricant must meet certain performance requirements prior to use. Such requirements are described in service classifications or specifications (ASTM D 4485). The following section describes these
based on the lubricant type.
Engine
Oils
238
HANDBOOK
bearing corrosion, and ASTM Sequence VIII for rust and corrosion [74]. API has stopped licensing GF-2 passenger car oils
since April 2002 [64]. The work on the next ILSAC upgrade,
GF-4, has already started. The new category will require oils
that are emission system catalyst compatible, have better fuel
economy, and provide better engine protection [65].
For diesel engine oils, API CF, CF-2, CF-4, CG-4, CH-4, and
CI-4 categories are active. API CF-2 is for severe-duty twostroke cycle engines. API CF is for four-stroke cycle engines
that are either turbocharged or use high sulfur fuel. Such engines are often for off-highway use. API CF-4 and CI-4 categories are for four-stroke cycle engines for on-highway use.
API CF-4 is for 1991 low emissions engines, API CG-4 is for
1994 low emissions engines, and API CH-4 is for 1998 low
emissions engines. API CI-4, the 2002 upgrade of the diesel engine oil standard, is suitable for use in engines that are
equipped with exhaust gas recirculation and other exhaust
emissions control mechanisms/components. Such engines are
designed to meet the 2004 exhaust emissions standard. In general, oils meeting higher service requirements are suitable for
use in the lower service class within the same category. New
proposed category, PC-8, for next generation heavy-duty
diesel engine oils has been under consideration for some time.
It is designed to address the Japanese OEM concerns over the
ability of the API CH-4/CI-4 qualified oils to protect their engines that use slider followers. The American engines use
roller followers. The CI-4 category includes eight fired engine
tests and seven bench tests [66]. The diesel engine tests include
Caterpillar IR, Cummins M i l , MackTSE (ASTM D 5967) and
T-10, and GM 6.5L Roller Follower Test (ASTM D 5966). This
category accommodated two major OEM specifications,
Cummins CES 20076 and Mack EO-M Plus, both of which require performance beyond that delivered by API CH-4.
In addition to API, two other organizations actively participate in establishing engine oil performance. These are U.S.
Military and original equipment manufacturers (OEMs). The
needs of the U.S. Military are different from those of the commercial users. Its fleets consist of vehicles that not only vary
in size (ranging from 2 to over 1000-hp), but they also operate under a variety of conditions. U.S. Military specifications
are designated by the prefix MIL. While largely similar to API
service designations, there can be subtle differences. Similarly, certain OEMs have additional requirements to qualify
oils for use in their equipment. Mack EO-M and Cummins
CES 20076 specifications are examples of such requirements.
ACEA establishes oil quality for use in Europe and JASO
and Bureau of Indian Standards (BIS) establishes oil quality
for use in Japan and India, respectively. ACEA specifies the
use of tests developed by the ASTM and CEC (Conseil Europeen de Coordination pour les Developments des Essais de
Performance des Lubrifiants et des Combustibles pour Moteurs; Coordinating European Council). ACEA 2002 Standard consists of four lubricant classes for gasoline engines,
Al-02, A2-96 (issue 3), A3-02 and A5-02; five lubricant classes
for light-duty diesel engines, Bl-02, B2-98 (Issue 2). B3-98
(Issue 2), B4-02, and B5-02; and four lubricant classes for
commercial diesel engines, E2-96 (Issue 4), E2-96 (Issue 4),
E4-99 (Issue 2), and E5-02. Current Japanese specifications
include JIS K 2215 for gasoline engine oils and JASO DH-1
for diesel engine oils.
Each active category has associated tests. These tests pri-
marily pertain to frictioucJ characteristics, oxidation resistance, deposit controlling ability, corrosion and wear preventing ability, and fuel efficiency of the oil. The current engine
and bench tests for gasoline engine lubricants are as follows.
U.S. and European Tests
Rust and corrosionCRC L-38, ASTM Sequence VIII
(ASTM D 6709), ASTM Sequence IID (ASTM D 5844), and
Ball Rust Test (ASTM 6557)
OxidationASTM Sequences HIE (ASTM D 5844) and
IIIF, CRC L-38, and Peugeot TU-3M High-temperature
Thermal and Oxidative StabilityThermo-oxidation Engine Oil Simulation Test (TEOST; ASTM D 6335), Hightemperature Deposit Test
Sludge, varnish, deposits, and v\;earCRC L-38, ASTM Sequence HIE (ASTM D 5533), ASTM Sequence VE (ASTM D
5302), and VG (ASTM 6593), M-B Ml 11 Black Sludge, VW
1302, and Peugeot TU-3M High-temperature
Valve Train WearASTM Sequence IVA and Peugeot TU3M Wear
Fuel EfficiencyASTM Sequence VI, VIA (ASTM D 6202),
and VIB (For GF-3), and M-B M i l l Fuel Economy
Extended drain capabilityVW T-4
Japanese and Indian Tests
Rust and corrosionCRC L-38/Petter Wl, ASTM Sequence
IID (ASTM D 5844)
OxidationToyota. IG-FE, CRC L-38/PetterWl, and ASTM
HID and HIE (ASTM D 5533)
Sludge, varnish, deposits, and wearToyota IG-FE, Nissan
VG-20E, Nissan SD22 (JASO 336-90), Nissan TD25 (JASO
336-97), CRC L-38/Petter Wl, CLR LTD, ASTM HID and
HIE, ASTM VD and VE (ASTM D 5302)
Valve train wearToyota 3A, Toyota 3E, Nissan KA-24E
The current diesel engine tests are as follows. These tests
are devised to measure protection against rust, varnish, deposits, sludge, wear, high-temperature oil-thickening, ring
sticking, fuel economy, and foaming tendency.
U.S. and European Tests
Piston deposits, ring sticking, oil consumption, and piston
liner and ring distressCaterpillar IK, IM-PC (ASTM D
6618), IN, IP (ASTM D 6681), and IR; Detroit Diesel 6V
92TA (two-stroke cycle engine; ASTM D 5862)); Mack T-6;
VW 1.6TC Diesel Intercooler and VW Direct Injection; Peugeot XUDl 1 ATE and XUDl IBTE; MAN 5305; and M-B OM
364A/LA and M-B OM 441LA
Roller follower wearRoller Follower (lifter pin wear), GM
6.2L and GM 6.5L (ASTM D 5966)
Soot thickeningMack T-6, T-7, T-8/T-8E (ASTM D 5967),
T-9 (ASTM D 6483), and T-10.
Engine oil corrosiveness^ASTM D 5968
Oxidative stability/Viscosity increaseVW Direct Injection
and Peugeot XUDl lATE and XUDl IBTE
Sludge, varnish, and wear/cleanlinessM-B OM 602A, M-B
OM 364A/LA, M-B OM 441 LA, and Cummins M-11
Fuel EconomyM-B M i l l Fuel Economy
Foaming tendencyNavistar 7.3L EOAT [Hydraulically Actuated Electronic Controlled Unit Injector (HEUI)]
Bore PolishingMAH 5305, M-B OM 364A/LA, M-B OM
441 LA
CHAPTER
Indian Tests
Piston deposits, sludge, varnish, and
wearCaterpillar
1H2/MWM-B, Caterpillar 1G2/MWM-B, M-B OM 364A, MBOM616
Soot ThickeningMack T-7
Bore PolishingM-B OM 616
Service classifications for two-stroke cycle engine oils are
described in the SAE Standard J2116 [67]. The API designations for oils approved for use in two-stroke cycle engines are
TA and TC, and NMMA (National Marine Manufacturers Association) designations are TC-W, TC-WII, and TC-W3. TA
oils are designed for use in low performance engines and TC
oils are designed for use in high performance engines, except
outboard engines (ASTM D 4859). TC-W, TC-WII, and TCW3 oils, on the other hand, are intended for use in watercooled outboard engines. The quality of two-stroke cycle oils
is assessed on the basis of their ability to prevent piston scuffing, exhaust system blocking, ring sticking, and deposit-induced pre-ignition ASTM D 4857 and D 4858). JASO and ISO
based two-stroke cycle categories are at present being developed. These will be based upon oil's lubricity and detergency,
and its ability to control exhaust smoke and exhaust system
blocking. The engine test requirements for NMMA's most recent category TC-W3 are listed below.
Piston varnish, deposits, and ring stickingOMC 40-hp,
OMC 70-hp
Scuffing, bearing stickiness, and compression
lossMercury 15-hp
Tightening and lubricityYamaha CE50S
Preignition^Yamaha CE50S
Many changes have occurred for water-cooled engine specifications since writing this article. NMMA's categories TCW, TC-WII, and TC-W3 are now obsolete and a recertified
TC-W3 category was introduced. At present, the availability
of the OMC 70-hp and OMC 40-hp engine test parts is in question.
Transmission
Fluids
The important functions of these fluids are lubrication, cooling, and to act as a hydraulic medium to transmit power.
These fluids are of three types: automatic transmission fluids, manual transmission fluids, and power transmission fluids. There is no official API classification system for these fluids. Performance requirements for transmission fluids are
established by the OEMs [68]. The most important features
of these fluids are their frictional consistency (durability) and
frictional compatibility with the transmission's components.
In a u t o m a t i c transmissions, such c o m p o n e n t s include
clutches and bands; in manual transmissions and manual
transaxles, they include cone or plate type synchronizers. Unlike automatic transmissions, which use transmission fluids
recommended only by the OEMs, manual transmissions use
a variety of fluids. Such fluids include automatic transmission fluids, engine oils (5W-30), some gear lubricants, and
specialty fluids. In addition to frictional properties, certain
OEMs require transmission fluids for their equipment to
have improved shear stability, low-temperature fluidity, and
other specific characteristics.
Automatic Transmission FluidsThe frictional compatibility
of automatic transmission fluids (ATFs) with the transmis-
9: ADDITIVES
AND ADDITIVE
CHEMISTRY
239
sion's clutch and band system is their most important feature. DEXRON and MERCON are the two major types of
a u t o m a t i c transmission fluids that are presently in use.
DEXRON fluids meet General Motors' performance specifications and are primarily designed for use in their transmissions. MERCON fluids meet Ford's performance requirements and are used in its transmissions. DEXRON-III,
MERCON , and MERCON-V fluids are the most current
specifications for transmission fluids. DEXRON-III, introduced in 1994, is suitable for use in GM transmissions that
were designed to improve fuel economy and emissions [69].
Design changes and operating environment for these transmissions called for fluids with good low-temperature properties, good thermo-oxidative stability (ASTM D 5579), and
frictional durability. DEXRON-III specification was designed to improve shift-feel smoothness, antiwear characteristics, low-temperature fluidity, and oxidation resistance of
the fluid. DEXRON-IV specification, proposed but not yet
in use, will require fluids of lower kinematic and Brookfield
viscosities so as to minimize energy losses and further improve fuel efficiency. Tests and evaluation criteria for automatic transmission fluids are provided below.
Friction and wearASTM D 2882, Band Clutch, Plate
Clutch Friction
Thermo-oxidative stability4L60 Transmission, ABOT Oxidation
Frictional consistency and durabilityCycling
(ASTM D
5579)
Smooth shifting of gearsShift Feel
Power Transmission
FluidsPower
transmission fluids
(PTF) aire used in heavy-duty automatic transmissions and
torque converters in off-highway equipment. Such equipment is commonly used in agriculture and construction industries. Viscosity and frictional properties of these fluids are
critical to their performance. Just like ATFs, the SAE and
OEM performance specifications are used to describe these
fluids [70]. Power transmission fluids are classified on the
basis of their performance in Allison C-4 and Caterpillar TO4 friction tests. Fluids meeting Allison C-4 requirements are
designed for equipment that has both torque conversion and
automatic transmission features.
Gear Oils
Gear oils are primarily formulated to provide extreme pressure protection for gears and axles to prevent fatigue, scoring, and wear under boundary lubrication conditions. Gears
are used in automobiles and industry to perform a number of
diverse functions. Because of differences in design, each gear
type places different demands on the lubricant.
Automotive Gear OilsPerformance
specifications for automotive gear oils are established by the API, U.S. Military, and
the OEMs. The API service designations for automotive gear
oils range from GL-1 to GL-6, specifying oils in increasing order of load-carrying capacity [71,72]. The abbreviation "GL"
stands for gear lubricant. The GL-6 classification, which was
previously used to describe antiscoring performance over
and above that provided by the GL-5 lubricants, is technically
obsolete. The GL-4 and GL-5 categories correspond to U.S.
Military specifications MIL-L-2105 and MIL-L-2105D, respectively, and define oils for service-fill only. The specifica-
240
HANDBOOK
tion MIL-PRF-2105E, issued in 1995, combines the GL-5 requirements of MIL-L-2105D and thermal oxidation stabihty,
antiwear, and seal compatibility requirements of the newly
released API specification MT-1. The new specification defines lubricants for nonsynchronized manual transmissions
used in buses and heavy-duty trucks. Factory-fill oils are defined by major car and truck manufacturers. Such oils have
performance characteristics that are critical to the satisfactory operation of a particular drive train and may include
break-in, bearing preload, and limited slip durability. Mack
GO-G/S and GO-H/S are examples of such specifications.
European OEMs use API GL-5 and MIL-L-2105D to define
minimum performance requirements for oils used in their
equipment. They have additioned requirements pertaining to
surface fatigue, component cleanliness, synchromesh durability, and viscometrics, depending upon their specific need/s.
Japanese OEMs recommend API GL-5 lubricants for vehicles
fitted with h3rpoid and spiral bevel axles and API GL-3 and GL4 lubricajits for cars and trucks equipped with manual transmissions. Most modem cars use transaxle drive train arrangement and hence do not need rear axle lubricants. A new
performance specification, PG-2, for automotive geetr oils is
presently under consideration [73]. It is a temporary designation for axle lubricants to be used in heavy-duty truck and bus
final drives that employ spiral bevel and hypoid gears. This
category is designed to qualify lubricants with higher thermal
durability, seal compatibility, and surface fatigue performance than the existing GL-5 lubricants.
The API and the military specifications have associated
bench and axle tests [74]. These include tests to evaluate the
oil's ability to protect gears and axles against fatigue, scoring,
and wear. Additional tests deal with a gear oil's oxidative stability, foaming tendency, and the ability to protect against
rust and corrosion. Axle tests are run according to methods
established by the American Coordinating Research Council
(CRC). Bench and axle tests used to qualify automotive gear
oils (ASTM D 5760) are given below.
Scoring resistance under high-speed shock load conditions
CRC L-19 and FTM 6504T, CRC L-42, Vehicle Rear Axle
Score
Resistance to gear distress under high-torque low-speed conditionsCRC L-20, CRC L-37 (ASTM D 6121)
Antiwear propertieskSlU D 5182, FZG (A/8.3/90), and
(A/10/90)
Gear surface fatigueMack Spalling
High-temperature stability of lubricantASTM D 5763,
Mack Transmission Test T-2180, CRC L-60, and CRC
L-60-1
Lubricant stability in motored axle testFord BJ 15-1
Corrosion resistance in the presence of waterCRC L-13 or
FTM 5313.1 and CRC L-21, CRC L-33
Copper corrosion^ASTM D 130
Oil seal compatibilityASTM D 471, ASTM D 5662
Foaming tendencyASTM D 892, CRC L-12
Transmission cyclic durabilityASTM D 5579
Material separated on centrifugation after 30 day storage at
room temperatureFTM 3440, modified
Channeling characteristics of lubricantFTM 3456.1, modified
Compatibility with existing gear lubricantsSS & C FEDSTD-791 Method D 3430 and D 3440
Fluids
The primary function of these fluids is to transmit power efficiently and control wear. Hydraulic fluids are of two general
types: those used to lubricate tractor hydraulics and those
used to lubricate industrial hydraulic equipment.
Tractor Hydraulic FluidsTractor hydraulic fluids (THFs)
are multipurpose lubricants that are used to lubricate transmissions, final drives, hydraulic systems, wet brakes, and wet
clutches [75]. To perform these functions properly, THFs
must combine hydraulic and transmission properties with
extreme-pressure properties. Their function as a transmission fluid and as a lubricant for wet brakes and wet clutches
requires them to possess proper frictional characteristics.
Tractor hydraulic fluids differ widely in performance requirements because OEMs can not agree on common specifications for a universal tractor hydraulic fluid. The specifications for these fluids, in general, deal with extreme
pressure (EP) and antiwear properties, and with matching
the frictional requirements of the equipment. The quality of
these fluids is assessed on the basis of their ability to meet individual OEM specifications as well as API GL-4 (for EP) and
Allison C-4 (for friction, oxidation, and wear) performance
requirements. There are eight major OEM specifications and
most tractor fluids are formulated to meet them. These specifications are:
JI Case MS 1207
John Deere J20C/D, and J27
New Holland FNHA-2-C-201.00 and M2C159B/C
AGCO Massey-Ferguson Ml 135, Ml 139, and Ml 141
Tests associated with these specifications include:
Wear and Extreme-pressure TestsDenison T-50 Vane
pump and P-46 Piston Pump; Vickers 35VQ-25 Vane and
Vickers V104C Vane Pump, Constant Volume Vane Pump
(ASTM D 2882); FZG EP/antiwear [DIN 51354 (Part 2)];
Four-Ball EP (ASTM D 2783); and Four-Ball Wear (ASTM
D4172)
Oxidation TestsTnrbme Oil (ASTM D 943); Sludge
(ASTM D 4310); and Rotary Bomb (ASTM D 2272); Universal Oxidation Test (ASTM D 5846)
Corrosion TestsTurhins Oil Rust (ASTM D 665) and Copper Strip (ASTM D 130)
Miscellaneous TestsTurbine Oil Demulsibility (ASTM D
1401); Hydrolytic Stability (ASTM D 2619); Cincinnati Milacron Thermal Stability (ASTM D 2070); Denison TP
02100 Filterability; Foam ASTM D 892; Air Separation
(DIN 51381); and Seal Compatibility [DIN 53538 (Part 1)]
241
Metalworking
Fluids
Metalworking fluids are used to convert metal into a component or a piece. These fluids are of four basic t3^es, straight
oils, soluble oils, semisynthetic fluids, and synthetic fluids. Soluble oils, semisynthetic fluids, and synthetic fluids are waterbased and differ from one another, mainly in their oil content
and emulsion type [76]. Straight oils are devoid of water.
They are mineral oil-based (primarily hydrotreated naphthenic basestocks) and usually contain sulfur, chlorine, and
phosphorus-derived additives. Soluble oils are water emulsions of mineral and/or fatty oils. An emulsifying agent or
surfactant is used to form these emulsions. Synthetic fluids
are oil-free and are simply solutions of additives in water.
Since most organic materials are hard to dissolve in water,
high polarity of the additives is necessary for solubility.
Soaps or other surfactants are sometimes added to help in
this regard. Semisynthetic fluids are in between soluble oils
and synthetic fluids as far as their oil content is concerned. In
242
MANUAL
HANDBOOK
R & O Oils
Wear TestsVane P u m p (ASTM D 2882), Denison P-46 Piston Pump, Four-Ball Wear (ASTM D 4172)
Oxidation TestsRotary Bomb (ASTM D 2272), Turbine
Oil (ASTM D 943), 1000-hour Sludge (ASTM D 4310),
Cincinnati Milacron Heat, FTMS 5308.6
Corrosion TestsRust (ASTM D 665), Copper Strip (ASTM
D 130)
Miscellaneous TestsTurbine Oil Demulsibility (ASTM D
1401), Neutralization N u m b e r (ASTM D 974 and D 664),
Foam (tendency/stability) (ASTM D 892), and Air Release
(DIN 51381, ASTM D 3427)
Turbine Oils
Oxidation TesfsTurbine Oil (ASTM D 943), 1000-hour
Sludge (ASTM D 4310), IP280 TOP, IP280 Sludge, Rotary
Bomb (ASTM D 2272), FTMS 5308.6, and Universal Oxidation Test (ASTM D 5846)
Corrosion TestsRust (ASTM D 665), Copper Strip (ASTM
D130)
Wear TestFZG (A/8.3/90), a n d Four-Ball EP (ASTM D
2783), Falex (ASTM D 2670), Ryder gear tests to fulfil U.S.
Military requirements.
Miscellaneous
TestsViscosity
Index (ASTM D 2270),
Flash Point (ASTM D 93), Pour Point (ASTM D 97), Neutralization N u m b e r (ASTM D 974 and D 664), Air Release
(DIN 51381, ASTM D 3427), F o a m (tendency/stability)
(ASTM D 892), Demulsibility (ASTM D 2711), and Turbine
Oil Demulsibility (ASTM D 1401)
Greases
The use of this lubricant goes back to ancient times [62]. Lubricating grease is defined as a "solid-to-semifluid products
of dispersion of a thickening agent in a liquid lubricant.
Other ingredients imparting special properties may be added
(ASTM D 288)." Such ingredients include additives that impart other desirable properties, such as EP, water resistance,
etc. The lubrication function is carried out by the small
amount of oil that is released during equipment operation.
Because of their semisolid nature, greases are used when
fluid lubricants are inefficient, the need for lubrication is infrequent, and/or the lubricant is required to maintain its original position in a mechanism.
Greases are formulated from both synthetic and mineral
oil basestocks by using a thickening agent and selected additive packages. The thickener, usually a metal soap (a carboxylic acid salt) and sometimes a gelled basic sulfonate,
243
IP No.
36/84 (89)
34/88
136/89
15/95
2160:1985
154/95
D 217-97
D 445-01
2137:1985
3104:1994
50/88
71/97
D 482-00
D 566-97
D 664-95 (2001)
2176:1995
6619:1988
132/96
177/96
D 665-99
7120:1987
135/93
D
D
D
D
808-00
874-00
892-01
942-90 (1995)
3987:1994
6247:1998
163/96
146/82 (88)
142/85 (92)
D
D
D
D
943-99
972-97
974-01
1078-95
4263:1986
280/96
6618:1997
139/93
195/90
3839:1978
130/92
D 1298-99
3675:1993
160/96
D
D
D
D
6614:1994
2049-1996
412/96
196/97
D
D
D
D
D
D
ASTM No.
92-01
93-00
94-00
97-96a
129-00
130-94(2000)
D 1091-00
D 1092-99
D 1159-01
D 1218-99
D 1263-94 (1999)
D 1264-00
1401-98
1500-98
1742-94 (2000)
1743-01
D 1744
366/84
D 1748-00
D 1831-00
D 2070-91 (2001)
D 2161-93 (1999)
D 2265-00
239/97
D 2266-91 (1996)
D 2270-93 (1998)
D 2272-98
2909:1981
226/91 (95)
D 2500-99
D 2509-93 (1998)
3015:1992
219/94
326/83 (88)
D 2596-97
D 2602-86
D 2603-01
Test
Test Method for Flash and Fire Points by Cleveland Open Cup
Test Method for Flash Point by Pensky-Martens Closed Cup Tester
Test Method for Saponification N u m b e r of Petroleum Products
Test Method for Pour Point of Petroleum Products
Test Method for Sulfur in Petroleum Products (General B o m b Method)
Test Method for Detection of Copper Corrosion from Petroleum Products by the
Copper Strip Tarnish Test
Test Method for Cone Penetration of Lubricating Grease
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the
Calculation of Dynamic Viscosity)
Test Method for Ash from Petroleum Products
Test Method for Dropping Point of Lubricating Grease
Test Method for Acid Number of Petroleum Products by Potentiometric Titration
Method
Test Method for Rust Preventing Characteristics of Inhibited Mineral Oil in the
Presence of Water
Test Method for Chlorine in New and Used Petroleum Products (Bomb Method)
Test Method for Sulfated Ash from Lubricating Oils and Additives
Test Method for Foaming Characteristics of Lubricating Oils
Test Method for Oxidation Stability of Lubricating Greases by the Oxygen B o m b
Method
Test Method for Oxidation Characteristics of Inhibited Mineral Oils
Test Method for Evaporation Loss of Lubricating Greases and Oils
Test Method for Acid and Base Number by Color-Indicator Titration
Test Method for t h e Determination of Distillation Characteristics of Volatile
Organic Liquids (ASTM Procedure Now Obsolete)
Test Method for Phosphorus in Lubricating Oils and Additives
Test Method for Measuring Apparent Viscosity of Lubricating Greases
Test Method for B r o m i n e N u m b e r s of Petroleum Distillates and Commercial
Aliphatic Olefins by Electrometric Titration
Test Method for Refractive Index a n d Refractive Dispersion of Hydrocarbon
Liquids
Test Method for Leakage Tendencies of Automotive Wheel Bearing Greases
Test Method for Determining the Water Washout Characteristics of Lubricating
Greases
Practice for Density, Relative Density (Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products
Test Method for Water Separability of Petroleum Oils and Synthetic Fluids
Test Method for ASTM Color of Petroleum Products (ASTM Color Scale)
Test Method for Oil Separation from Lubricating Grease During Storage
Test Method for Determining Corrosion Preventive Properties of Lubricating
Greases
Test Method for Determination of Water in Liquid Petroleum Products by Karl
Fischer Reagent (Discontinued 2000)
Standard Test Method for Rust Protection by Metal Preservatives in the Humidity
Cabinet
Test Method for Roll Stability of Lubricating Grease
Test Method for Thermal Stability of Hydraulic Oils
Practice for Conversion of Kinematic Viscosity to Saybolt Universal Viscosity or to
Saybolt Universal Viscosity
Test Method for Dropping Point of Lubricating Grease Over Wide Temperature
Range
Test Method for Wear Preventive Characteristics of Lubricating Grease (Four-Ball
Method)
Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100C
Test Method for Oxidation Stability of Steam Turbine Oils by Rotating Pressure
Vessel
Test Method for Cloud Point of Petroleum Products
Test Method for Measurement of Load-Carrying Capacity of Lubricating Grease
(Timken Method)
Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Grease (Four-Ball Method)
Test Method for Apparent Viscosity of Engine Oils at Low Temperature Using
Cold-cranking Simulator (Replaced in 1993 with D 5293)
Test Method for Sonic Shear Stability of Polymer-Containing Oils
(Continues)
ISO No.
IP No.
D 2619-95
D 2622-98
D 2670-95 (1999)
D 2710-99
D2711-01a
D 2782-01
D 2783-88 (1998)
293/97
D 2882-00
D 2893-99
D 2896-01
3771:1994
D 2983-01
276/95
267/84
D 3228-96
D 3233-93 (1998)
D 3336-97
D 3339-95 (2000)
7537:1989
BS7393
3679:1983
3680:1983
303/83 (88)
4265:1986
149/93
D 3427-99
D 3520-88 (1998)
D 3527-95
D 3825-90 (2000)
D 3828-98
D 3829-93 (1998)
D 4047-00
D
D
D
D
4048-97
4049-99
4170-97
4172-94 (1999)
293/97
D 4289-97
D 4290-94 (1999)
D 4310-98
D 4377-00
D 4485-01
D 4624-93 (1998)
356/93
D 4627-92
287/94
125/82
D 4628-97
D 4682-87 (1996)
D 4683-96
D 4684-99
D 4693-97
D 4739-96
D 4741-00
D 4857-Ola
D 4858-00
276/95
417/96
Test
Test Method for Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle Method)
Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-Ray
Fluorescence Spectrometiy
Test Method for Measuring Wear Properties of Fluid Lubricants (Falex Pin and Vee
Block Method)
Test Method for Bromine Index of Petroleum Hydrocarbons by Electrometric
Titration
Test Method for Demusibility Characteristics of Lubricating Oils
Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Fluids (Timken Method)
Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Fluids (Four-Ball Method)
Test Method for Indicating Wear Characteristics of Petroleum and Non-Petroleum
Hydraulic Fluids in Constant Volume Vane Pump
Test Method for Oxidation Characteristics of Extreme-Pressure Lubricating Oils
Test Method for Base Number of Petroleum Products by Potentiometric Perchloric
Acid Titration
Test Method for Low-Temperature Viscosity of Automotive Fluid Lubricants
Measured by Brookfield Viscometer
Test Method for Total Nitrogen in Lubricating Oils and Fuel Oils by Modified
Kjeldahl Method
Test Method for Measurement of Extreme Pressure Properties of Fluid Lubricants
(Falex Pin and Vee Block Methods)
Test Method for Life of Lubricating Greases in Ball Bearings at Elevated
Temperatures
Test Method for Acid Number of Petroleum Products by Semi-Micro Color Indicator Titration
Test Method for Air Release Properties of Petroleum Oils
Test Method for Quenching Time of Heat-Treating Fluids (Magnetic Quenchometer Method)
Test Method for Life Perforraance of Automotive Wheel Bearing Grease
Test Method for Dynamic Surface Tension by the Fast Bubble Technique
Test Method for Flash Point by Small Scale Closed Tester
Test Method for Predicting the Borderline Pumping Temperature of Engine Oil
Test Method for Phosphorus in Lubricating Oils and Additives by Quinoline
Phosphomolybdate Method
Test Method for Detection of Copper Corrosion from Lubricating Grease
Test Method for Determining the Resistance of Lubricating Grease to Water Spray
Test Method for Fretting Wear Protection by Lubricating Greases
Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four-Ball
Method)
Test Method for Elastomer Compatibility of Lubricating Greases and Fluids
Test Method for Determining the Leaking Tendencies of Automotive Wheel
Bearing Grease Under Accelerated Conditions
Test Method for Determination of the Sludging and Corrosion Tendencies of
Inhibited Mineral Oils
Test Method for Water in Crude Oils by Potentiometric Karl Fischer Titration
Specification for Performance of Engine Oils
Test Method for Measuring Apparent Viscosity by Capillary Viscometer at HighTemperature and High-Shear Rates
Test Method for Iron Chip Corrosion for Water-Dilutable Metalworking Fluids
Test Method for Analysis of Barium, Cadmium, Magnesium, and Zinc in Unused
Lubricating Oils by Atomic Absorption Spectrometry
Specification for Miscibility with Gasoline and Fluidity of Two-Stroke Cycle Gasoline Engine Lubricants
Test Method for Measuring Viscosity at High Shear Rate and High Temperature by
Tapered Bearing Simulator
Test Method for Determination of Yield Stress and Apparent Viscosity of Engine
Oils at Low Temperature
Test Method for Low-Temperature Torque of Grease-Lubricated Wheel Bearings
Standard Test Method for Base Number Determination by Potentiometric
Titration
Test Method for Measuring Viscosity at High Temperature and High Shear Rate by
Tapered-Plug Viscometer
Test Method for Determination of the Ability of Lubricants to Minimize Ring
Sticking and Piston Deposits in Two-Stroke-Cycle Gasoline Engines Other Than
Outboards
Test Method for Determination of the Tendency of Lubricants to Promote Preignition in Two-Stroke-Cycle Gasoline Engines
ISO No.
IP No.
D 4863-00
D 4927-96
D 4928-00
D 4950-95 (2000)
D 4951-00
D 4998-95
D 5133-99
D 5182-97
D 5185-97
D 5291-96
D 5293-99a
D 5302-01
D 5480-95 (1999)
D5481- 96
D 5533-98
D 5579- 01
D 5 6 1 9 00
D 5662
D 5706- 97
D 5707.
D 5760- 95
D 5763- 95
D 5800 00a
D 5844. 98
D 5846- 99
D 5862- 99a
D 5949- 96
D 5950- 96
D 5966- 99
D 5967- 99a
D 5968 00a
D 5985- 96
D 6082- 00
D6121- 01
D 6202 -01
D 6335
D 6375 99a
D 6417 99
334/93
245
Test
Specification for Lubricants for Two-Stroke-Cycle Spark-Ignition Gasoline
Engines-TC
Test Method for Determination of Lubricity of Two-Stroke-Cycle Gasoline Engine
Lubricants
Test Methods for Elemental Analysis of Lubricant and Additive Components
B a r i u m , Calcium, P h o s p h o r u s , Sulfur, and Zinc by Wavelength-Dispersive
X-Ray Fluorescence Spectroscopy
Test Methods for Water in Crude Oils by Coulometric Karl Fischer Titration
Classification and Specification for Automotive Service Greases
Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectroscopy
Test Method for Evaluating Wear Characteristics of Tractor Hydraulic Fluids
Test Method for Low T e m p e r a t u r e , Low Shear Rate, Viscosity/Temperature
Dependence of Lubricating Oils Using a Temperature Scanning Technique
Standard Test Method for Evaluating the Scuffing Load Capacity of Oils (FZG
Visual Method)
Test Method for Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base
Oils by Inductively Coupled Plasma Emission Spectroscopy (ICP-AES)
Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen
in Petroleum Products and Lubricants
Test Method for Apparent Viscosity of Engine Oils Between - 5 and 35C Using
the Cold Cranking Simulator
Test Method for Eveduation of Automotive Engine Oils for Inhibition of Deposit
Formation and Wear in a Spark-Ignition Internal Combustion Engine Fueled
with Gasoline and Operated Under Low-Temperature, Light-Duty Conditions
(Sequence VE)
Test Method for Engine Oil Volatility by Gas Chromatography
Test Method for Measuring Apparent Viscosity at High-Temperature and HighShear Rate by Multicell Capillary Viscometer
Test Method for Evaluation of Automotive Engine Oils in Sequence IIIE, SparkIgnition Engine
Test Method for Evaluating the Thermal Stability of Manual Transmission Lubricants in a Cyclic Durability Test
Test Method for Comparing Metal Removal Fluids Using the Tapping Torque Test
Machine
Test Method for Determining Automotive Gear Oil Compatibility with Typical Oil
Seal Elastomers
Test Method for Determining Extreme Pressure Properties of Lubricating Greases
Using a High-Frequency, Linear-Oscillation (SRV) Test Machine
Test Method for Measuring Friction and Wear Properties of Lubricating Greases
Using a High-Frequency, Linear-Oscillation (SRV) Test Machine
Specification for Performance of Manual Transmission Gear Lubricants
Test Method for Oxidation and Thermal Stability Characteristics of Gear Oils
Using Universal Glassware
Test Method for Evaporation Loss of Lubricating Oils by the Noack Method
Test Method for Evaluation of Automotive Engine Oils for Inhibition of Rusting
(Sequence IID)
Test Method for Universal Oxidation Test for Hydraulic and Turbine Oils Using the
Universal Oxidation Test Apparatus
Test Method for Evaluation of Engine Oils in Two-Stroke Cycle Turbo-SuperCharged 6V92TA Diesel Engine
Test Method for Pour Point of Petroleum Products (Automatic Pressure Pulsing
Method)
Test Method for Pour Point of Petroleum Products (Automatic Tilt Method)
Test Method for Evaluation of Engine Oils for Roller Follower Wear in Light-Duty
Diesel Engine
The Method of Evaluation of Diesel Engine Oils in T-8 Engine
Test Method for the Corrosiveness of Diesel Engine Oil
Test Method for Pour Point of Petroleum Products (Rotational Method)
Test Method for High Temperature Foaming Characteristics of Lubricating Oils
Test Method for Evaluation of the Load Carrying Capacity of Lubricants Under
Conditions of Low Speed and High Torque Used for Final Hypoid Drive Axles
Test Method for Automotive Engine Oils on the Fuel Economy of Passenger Cars
and Light Duty Trucks in t h e Sequence VIA Spark Ignition Engine
Test Method for Determination of High T e m p e r a t u r e Deposits by ThermoOxidation Engine Oil Simulation Test
Test Method for Evaporation Loss of Lubricating Oils by Thermogravimetric
Analyzer (TGA) Noack Method
Test Method for Estimation of Engine Oil Volatility by Capillary Gas Chromatography
(Continues)
D 6443-99
D 6481-99
D 6483-99
D 6557-00
D 6593-00
D 6616-01
D 6618-00
D 6681-01
D 6709-01
ISO No.
IP No.
Test
Test Method for Determination of Calcium, Chlorine, Copper, Magnesium, Phosphorus, Sulfur, and Zinc in Unused Oils and Additives by Wavelength Dispersive
X-ray Fluorescence Spectrometry (Mathematical Correction Method)
Test Method for Determination of Phosphorus, Sulfur, Calcium, and Zinc in
Lubrication Oils by Energy Dispersive X-ray Fluorescence Spectrometry
Test Method for Evaluation of Diesel Engine Oils in T-9 Engine
Test Method for Evaluation of Rust Preventive Characteristics of Automotive
Engine Oils (Ball Rust Test)
Test Method for Evaluation of Automotive Engine Oils for Inhibition of Deposit
Formation in a Spark-Ignition Internal Combustion Engine Fueled with
Gasoline and Operated Under Low-Temperature, Light Duty Conditions
(Sequence VG)
Test Method for Measuring Viscosity at High Shear Rate by Tapered Bearing
Simulator Viscometer at 100C
Test Method for Evaluation of Engine Oils in Diesel Four-Stroke-Cycle SuperCharged IM-PC Single Cylinder Oil Test Engine
Test Method for Evaluation of Engine Oils in a High Speed, Single-Cylinder Diesel
EngineCaterpillar IP Test Procedure
Test Method for Evaluation of Automotive Engine Oils in the Sequence VIII SparkIgnition Engine (CLR Oil Test Engine)
REFERENCES
[1] Obert, E. F., "Lubrication," Ch. 16, Internal Combustion Engines
and Air Pollution, Intext Educational Publishing, NY, 1968, pp.
633-677.
[2] Modler, R., Anderson E., and Yoshida Y., "Lubricant Oil Additives," Specialty Chemicals, Strategies for Success, Vol. 9, SRI International, December 1996.
[3] Rizvi, S. Q. A., "Additives: Chemistry and Testing," Tribology
Data HandbookAn Excellent Friction, Lubrication, and Wear
Resource, CRC Press, Boca Raton, FL, 1997, pp. 117-137.
[4] Klamann, D., Lubricants and Related ProductsSynthesis, Properties, Applications, International Standards, Verlag Chemie,
Hamburg, 1984. (a) "Analysis and Testing," Ch. 10, pp. 218-247.
(b) "Additives," Ch. 9, pp. 177-217. (c) Appendix A, pp. 437-442.
[5] Gergel, W. C, "Lubricant Additive Chemistry," Presented at the
International Symposium on Technical Organic Additives and
Environment, Interlaken, Switzerland, 24-25 May 1984.
[6] Ford, J. F., "Lubricating Oil Additives^A Chemist's Eye View,"
Journal of the Institute of Petroleum, Vol. 54, July 1968, pp.
188-210.
[7] Schilling, A., Motor Oils and Engine Lubrication, Scientific Publications, Great Britain, 1968.
[8] Ingold, K. U., "Inhibition of Autoxidation of Organic Substances
in Liquid Phase," Chemical Reviews, Vol. 61, 1961, pp. 563-589.
[9] Johnson, M. D., Korcek, S., and Zinbo, M., "Inhibition of Oxidation by ZDTP and Ashless Antioxidants in the Presence of Hydroperoxides at 160C," Lubricant and Additive Effects on Engine
Wear, SP-558, Fuels and Lubricants Meeting, San Francisco, CA,
31 Oct.-3 Nov., 1983, pp. 71-81.
[10] Al-Malaika, S., Marogi, A., and Scott, G., Journal ofApplied Polymer Science, Vol. 33, 1987, pp. 1455-71.
[11] Abou El Naga, H. H. and Salem, A. E. M., "Effect of Worn Metals on the Oxidation of Lubricating Oils," Wear, Vol. 96, 1984,
pp.267-283.
[12] Vijh, A. K., "Electrochemical Mechanisms of the Dissolution of
Metals Eind the Contaminants Oxidation of Lubricating Oils Under High-temperature Friction Conditions," Wear, Vol. 104,
1985,pp.l51-158.
[13] HambUn, P. C, Kristen U., and Chasan D., "A Review: Ashless
Antioxidants, Copper Deactivators, and Corrosion Inhibitors,
Their Use in Lubricating Oils," Lubrication Science, Vol. 2, 1990,
pp. 287-318.
[14] Kreuz, K. L., "Gasoline Engine Chemistry as Applied to Lubricant Problems," Lubrication, Vol. 55, 1969, pp. 53-64.
[15] Lachowicz, D. R. and Kreuz, K. L., "Peroxynitrates. The Unstable Products of Olefin Nitration with Dinitrogen Tetroxide in
the Presence of Oxygen. A New Route to a-Nitroketones," Journal of Organic Chemistry, Vol. 32, 1967, pp. 3885-3888.
[16] Kreuz, K. L., "Diesel Engine Chemistry as Applied to Lubricant
Problems," Lubrication, Vol. 56, 1970, pp. 77-88.
[17] Covitch, M. J., Graf, R. T., and Gundic, D. T., "Microstructure of
Carbonaceous Diesel Engine Piston Deposits," Lubricant Engineering, Vol. 44, 1988, p. 128. (b) Covitch, M. J., Richardson, J.
P., and Graf, R. T., "Structural Aspects of European and American Diesel Engine Piston Deposits," Lubrication Science, Vol. 2,
1990, pp. 231-251.
[18] Kombrekke, R. E., Personal Communication, Research and Development, The Lubrizol Corporation, Wickliffe, OH.
[19] Boner, C. J., "Theory of Action and Performance," Ch. 8, Gear
and Transmission Lubricants, Reinhold Publishing Company,
NY, 1964.
[20] Bhushan, B. and Gupta, B. K., "Physics of Tribological Materials," Ch. 3, Handbook of Tribology; Materials, Coatings, and Surface Treatments, McGraw-Hill, Inc., NY, 1991. (c) Buckley, D.
H., "Properties of Surfaces," CRC Handbook of Lubrication,
(Theory and Practice of Tribology), Vol. II, Theory and Design,
Richard E. Booser, Ed., CRC Press, Boca Raton, FL, 1983, pp.
17-30.
[21] Lansdown, A. R., "Extreme Pressure and Anti-wear Additives,"
Ch. 12, Chemistry and Technology of Lubricants, R. M. Mortier
and S. T. Orszulik, Eds., VCH Publishers, Inc., NY, 1992, pp.
269-281.
[22] O'Brien, J. A., "Lubricant Additives," CRC Handbook of Lubrication, (Theory and Practice of Tribology), Vol. II, Theory and Design, Richard E. Booser, Ed., CRC Press, Boca Raton, FL, 1983,
pp. 301-315.
[23] "Engine Service Classification System and Guide to Crankcase
Oil Selection," API Publication 1509, American Petroleum Institute, Washington, D.C., 1996.
[24] Oliver, C. R., Renter, R. M., and Sendra, J. C, "Fuel Efficient
Gasoline-Engine Oils," Lubrication, Vol. 67, 1981, pp. 1-12.
[25] Jayne, G. J., Matthews, B. M., and Thomas, A. S., "Hypoid Gear
Oils for the 1980s," Ch. 19, Performance and Testing of Gear Oils
and Transmission Fluids, R. Tourret and E. P. Wright, Eds.,
Heyden and Son, 1981, pp. 307-319.
247
Encyclopedia of Polymer Science and Engineering, Second Edition, John Wiley and Sons, NY, 1988, Vol. 11, p. 22.
[46] MuUer, H. G., "Mechanism of Action of Viscosity Index Improvers," Tribology International, June 1978, pp. 189-192.
[47] Watson, R. W. and McDonnell, T. F., Jr., "AdditivesThe Right
Stuff for Automotive Engine Oils," Fuels and Lubricants Technology: An Overview, SP. 603, Society of Automotive Engineers,
Warrendale, PA, October 1984, pp. 17-28.
[48] Stambaugh, R. L "Viscosity Index Improvers and Thickeners,"
Chemistry and Technology of Lubricants, R. M. Mortier and S. T.
Orszulik, Eds., VCH Publishers, Inc., NY, 1992, pp. 124-159.
[49] Becher, P., Emulsions: Theory and Practice, American Chemical
Society Monograph Series, Ch. 6, Reinhold Publishing Corporation, NY, 1957, pp. 209-231.
[50] Karsa, D. R., "Industrial Applications of Surfactants," Industrial
Applications of SurfactantsAn Overview, D. R. Karsa, Ed., Published by Royal Society of Chemistry, Cambridge, England,
1987.
[51] Hancock, R. I., "Macromolecular Surfactants," Surfactants, T. F.
Tadros, Ed., Academic Press, San Diego, CA, 1984, pp. 287- 321.
[52] Lubricant Additives and the Environment, CEFIC, Brussels, Belgium, 1993, an ATC (Technical Committee of Petroleum Additive Manufacturers) Technical Publication.
[53] Fuel Additives and the Environment, CEFIC, an ATC (Technical
Committee of Petroleum Additive Manufacturers) Technical
Publication, Brussels, Belgium, 1994,
[54] De Hoffmann, E., Charette, J., and Stroobant, V., Mass Spectrometry: Principles and Applications, John Wiley & Sons, NY,
December 1996. (b) Colthup, N. B., Daly, L. H., and. Wiberley,
5. E., Introduction to Infrared and Raman Spectroscopy, 3rd edition. Academic Press, San Diego, CA, September 1990. (c) Macomber, R. S., A Complete Introduction to Modem NMR Spectroscopy, John Wiley & Sons, NY, December 1997. (d) Derome,
A. E., "Modem NMR Techniques for Chemistry Research," Vol.
6, Tetrahedron Organic Chemistry Series, J. E. Baldwin and P. D.
Magnus, Eds., Pergamon Press, Oxford, 1993.
[55] Hsu, S. M. and Cummings, A. L., "Interactions of Additives and
Lubricating Basestocks," Lubricant and Additive Effects on Engine Wear, SP - 558, Fuels and Lubricants Meeting, San Francisco, CA, 31 Oct.-3 Nov. 1983, pp. 61-70.
[56] Annual Book of ASTM Standards, ASTM International, West
Conshohocken, PA, 1998, and the later revisions.
[57] Rein, S. W., "Viscosity-I," Lubrication, Vol. 64, No. 1, 1978, pp.
1-12. (b) Rein, S. W., "Viscosity-II," Lubrication, Vol. 64, No. 1,
p p . 13-32, 1978. (c) "Viscosity," Lubrication, Vol. 52, No. 3,
1966, pp. 2 1 ^ 8 .
[58] SAE J300: "Engine Oil Viscosity Classification," Society of Automotive Engineers, Warrendale, PA, 1995, and the later revisions.
[59] SAE J1536: "Two-stroke Cycle Engine Oil Miscibility/Fluidity
Classification," Society of Automotive Engineers, Warrendale,
PA, 1995, and the later revisions.
[60] SAE J306: "Axle and Manual Transmission Lubricant Viscosity
Classification," Society of Automotive Engineers, Warrendale,
PA, 1985. (b) "Revision to SAE J306 Approved," Lubrizol
NewsLine, Vol. 16, No. 3, June 1998.
[61] SAE J2227: "International Tests and Specifications for Automotive Oils," Surface Vehicles Information Report, Society of Automotive Engineers, Warrendale, PA, July 1998. (b) "ACEA Issues
New Engine Oil Specification," Lubrizol NewsLine, Vol. 16, No.
3, June 1998.
[62] Rizvi, S. Q. A., "History of Automotive Lubrication," SAE Technical Paper 961949, Presented at Fuels and Lubricant Meeting,
San Antonio, TX, 14-17 Oct. 1996, Society of Automotive Engineers, Warrendale, PA.
[63] SAE J183: "Engine Oil Performance and Engine Service Classification (Other Than "Energy Conserving")," SAE 1995 Hand-
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71] "Lubricant Service Designations for Automotive Manual Transmissions a n d Axles," API Publication No. 1560, American
Petroleum Institute, Washington DC, 1981.
[72] Sutherland, J. M., "Proposed Automotive Gear Lubricant Categories: Their Impact on the Industry," Presented at NPRA National Fuels and Lubricants Meeting, Houston, TX, 2-3 Nov. 1989.
[73] "Progress is Slow on PG-1 and PG-2," Lubrizol NewsLine, Vol.
11, No. 1, January 1993.
[74] (a) "Ready Reference for Lubricant and Fuel Performance,"
Publication 1288 240-94R1, The Lubrizol Corporation, Wickliffe, OH, 1999/2002. (b) Reference Library, Lubrizol web site,
www.lubrizol.com.
[75] "Tractor Wet Brake and Wet Clutch Friction Properties," W. K.
S. Cleveland, NLGI Sopkesman, July 1987, p p . 135-138.
[76] Laemmle, J. T., "Metalworking Lubricants," American Society
of Metals Handbook, Friction, Lubrication, and Wear Technology, S. D. Henry, Ed., ASM International 1992, Vol. 18,
pp. 139-149.
[77] "NLGI Lubricating Grease Guide," National Grease Institute,
Kansas City, MO, 1987.
[78] SAE J310; "Automotive Lubrication Greases," SAE 1995 Handbook, Society of Automotive Engineers, Warrendale, PA, 1995.
MNL37-EB/Jun. 2003
Synthetic Lubricants
Non Aqueous
Thomas F. Buenemann,
and Ian Thompson^
In addition to their good properties at extreme temperatures, synthetic esters have other desirable characteristics including good lubricity, high viscosity index, low volatility,
and compatibility with s t a n d a r d lubricant additives a n d
basefluids. The fundamental chemistry is flexible and a wide
range of raw materials is available, which means that ester
base fluids can be designed having a wide raxige of viscosities.
Other key properties such as biodegradability can also be
controlled by molecular design [3]. Consequently, synthetic
esters have found use in many applications outside aviation.
Examples include automotive crankcase a n d gear oils, 2stroke lubricants, industrial gear oils, hydraulic fluids, textile
yarn lubricants, metal cutting and rolling fluids, air compressor lubricants, and refrigeration compressor lubricants
[4].
Raw
Materials
249
2003 by A S I M International
Groups
Esters are defined as the class of chemical compounds containing the ester functional group. They are normally manufactured by reaction of a carboxylic acid with an alcohol (Fig.
1), optionally in the presence of an esterification catalyst, and
with elimination of water [5].
The properties of the product esters can be controlled by
appropriate selection of the raw materials used. The final
product properties are mainly dependent on the molecular
weight, the n u m b e r of ester groups per molecule, and the degree of branching in alkyl substituent groups. A mixture of
raw materials may be used to deliver the precise combination
of properties required.
There are three main classes of synthetic esters currently in
use as lubricant base fluids: aromatic esters, aliphatic diesters,
and polyol esters. Aromatic esters, shown in Fig. 2, are manufactured by the reaction of an aromatic di or poly acid or anhydride, such as phthalic anhydride, tiimellitic anhydride, or
pyromeUitic anhydride, with a monoalcohol or mixture of
monoalcohols. Diesters, shown in Fig. 3, are manufactured by
the reaction of an aliphatic alpha, omega diacid with a monoalcohol or mixture of monoalcohols. Polyol esters, shown in Fig.
4, are manufactured by reaction of a diol or polyol having the
neopentyl structure, such as neopentyl glycol, trimethylol
propane or pentaerythritol, with a monoacid or mixture of
monoacids. Oligomeric esters, generally known as complex esters, can be manufactured by reaction of a diol or polyol with
a di or polyacid/anhydride, with a monoacid or monoalcohol
to act as capping reagent. This allows preparation of materials
having higher average molecular weights and consequently
higher viscosities, than can be achieved with simple diesters or
polyol esters. However, complex esters also have a distribution
of molecular weights, which means that their volatility characteristics are not as good as simple esters of the same number
average molecular weight.
Copyright'
and Product
www.astm.org
250
HANDBOOK
whereas azelaic, sebacic, and C36 dimer acids are derived from
natural fatty acids [8]. The monoalcohols used in diesters are
mainly manufactured by carbonylation of olefin feedstocks.
These alcohols are also used in the manufacture of plasticizers
and ethoxylate surfactants. They are generally commercially
available as a mixture of isomers and/or carbon chain numbers. Exceptions include 2-ethylhexanol, a derivative of butanol, which is a single isomer, and the linear C-even alcohols
(eg Cg, Cio alcohol), which are manufactured by chemical reduction of naturally occurring fatty acids [9],
The mono acids (fatty acids) used in polyol esters may be
derived either from petrochemical or natural sources. Naturally occurring fatty acids are almost always linear and have
an even number of carbon atoms. Lower carbon numbers
Polyol esters
R'"
R"-
CK
O ^
R = C4-C17linearor
branched aikyi
groups
^R
R"
PE; Pentaerythritol; R' = R" = R'" = CH20COR
TMP; Trimethylol propane; R" R" = CH20C0R, R" = Et
NPG; Neopentyl glycol; R' = CH20C0R, R" = R" = Me
FIG. 4Examples of polyolesters.
Acid
st(^r:'
nWater
Aromatic esters
o
I ^ I
II
Phthalate O
Trimellitate
II
Diesters
R'
>^'
% C
( ^ " 2 > n - \
. /
0 ~ R '
n = 4 - adipates
n = 7 - azelates
n - 8 - sebacates
n = 10 - dodecanedioates
R' - C8 - C13 linear or branched alkyl groups
FIG. 3Examples of diesters.
LUBRICANTSNON
AQUEOUS
251
252
MANUAL
HANDBOOK
and polyol esters are typically used. The more polar ester
serves to enhance solubility of less polar additives in PAO,
and confer seal swelling properties, as well as superior thermal stability. PhthaJate esters have been used where a low
cost seal swellant is required.
Diesters based on C36 dimer acid and polyol esters are frequently used in two stroke cycle formulations to provide low
smoke properties and biodegradability for spilled or uncombusted oil, particularly in marine applications.
Hydraulic fluids are formulated using synthetic polyol esters or diesters where a combination of good oxidative stability and biodegradability is required. Organic esters also
have better flame retardancy than mineral oils, although not
as good as phosphate esters.
As noted above, polyol esters remain the lubricant base fluid
of choice for aviation turbine lubricants, even in military applications. Polyol ester- derived aviation turbine lubricants
are generally formulated containing aminic antioxidants and
ashless phosphate ester antiwear agents. There is continuing
interest in increasing the upper temperature limit for aviation
turbine lubricants, but the thrust of current research has
moved away from investigation of alternative base fluids towards optimization of ester chemistry.
The relatively recent development of hydrofluorocarbon
(HFC) compatible refrigeration compressor lubricants has
led to increased demand for polyol esters [20].
Concern over the environmental impact of the ozone
depleting chlorofluorocarbons (CFCs) previously used as refrigerant fluids has led to international legislation prohibiting
their use. This has resulted in a change to alternative refrigerants including the zero ozone depletion potential HFCs. The
HFCs are not miscible with the hydrocarbon lubricants that
were generally used in CFC systems. Lubricant immiscibility
was found to cause poor oil return leading to lubricant starvation in the compressor and fouling of low temperature heat
exchange surfaces. Consequently, it has been necessary to develop new HFC-miscible synthetic lubricants. Polyol esters
have been generally adopted as the preferred basefluid for
most HFC compatible refrigeration applications.
POLYALKYLENE GLYCOLS
Polyalkylene glycol (PAG) is a generic name used to describe
a family of products formed from the polymerization of one
or more alkylene oxides. Such products are also known as
polyethers, polyoxyalkylene glycols, polyalkylene glycol
ethers, polyglycols, and PAGs [21,22]. PAGs are an extremely
versatile family of products, which can exhibit a wide range of
physical and chemical properties. They are excellent lubricants in their own right [22-25], which makes them the fluid
of choice for a large n u m b e r of engineering and lubricant
applications.
The history of PAGs is a long one. The earliest reported
polymerization of ethylene oxide dates back to 1863 [26],
with the first commercial products (polyethylene glycols)
available in 1939 [27]. The range of viscosities now covered
by PAGs is vast, making these products suitable as lubricants
in their own right, but also as thickeners and lubricity improvers in water based systems.
4.5
polyether section
(CH2-CH(R)-0)
end group
-
R2
- * R-O-K+ + H2O
R-OK* + CH2-CH2"
R-0-CH2-CH,-0-K+
AK
R-O-CH2 - CH2 - O- K+ + n-1 (CHj - CH2 )
Post-treatment:
R-(0-CH2 - CHj ) - O - K+ + 'H+'
R-(0-CH2-CH2)-0-H
FIG. 6Reaction scheme for PAG production.
254
HANDBOOK
Physical Properties
The physical properties of a selection of commercially available PAGs are shown in Table 1, to illustrate the range of
physical properties.
VI
Mol
Weight
Density
(g/cm^)
@20C
Cloud
Point
CC)
Flash
Point
Open Cup
ASTM D 92
(C)
D2270
103
204
184
242
157
225
287
408
489
350
1900
2000
2600
1200
1650
4500
12500
25000
D70
0.9573
0.9940
1.0035
1.0031
1.0951
1.0564
1.0574
1.0908
1.0905
D2024
insol
insol
insol
insol
>100
59
53
81
76
D92-97
80
225
230
232
254
230
230
240
240
Viscosity
(mm?/s)
Functionality
of Initiator
EO/PO
Ratio
40C
100C
ASTM Method
Mono
Mono (a)
Di(b)
Di
Tri (c)
Mono (d)
Mono
Di
Tri
0:1
0:1
0:1
0:1
3:1
1:1
1:1
3:1
3:1
D445
11
126
142
387
127
132
1050
19500
45000
D445
3
22.5
22.2
65
18
25
180
2400
6500
NOTE: the molecular weight is calculated from Mol Weight = functionality of initiator * 56100/OH value.
Point
Pour
Point
CO
D97
-53
-36
-36
-23
-28
-42
-28
4
7
LUBRICANTSNON
AQUEOUS
255
.2
(0
o
a.
"Q.
(S
I
I
3
o
o
(0
a>
I
(3
<
E
o
I
f
CO
o
a
#
o
CO
.2
(0
'a.
a
CO
a
CO
u
4)
E
v
oa
LL
/-I
Polyalphaolefiin fluids, or PAOs, are synthetic, saturated hydrocarbons that are manufactured by a two-step process from
hnear alpha-olefins, that are themselves manufactured form
ethylene. These synthetic hydrocarbons are generically described by their viscosity at 100C. The most common commercially used PAOs are 2, 4, 6, 8, and 10 cSt and the higher
viscosity grades 40 and 100 cSt. PAOs have excellent physical
properties when compared with conventional mineral oils, a
wide operating temperature range, including high flash and
firepoints, high viscosity indices and low volatilities. When
compared with certain natural and synthetic esters, PAO fluids have excellent thermal, oxidative, and hydrolytic stability.
Since the mid 1980s PAOs have quickly gained market share
in the synthetic lubricant base fluid market, particularly in
Europe [48]. The major application area was and continues to
be the automotive sector for crankcase oils answering the
quest for tighter specifications for lower oil volatility. Today,
automotive crankcase lubrication is still the main application
area for PAOs globally. Other automotive application sectors
are now two-stroke cycle engine oils, automatic transmission
oils, gear oils (multigrade), and greases. Industrial applications include: hydraulic oils, compressor oils, heat transfer
fluids, and food grade oils and greases.
The milestones of the technical history are marked by three
patents, one by Brennan [49] at Mobil Oil in 1968 and two by
Shubkin [50,51] of Ethyl Corporation in 1973. Brennan first
described a process for oligomerization of alpha-olefins
using a BF3ROH catalyst system [49] whereby the combination of the selected process conditions and the catalyst system yielded a product consisting of a mixture of oligomers
with a high concentration of trimers. Shubkin showed that
instead of ROH as a co-catalyst, H2O [50] or alcohols and
carboxylic acids [51] could be also used in combination with
BF3 to produce oligomers of uniform quality.
The U.S. Army and U.S. Navy took an early interest in this
new synthetic base fluid. In July 1970 the MIL-H-83282 specification for fire resistant hydraulic fluids based on PAOs was
established in cooperation with the industry [52].
Chemistry and Meinufacturing
As the name implies, Polyalphaolefines are synthesized up
from alphaolefines. The starting material of the chemical
CH2 = CH2
Catalyst
>
BF3
Unsaturated
R-CH=CH2
>
ROH
Unsaturated Oligomers + H2
aigomeric
Mixture
Dimer
Trimer
Tetramer
Pentamer
Higher
NIorPd
DIstilatlon
Oligomers
DImer
Trimer
Tetramer
Pentamer
Higher
Viscosity
Grades
Qimsr
synthesis is ethylene as shown in Fig. 8. The reaction products of the first step are linear unsaturated alphaolefins
(LAO). These LAOs are used for the manufacture of a variety
of chemicals, mainly as detergents. For the synthetic lubricant base fluids (PAOs 2-10 cSt), mainly 1-Decene is
oligomerized with the catalyst BF3 and a protic co-catalyst
such as water or an alcohol. For the higher viscosity PAO 40
and PAO 100 Ziegler-Natta (Aluminium chloride based), catalysts are used. The unsaturated oligomer mixture is hydrogenated using either Nickel or Palladium catalysts. Finally, a
distillation step is applied to remove unreacted monomers
and to separate the various product grades. Sometimes the
distillation step is carried out prior to hydrogenation [54].
The tjrpical molecular structures of a dimer, trimer and a
tetramer of 1-decene are shown in Fig. 9. Every oligomer is
branched and is present as a number of different isomers.
Though 1 -decene is the pre-dominantly used alphaolefine for
PAO manufacturing, shorter or longer chain length olefines
may also be used. In particular, 1-dodecene has recently
gained importance for the synthesis of PAO 5 and PAO 9 [57].
Tailor made products can also be obtained by changing
reaction vsiriables such as temperature, time, catalyst concentration, co-catalyst t3^e, and concentration and distillation conditions [57].
Physical Properties
The physical properties of the common commercially available PAOs are shown in Table 2. The given properties are typical values and do not represent values for PAOs from a
particular supplier. The low viscosity PAOs 2-10 have
excellent low temperature properties which make them very
suitable for applications in cold climate. The average viscosity index (VI) calculated by ASTM D 2270, Practice for Calculating Viscosity Index from Kinematic Viscosity at 40C and
lOOX (DIN/ISO 2909) for PAOs is 135. This has the advantage
that the viscosity changes much less with increasing temperature compared to a product with low VI. For PAO 2 no VI is
given because VI is undefined for fluids having a kinematic
viscosity ofless than 2.0 cSt at 100C. The advantage of a high
VI is that addition of viscosity index improvers is not required
for the formulation of lubricants for many applications. Also,
the addition of pour point depressants is often not necessary
as the pour points for PAOs are very low. In Table 2 some other
physical properties are given which are important to the lubricant formulator. The flash point is important for safety reasons and the given flash points in Table 2 are at least as high
258
MANUAL
HANDBOOK
Test Method"
PA0 2
PA0 4
PA0 6
PAO 10
PAO 40
PAO 100
KV @ 100 C cSt
KV @ 40 C cSt
KV @ - 4 0 C cSt
Viscosity Index
Pour Point, C
Flash Point, C
Noack, % Loss
ASTM D445
ASTM D445
ASTM D445
ASTM D2270
ASTM D79
ASTM D92
DIN 51581
1.80
5.5
310
3.90
16.8
2540
122
-69
215
12.0
5.90
31.0
7800
137
-63
225
6.7
9.60
45.8
19000
134
-54
264
2.0
40.0
395
100
1250
150
-34
280
0.8
170
-20
290
0.6
-63
>155
99
T (onset) [C]
187
187
210
198
196
196
254
260
262
274
as those of mineral oil of the same viscosity. Volatility is measured by the standard NOACK volatility test at 250C for 1 h.
Except for PAO 2, all other PAOs have very low volatility,
which makes them very suitable for high temperature applications and engine oils to reduce the need for "topping-up."
Low volatility is also an important property for a fluid to retain the original viscosity during its working life.
The highly viscous PAO 40 and PAO 100 hsted in Table 2
are similar to low viscosity PAOs and have good viscometric
properties and allow operation over a broad temperature
range. New PAOs with m e d i u m viscosity grades 5, 7, and 9
and very high viscosity grades, u p to 3000 cSt, and have recently been developed as custom-synthesized products [56].
Chemical Properties and Performance
Characteristics
Oxidation stability is one of the most important properties of
automotive lubricants, which are mainly responsible for the
oil renewal time. Essiger [57] investigated the oxidation stability of different motor oil qualities with High Pressure Differential Scanning Calorimetry (PDSC) as shown in Table 3.
PAO without anti-oxidants is as stable as mineral base oil,
blends with synthetic ester, a n d shows superior oxidation
stability. In the presence of anti-oxidants, such blends were
significantly more stable than mineral oil based engine lubes.
The use of PAO is also c o m m o n today in high performance
greases. The lifetime of such greases is said to be three to five
fold c o m p a r e d to mineral oil based products. Wunsch
recommends operating temperatures of u p to 150-160C for
Lithium-12-hydroxystearate greases based on PAO [57].
Silicones
Silicones are polymers containing the siloxane (SiOSi)
backbone structure with pendant alkyl side chains, normally
methyl groups. The chemistry is well established and silicone
fluids have been commercially available since the 1940s
[59,60]. They are manufactured by hydrolysis of dialkyldichlorosilane themselves p r e p a r e d by reaction of
methyl chloride (or other alkyl chlorides) with silicon metal.
Trialkyl monochlorosilanes are introduced into the reaction
in controlled stoichiometry to act as end capping reagents
and control the molecular weight.
Silicone fluids can be prepared with viscosities ranging
from < 1 to > 500 000 cSt. They are characterized by low pour
points, low surface tension, high compressibility and little
change in viscosity with temperature. The standard viscosity
index calculation is not appropriate for silicones and other
materials with such low temperature coefficients of viscosity.
Methyl groups m a y be substituted by other functional
groups to modify the inherent properties of the basefluid.
LUBRICANTSNON
AQUEOUS
259
Polyphenyl Ethers
Polypheny] ethers (PPEs) consist of benzene rings joined by
ether links, with the ether links in bridging monomer units
being arranged in meta geometry. They were developed during the 1950s for high thermal, oxidative, and radiation
stability [61].
PPEs are manufactured by reaction of phenols and halides.
The simplest member of the family is diphenyl oxide; longer
chain analogues are available up to six benzene rings and are
coded according to the number of benzene rings and ether
groups they contain; thus 5P4E contains five benzene rings
and four ether linkages.
PPEs have very high pour points and most are not liquids
at room temperature. For example, the only example which
is currently commercially available, 5P4E, crystallizes at
43C in the pure state, and therefore must be mixed with
other fluids to extend the liquid range and inhibit
crystallization, or used only in applications where it will re-
260
HANDBOOK
SUJVIMARY
Synthetic lubricants possess superior performance capabilities compared to mineral oils. There are three main reasons
why synthetic lubricants are selected in preference to mineral
oils:
improved stability, usually oxidative,
improved lubricity, usually at very high or very low temperatures and
reduced environmental impact, usually high biodegradability or reduced toxicity.
Oxidative
Stability
Their volatility is therefore highly dependent on the test temperature. The types of additives used also play an important
role. Therefore, the table should only be used as a rough
guideline.
The generation of heat from friction causes the temperature of the oil film to increase. This higher temperature reduces the viscosity of the oil. As the oil's ability to remove
heat is increased, this may lead t o lower operating
temperatures. A lower temperature will reduce the decrease
in viscosity of the lubricant and also reduce the oxidative
degradation of the lubricant, potentially increasing the life of
other components in the system. The heat transfer of various
lubricants can be compared by using a simplified version of
the Sieder and Tate equation given below [69]. This equation
is applicable to areas of turbulent flow. The equation can be
further simplified for areas of laminar flow.
LrO.bl pO.8^0.33
ha
snnHEtic HnmocAfaoNS
Where:
h =
K =
p =
X=
Cp =
SUGON^
too
aoo
300
TEMPERA-niRE ' C
FIG. 10A comparison of oil lifes for a range of synthetic lubricants [66].
Volatility
at 250 "C
Poor
Good
Fair
Very good
Poor
Very poor
Excellent
Good to excellent
Deposit Formation
at 250C
Poor
Fair
Fair
Excellent
Very good
Good
Very good
Very good
TABLE 5-
Lubricant Type
Thermal Conductivity
at 100C
m W m " ' C"'
Density at 100C
gcni~^
(ASTM D 70)
Lube Heat
Transfer Coeft.
Mineral Oil
PAO 6 [67]
Polyol ester [68]
PAG
0.52
0.55
0.55
0.46
127
144
150
185
0.82
0.77
0.93
1.02
6.49
4.54
5.58
7.75
7.33
9.14
9.91
9.21
Lubricant
Viscosity at 100C
icSt)
(ASTM 445-97
DIN 51550)
3.8
3.9
4.5
1300
500
550
Type of
Lubricant
Index
(ASTM 2270)
0-80
80-120
120-150
50-150
50-170
150-280
<0-110
Viscosity Pressure
Coefficients (GPa~"
18.0 -is.ot^" -10.5^"] -5.3[] -5.3^=5 _7 7[72] _11.8--
36.0^^"
23.0C72]
12.6
19.9
21.1
19 jpo]
33.4
Mineral Oil
PAOs
Esters
PAGs
Suitable
Not Suitable
HFC/HFCs, CO2
HFCs
Ammonia
Hydrocarbon
Acceptability
CHAPTER
Eco-labels for lubricant applications are starting to appear
in both the United States and Europe. Initially these have
been focused a r o u n d hydraulic fluids (Blue Angel in Germany, Nordic Swan in Scandinavia, and ASTM D 6046 in the
U.S.) but this is likely to be extended to other application areas in the future. The schemes are voluntary and have been
set u p to allow products to be differentiated using an agreedupon environmentally friendly labelling classification. The
biodegradability of the lubricant is an important part of the
legislation and can be measured by a variety of different test
methods (CEC-L-33-A-94, OECD 301B, ASTM D 5864, etc.).
The biodegradability of a variety of synthetic lubricants is
shown in Table 9. Even within a class of synthetics, the
biodegradability can cover a large range. Different
biodegradability tests can also give very different results for
the same chemistry. Results can also be highly dependent on
where the activated sludge used in the tests is obtained from.
However, in general high viscosity, aromaticity, and a high
degree of branching all have a negative impact on biodegradability. ASTM D 6006 and D 6384 are useful guidelines to
biodegradability testing and the terminology used to describe
the results.
Food and Drug Administration (FDA) approved low toxicity lubricants are required increasingly for applications connected to the food industry. The FDA food approval system is
undergoing major changes and will be replaced shortly by a
new system. However, the old FDA classification system is
still being used. See Table 10. The cost of registration of a
new lubricant for food use can be considerable.
For many of the lubricants, several limitations of use are
listed, such as maximum dose rate or effect (e.g., can only be
used at a dose rate of bellow 0.5% in another FDA approved
oil).
Relative
Cost of
Synthetics.
Synthetic lubricants are made from a range of relatively expensive raw materials via a whole range of chemical interacTABLE 9Biodegradability of synthetic lubricants.
Lubricant Type
% Biodegradability
by CEC-L-33-A-94 Test
After 21 Days
% Biodegradability
by OECD 301B Test
After 28 Days
Mineral oil
PAOs
Diesters
Aromatic Esters
Polyol Esters
Alkyl Benzenes
PAGs
Polybutenes
10-45
20-80
75-100
0-95
0-100
5-20
5-70
5-20
10-40
5-60
25-80
5-45
0-80
0-20
5-80
0-20
FDA Registered
No
Yes
Glycine ester (CAS No 110-25-8) and
Isopropyl oleate
Several water soluble and insoluble PAGs >
RMM = 1000
Hydrogenated polybutenes listed under
178.3740
10: SYNTHETIC
LUBRICANTSNON
AQUEOUS
263
2-3
10-50
50-250
75-300
ASTM STANDARDS
No.
D70
D86
D91
D92
D93
D94
D97
D 130
D 189
D445
D471
D524
D664
D665
D873
D892
D 892 (Option A)
D943
D972
D974
D
D
D
D
1209
1218
1298
1401
Subject
Density
Distillation
Precipitation n u m b e r (Sludge Formation)
Flash Point - Cleveland Open Cup
Flash Point - Pensky-Martins
Saponification Number
Pour Point
Copper Strip Corrosion
Carbon Residue - Conradson
Viscosity - Kinematic
Elastomer Seal Compatability
Carbon Residue - Ramsbottom
Acid Number, Potentiometric
Rust Prevention
Potential Residue
Foaming Characteristics (Sequence IHI)
Foaming Characteristics (Sequence IIII) (Option A)
Turbine Oil Stability Test (TOST)
Volatility - Evaporation loss
Acid/ Base N u m b e r by Color Indicator
Titration
Color - APHA
Refractive Index
Density
Emulsion Characteristics
Color - ASTM
Water Content by Karl Fisher
Rust Protection
Thermal Stability
Viscosity Index
Rotating B o m b Oxidation Test
Cloud Point
Cold Cranking Simulator
Hydrolytic Stability (93C)
Volatility - NOACK at 250C / TGA
method
Falex PinA^ee
Demulsibility Characteristics
Gas Solubility
Timken OK Load
EP, 4-Ball E P
Viscosity -Brookfield
Falex Pin/Vee
Air release
Gas Solubility
Specific Gravity
Four ball wear
Base N u m b e r
Thin Film Oxygen Uptake Test
Ball on Cylinder Lubricity Evaluation
Brookfield - Scanning
Elemental Analysis
Vapour Pressure, Reid
Viscosity - High T e m p e r a t u r e High
Shear by capillary
Volatihty - NOACK at 250C / TGA
method
High Frequency Reciprocating Rig
Foam, High Temperature
Foam, High Temperature (Option A) TMC Certified
Phthalate Esterification
Coulometric Karl-Fischer Titration
Specific Heat Capacity
OTHER STANDARDS
No.
D I N 51 5 5 0
DIN/ISO 2909
D I N 51 5 9 7
D I N 51 3 7 6
D I N 51 5 5 9 P a r t 1
DIN 51 777 Part 1
Subject
K i n e m a t i c Viscosity
K i n e m a t i c Viscosity Index
P o u r P o i n t of P e t r o l e u m P r o d u c t s
Cleveland Open C u p
Calorimetric Titration
Coulometric Karl-Fischer Titration
REFERENCES
[1] Barnes, R. S. a n d F a i n m a n , M. Z., Lubrication
Engineering,
1957, p. 454.
[2] Smith, T. G., "Neopentyl Polyol Esters," Synthetic Lubricants, R.
C. Gunderson and A. W. Hart, Eds., Reinhold, NY, 1962, p. 388.
[3] Randies, S. J., "Esters," Synthetic Lubricants and High Performance Functional Fluids, R. L. Rudnick and R. L. Shubkin, Eds.,
Marcel Dekker Inc., NY, 1999, p. 63.
Mortier and S. T. Orszulik, Eds., Blackie Academic and Professional, London, 1997.
[81] Smeeth, M. and Spikes, H. A., "The Formation of Viscous Surface Films by Polymer Solutions: Boundary or Elastrodynamic
Lubrication?," Paper 95-NP-7D-2, Presented at the 50th Annual
Meeting, STLE, Chicago, IL, 14-19 May 1995.
[82] Summers-Smith, D., An Introduction to Tribology in Industry,
The Machining Publishing Co. Ltd., Brighton, UK, 1969.
[83] CONCAWE (Conservation of Clean Air and Water Europe), The
Collection, Disposal and Regeneration of Waste Oil and Related
Materials, Report 85/33, The Hague, 1985.
[84] Betton, C. I., "Lubricants and Their Environmental Impact,"
Chemistry and Technology of Lubricants, 2nd Edition, R. M.
Mortier and S. T. Orszulik, Eds., Blackie Academic and Professional, London, 1997.
MNL37-EB/Jun. 2003
A
Cs
d
FM
g
P
Q
T
V
V
P
DIN
EP
HEES
HEPG
HETG
HFA
HFC
NZ
ppm
TMP
VI
WGK
C
CI
CO2
H
H2O
N
O
VCI
Units
,2
m
area
J/(kgK)
heat capacity
mm
diameter
N
force
gravity
m^/s
bar (lO^N/m^)
pressure
flow
m^/s
C
temperature
m^
capacity
Ns/m^
dynamic viscosity
mm'^/s
kinematic viscosity
kg/m^
density
Deutsches Institut fiir Normung
Extreme Pressure
Hydraulic-Environmental group ES (synthetic
ester)
Hydraulic-Environmental group PG (polyglycol)
Hydraulic-Environmental group TG (tri-glycerid)
Hydraulic-Fire-resistant group A (water-based)
Hydraulic-Fire-Resistant group C (water glycol)
Neutralization N u m b e r
Parts-Per-Million
tri-methylol-propan
Viscosity-Index
Water Hazard Class
Carbon
Chlorine
Carbon Dioxide
Hydrogen
Water
Nitrogen
Oxygen
Verband Chemischer Ingenieure
Pressure Media
In a variety of technical systems, hydraulic drives are the preferred alternative because of their versatility and efficiency.
To perform the drive functions over the life of the system, the
hydraulic fluid must be considered as a system component
during the design stage. Due to a societal increase in
' Executive Director, Institute of Fluid Power Transmission and
Control, IFAS, University of Teciinology Aachen, Steinbachstr. 53, D52074 Aachen, Germany.
^ Product Engineering Hydraulics, John Deere Works Mannheim,
Windeckstr. 90, 68163 Mannheim, Germany.
267
Copyright'
www.astm.org
268
MANUAL
HANDBOOK
for high loads [16]. In addition, the fluid must provide good
lubricating film wetting between surfaces moving relative to
each other that reduce wear and stick slip. Materials used in
hydraulic components such as bronze or other alloys are susceptible to corrosion. Consequently, the fluid should contain
only a m i n i m u m a m o u n t of free acid, if any. The by-products
created by the aging process must be neutralized or adsorbed
by additives contained in the fluid to eliminate any acid
build-up. In addition, the fluid properties must vary only
slightly over extended time [31].
Elastomers and other non-metal components may also
be attacked by these by-products. Increased elastomer
swelling may result in complete decomposition and sealing
failure.
Mechanical and volumetric losses in hydraulic units are responsible for heat generation. This heat is partially released
to the environment by convection. The pressure media itself,
however, accounts for the major part of the heat loss. To limit
the temperature increase of the fluid, it must possess high
heat capacity and thermal conductivity.
These demands are directly related to the use of the pressure media in a hydraulic system. The development of fluids
is significantly influenced by external requirements. For ex-
FRIENDLY OILS
269
Base Fluid
Saturation
Origin
HETG
HEES
Native ester
Synthetic ester
Unsaturated
Unsaturated
Saturated
HEPG
Poly-glycol
Native materials
Native materials
Chemical industry
Chemical industry
for the production of synthetic esters, a wide variety of technical performance properties is possible. Early synthetic esters possessed a chemical structure similar to rapeseed oil.
HEPG fluids is the third fluid type and is the only type that
is water-soluble. This can be an advantage for the biological
degradation in water. On the other hand, there is the danger
of fluid-contaminated water penetrating more deeply into the
soil layers, thus reaching ground water. For that reason, in
some countries, polyglycols are not considered environmentally friendly fluids.
CHEMICAL B A S E S O F N A T I V E A N D
SYNTHETIC ESTERS
Functional Groups and Elementary Compound
Pressure media based on native and synthetic esters consist
of carbon-hydrogen bonds as do mineral oils. However, the
structure differs significantly from that of mineral oil, which
explains the different properties and performance characteristics exhibited by these fluids. Examples of the different
functional groups can be seen in Fig. 4.
The characteristic group for an alcohol is the hydroxy
group (OH-group). In a case where the OH-group of aliphatic
alcohols is connected to a carbon-atom, the alcohol is described as primary alcohol. In a case where the OH-group is
connected to a carbon-atom in the center of the molecule, it
is considered secondary alcohol. Tertiary alcohols are those
with an OH-group connected at a branch site in the molecule.
The hydroxy group of alcohols is responsible for their
higher boiling points compared to those of the comparable
270
MANUAL
carbonyl-group
HANDBOOK
alkyl-group
Mechanism of Esterification
CH
OH
H
carboxyl-group
aldehyde
O
CH
COH
ketone
0
II
carboxylic acid
R1-CR2
alcohol
ester
R 2 - C OH
R^-OH
R^-OC R2
R^
\
-.1
OH
R'
OH
In Fig. 8, the general equation of a reaction for the production of esters is shown. This chemical reaction produces ester and water. Water must be removed during reaction to
achieve a complete conversion of the alcohol reaction with
the acid to produce a n ester (by shifting the equilibrium to
the right).
The equilibrium constant (K) for the ester producing reaction is [30]:
-.1
R'
+\ *
OH - - 0 H
alkanes, because of the shared hydrogen bond of the hydroxyl groups. A strong polarity of the OH-connection is
based on the electro-negativity of oxygen. The result is a positive shifting of the hydrogen a t o m so that the hydrogen
bonding connection shown in Fig. 5 becomes feasible.
The possibility for hydrogen bonding is the reason for the
still unlimited miscibility of simple alcohols with water.
However, with increasing size of the non-polar organic alcohol residue, this characteristic decreases.
The abbreviation R used in Fig. 5 represents a n alkylgroup. This is a n acylic saturated carbon-hydrogen compound, called an aJkane, from which a hydrogen molecule is
split off. According to their bonding capability, alcohols are
considered to be monovalent, bivalent, or trivalent.
To produce a synthetic ester hydraulic fluid with good performance properties, carboxylic acids are used. The carboxy
g r o u p COOH is the functional g r o u p of carbon acids. Its
nomenclature is based on the combination of the carbonyl
and hydroxy group. Carboxylic acids with long-chain Rgroups attached are called fatty acids. The capability of carbon acids to hydrogen bond as with alcohols, is based on
their chemical structure. This is the reason for their relatively
high boiling point, which is comparable to alcohols due to its
dimeric structure resulting from the hydrogen bonds shown
in Fig. 6.
Small carbon acids like the corresponding small alcohols
are still soluble in water. However, the solubility diminishes
with increasing molecular size. When carboxylic acids contain only single bonds, they are considered saturated.
Unsaturated acids contain at least one double bond. The
n u m b e r of double bonds influences chemical properties. Furthermore, carboxylic acids are distinguished by different isomers resulting in different chemical and physical properties
(Fig. 7).
[ester] [water]
[acid] [alcohol]
R ' - Cy
.
+
O H
,0HO
C R^
R^ - C
CR^
OHO
cis-configuration
trans-configuration
C=C
H
FIG. 7Isomers of carboxylic acids, cis and trans structure.
carboxylic acid
aicohd
ester
water
H
O
R^-C OH
R} - O H
R' - O C R 2
OH
FRIENDLY OILS
271
R3C-O
- >
R3C
H2O
H
3. step: electrophilic carboxyl group attack
1. step: carbonyl oxygen protonation
o
1 II
OH'
R^ - C
^
H
1 II
*
R^ - C O H
~*'
R^ - C O H
4. step:proton migration
0^CR,
OH*
OH
R^ - G
R 2 --OH
R^- - c 0
~*
R^ - C O *
- C = 0 H " '
OCR3
OCR3
R^-C=O
R^1 - CI O R 2
Alcohol Bonds
L V
4. step: water split off
OH
R1
^ - CI O R^
Ri
OH
OCR3
R^-C=OH'
R1^ - CII O H
FIG. 9aEster synthesis with primary and secondary alcohols under acid conditions [22-30].
OR""
R,1' - C
H.O
II .
OH
5. step: proton split off
0 R-"
1
R^ - C
//
\
OH
Rfi^
I
OH
R' - C
"^
R^ - C
OH
o'^CRj
OR"
FIG. 9bEster synthesis with primary and secondary alcohols under acid conditions.
272
trimethylolpropane
HH
glycerin
OH
OH
C H
HC H
H
H-CC
H
HANDBOOK
-C O H
-OH
H
HCH
HCH
OH
OH
trimethylolethane
pentaerythritol
OH
OH
vinegar acid
H C H
stearic acid
HC H
O
H
-C OH
-c-
OH-C-
-OH
OH
neopentylglycol
-C
I
C
CH
"*^17'^35
OH-CC^H,-^H
-c-
HCH
II
OH
H0CCH
"T"
-CH
H
H CH
"^8^17
OH-CC,H;
OH
'^5^n
Carboxylic Acids
-CC^C-
mono aster
II
II-
II
R1-0CR2
R1-0CR2-C0R3
glycerin ester
0
II
II
CHj-OCR1
CHj-OCR1
C,H,-C*
Q[_|__Q
HC
-R1
CI H j - O C R 1
CJ H j - O C R 1
complex ester
0
0
II
II
CH^-O0R1
C^riy - 0 - - C R 2
0
C,H,-( ; C H j - o c -R1
C,Hg<
II
-CH,- 0 C R 2
CH,-0CR1 - C O C H ,
II
The position of the double bond within the fatty acid has
no significant influence on the pour point. However, slight
differences can be observed depending on the degree of distortion imparted by the double bond of the molecule. Depending on the position of the double bond, the distance between molecules increases, resulting in slightly different
pour points (Fig. 16).
Besides the number of double bonds, their steroconfiguration has a decisive influence on the viscosity properties. Ester with cis- double bonds will flow at low temperatures,
whereas fluids with trans- double bonds exhibit pour point at
comparable temperatures.
Branching exerts similar influence as double bonds. With
increasing branching at a constant carbon number, the cold
flow behavior of the ester increases and viscosity decreases.
In contrast, an increased chain length with the same structure results in an increase of viscosity.
Reduction of the pour point is also obtainable by using esters with acid mixtures. These mixtures do not crystallize as
readily thus leading to a decreased pour point.
With the more complex esters there is no correlation between viscosity and carbon number, since the viscosity increase is compensated by branching, due to increasing carbon number.
g 60"o
Q.
3
O
ziU
-40 -
6:0
8:0
45
40
"
'*
^>
< - -
4*
''
35
B
O 30
cis
.e 25
o
a.
S 20
o
- 15
10
pentaerithritol
trimethylolhexane
trimethylolpropane
trimethylolethane
glycerin
neopentylglycol
D5
D7
D9
D11
D13
274
MANUAL
HANDBOOK
Hydrolysis
The chemical reaction for ester production is an equihbrium
reaction. Consequently, all esters-based fluids cleave into
their alcohol and acid components upon hydrolosis. This directly influences the ester bond. This reaction, also called
"hydrolytic splitting," which continues until the chemical
equilibrium is restored. Thus, hydrolytic stability of an ester
is influenced by its chemical structure.
Steric hindrance of the ester bond improves hydrolj^ic stability. This protection is due to the presence of methyl groups
instead of hydrogen atoms relative to the ester group. Those
methyl groups sterically protect the ester bond against water
attack. Depending on the n u m b e r of methyl groups positioned around the ester group, the reaction rate may be reduced many times. Table 2 provides a survey of the reaction
rate as a function of the amount of branching.
With mono-esters, hydrolytic stability is primarily increased using linear short-chain alcohols. Even short alkyl
chains in these alcohols yield a significant increase of hy-
CHAPTER
tion stability. As a rule, saturated alcohols are used for the
production of lubricants and pressure media. For that reason, the oxidative stability is mainly determined by the degree saturation of the carboxylic acids. In general, the tendency of an ester molecule towards oxidation continually
increases with increasing amounts of unsaturated carboxylic
acids. Figure 18 shows this for three different saturated
polyol-esters a n d rapeseed oil. The oxidation stability of
those fluids was determined by the viscosity increase after an
aging process according to the Baader-test (DIN 51587).
The dependency of the oxidation time for vegetable oils can
be taken from Fig. 19. These results were obtained by the
R a n k i m a t method, which provides a significant improvem e n t in the precision of the test. Rapeseed oils, which are low
in euricic-acid content and sunflower oils, which are high in
oleic acid content were used as hydraulic fluids. Mixing those
oils provided the required degrees of saturation. The strong
dependency of the stability on the a m o u n t of double bonds is
evident.
Oxidative stability may be enhanced by sterically protecting the double bond, e.g., by branchings. The effects of steric
b r a n c h i n g on oxidative stability are comparable to the
180
160
140
10
'1
F
>
120
rapseed oil
unsaturated polyol-ester
partial saturated polyolestsr
saturated polyol-ester
10(1
+ j
(A
O
O
an
ID
3
4
5
aging time [days]
^\l
le" 1R
(1>
14 -
19 IZ -
o T"
o o
5
fi0
O
.E 4
O
03
3.25
3.5
3.75
4.25
4.5
4.75
FRIENDLY
OILS
275
amount of increased hydrolytic stability obtained. In addition to the amount of unsaturated carboxylic acids (relative
to s a t u r a t e d esters), the n u m b e r of double bonds in carboxylic acid also influences oxidative stability. In general, increasing the number of soluble bonds in a carboxylic acid (increasing unsaturation) decreases oxidative stability.
The foregoing discussion provides only an overview of
structure-performance consideration of ester base stock.
However, the generalizations m a d e t h u s far will aid the
reader in understanding lubricant formulation to provide
high load capacity and good chemical and physical properties. The summary of the effects is illustrated in Fig. 20.
PRODUCTION OF ENVIRONMENTALLY
FRIENDLY FLUIDS BASED ON NATURAL
AND SYNTHETIC ESTERS
Native Esters
Oil is removed from rapeseeds by milling, pressing, or extraction. These seeds contain approximately 40% oil and
8-10% water by weight. In the milling process the seeds are
fed into rollers to break down the cells so the oil can be released. Next, the milled seeds are conditioned by heating to
80-90C to control the humidity to a m a x i m u m of 8% (Fig.
21). By this procedure, the vegetable oil becomes lighter and
thinner. The seeds are then squeezed in a screw press under
a pressure of 200 bcir. This procedure yields between 40-60%
of oil. A higher yield can be obtained by either a finishing or
by solvent extraction. The finishing process removes 90-96%
of the oil. For economic reasons the extraction method is the
procedure of choice.
A higher oil yield can be obtained either by another pressing process, the finish pressing, or by extracting the prepressed coarse-ground grain. By finish pressing, the oil concentration decreases to values between 4 and 10%. An
extraction reduces the residual oil contents to below 2% in
the seeds. The individual production steps are shown
schematically in Fig. 22.
For extraction, a solvent is used to dissolve the glycerides
from the seeds, not the undesirable accompanying substances like gums or resins, slime, and dye materials. Moreover, the solvent must not contain any toxic substances that
are nonvolatile and thus unremovable. The solvent also must
be separated from the extracted material. Aliphatic hydrocarbons are used for this purpose, especially n-hexane, which
can, due to its boiling point of 55-70C, be separated easily
from the coarse-ground grain. After those steps, the extracted
raw material contains between 1 and 2% free fatty acids as
well as 300 p p m phosphatides and 0.35 to 0.5% sterines. To
achieve the desired quality of the vegetable oil, a refining process follows the extraction of the crude oil. Refining serves
the purpose of reducing the contents of free fatty acids to
0.05% and that of the phosphatides to 0.02 ppm. The following refining steps are necessary:
60
>
11: ENVIRONMENTALLY
276
HANDBOOK
hydrolysis
staWlity
viscosity
low
temperature
viscosity
oxidation
stability
viscosity
index
air release
property
L
,\
linearity
11
1,
. I
i,
i,
1,
, 1
1 I
1 1
It
Synthetic Esters
Raw materiaJs for the production of synthetic esters are derived mainly from petro-chemistry. However, it is also possible to use natural raw materials or their transformation products. In any case, this requires re-esterification or an
additional chemiced treatment, e.g., hydrogenation. Besides
the esterification procedure described previously, ester synthesis can be subdivided into the production of different alcohols and acids. The great majority of those products originate from other applications. The systematic production of
lubricants can be considered rather insignificant at this time.
Quantitatively, the largest portion of esters is the softener
sector. Long-chain alcohols and fatty acids cire mainly used
for the production of washing and cleaning agents, surfactants, and detergents. The fundamental path of synthesis will
be explained using a few examples.
MultifunctioncJ alcohols are produced using the so-called
"aldol condensation". This is a catalytic addition of carbanions by bases to the carbonyl group of aldehydes or ketones.
The carbanions are produced from activated methylene
groups. After this reaction step, water is eliminated. Figure
23 shows this process for the alcohol pentaerythritol. The
production process for trimethylol propane is very simple except when formaldehyde and n-butanal are used.
For the production of neopentyl glycol, the aldol reaction
is conducted in a slightly different way utilizing formaldehyde and i-butanal. However, as a catalytic agent, sodium hydroxide is used (Fig. 24).
The production of carboxylic acids can be divided into two
major processes. On the one hand, from natural oils and fats
the corresponding fatty acids can be generated directly by hydrolysis. On the other hand, an alternative process is to direct
re-esterification of natural oils with synthetic alcohols. In addition to those two possibilities, acids may also be produced using chemical processes. Figure 25 shows this process for adipic
acids being used for the production of di-carboxylic acid esters.
Large-scale production of synthetic esters are typically
batch processes. Depending on the desired degree of esterification, different catalysts are added to the process, leading to
an accelerated conversion. During esterification, undesirable
water is continuously removed from the alcohol and fatty acid
reactants to optimize the conversion process. The reaction is
stopped once the desired acid number, a measure for the completeness of the esterification, has been attained. To achieve
very low acid numbers (<0,5), another refining step is necessary. Undesired substances are eliminated from the ester by a
subsequent bleaching earth treatment. Finally, a filtration
step is required to eliminate the bleaching earth from the ester. A survey of the ester production process can be taken
from Fig. 26.
FRIENDLY OILS
277
seeds
milling
u.1
f steam ^
conditioning
squeezing
pelletextraction
n-hexane
j r
drying
n-tiexane
9^i:r^.':''i-'^'-''''-' -.y'-^wl
Vi
misceiia
.i a
filtration
L_n_
steam ^
toasting
D used n-hexane
drying
cooling
h'
vaporization
"P
filter
backlog
disposal
feeding stuff
LOADS O N P R E S S U R E MEDIA IN
OPERATION
Oxidation
During operation, the pressure media goes through a continuous change of its chemical properties due to the hydraulic load
in the system. Over the long service life of the pressure media,
its properties should change very slowly; this requires aging
stability. During operation, the hydraulic load parameters
such as pressure and temperature as well as shear stress affect
the fluid. During operation, different types of contamination
influence the service life of the pressure media. These can be
liquids such as water or foreign oils, and solid particles such
as abrasive materials or environmental dust. Those loads can
affect the fluid chemically as well as physically.
Of special importance for the stability of a pressure
medium is its resistance against oxidative attack. Oxidative
stability problems are aggravated by contact of the fluid with
the ambient air in the tank of the system or with the air dissolved in the fluid, leading to a change of the chemical and
physical properties.
For the stability of lubricEints based on natural or sjmthetic
esters, their resistance against the so-called autoxidation processes is of importance, since those reactions already start at
NaOH )
neutralisation
Tt.
H3P04 (75%
ik
rotational
separation
separation
i r
H?n
H-RBntnnil
crude oil
M .iiJ 1
washing
HCI active
bleaching
soapy contents ^
H2SO4(30%)j
& steam I
fatty acid
raffination
H
steaming
filtration
H
I
steam J
P(
L ^ desodoration
2mbar/250C
drying
filter backlog
disposal
bleach
disposal
PI
refined oil
CH3-CH
OH-CH2-CCH
+ NaOH
9^3 O
formaldehyde
9^30
acetal
HCH
HCCH
CH2-OH
HO-CH^CC-
CH,
formaldehyde
CH,
i-butanal
CHj-OH
+ HCHO, H2O
O
OH-CH2-CCH
-HCOOH
CH2-OH
OH-CH2-CCH2-OH
CHj-OH
CH2-OH
pentaerythrltol
9H3O
HO-CHj-CCH
CH,
+ H,
CH,
HO-CHj-CCHj-OH
CH,
CHAPTER
11: ENVIRONMENTALLY
FRIENDLY
OILS
279
H2O
1. Start
Hydrolysis
Hydrolj^ic cleavage of the pressure media based on natural
and sjTithetic esters represents a reaJ danger for the fluid,
since the reaction to produce synthetic esters is an equilibrium reaction producing water. Since equilibrium reactions
may proceed in either the forward or reverse directions, esters exposed to water cleave again into their alcohol and acid
components. At room temperature and without mechanical
load, this reverse reaction proceeds very slowly with synthetic esters so that no direct damage of the fluid contaminated with water is expected. However, u n d e r mechanical
load and increased temperatures such as the t5rpical conditions that occur in a hydraulic system, the hydrolysis process
is accelerated. In general, hydrolosis may follow two different paths: saponification or acid catalyzed hydrolysis [17].
Alkali saponification starts by adding a hydroxide ion to
the carbonyl carbon atom of the ester. The hydroxide ion can
be added to the reaction, e.g., by mixing sodium or potassium
hydroxide to it. The reaction intermediate produces a very
-> XH
2. Chain building
-> ROO
ROD
RH
-> ROOH
RO
RH
-> ROH
RO
3. Chain splitting
ROOH
ROOH
cyclohexanol
RH
-> RO
+
ROOH
OH
ROO
adipic acid
^CH,
CH-OH
HNO, or
o.
II
I
I
I
I
I I II
CCCOH
I I
HOCCC
H
CH,
4. Chain termination
adipic acid
cyclohexanone
^CH,
CH,
HN03or
o,
II
II
>
R-R
ROO
- ROOR
HOCCC CCCOH
alcohol
alcohol synthesis
carbon acids
acid synthesis
bleaching
mineral acid
280
HANDBOOK
R1-COR2
R1-COR2
OH
HO
2. step: all^oxide ion formation
0~
R1-COR2
~*"
R1-COH
-h
OR2
HO
3. step: alkoxide deprotonation
O
-h
_
II _
' OR2
R1-CO
FIG. 29Alkalic saponification of esters.
R1-COH
R1-C
-f-
R2-0H
0 R2
+
R1 - c
II .
OH
0
2.step: water addition
H-- O H
0 R2
R1-C
HP
-h
il .
OH
OH
R1 - C 0 R2
R1-CO*
OH
OH
R2
1 1
OH R2
OH
1
1
R1-C
R2-0H
II .
OH
R1-C
M
-f
R2-0H
R1-COH
R2-0H
OH
FIG. 30Ester splitting under acid conditions.
CHAPTER
is produced after a H^-ion is removed. The H"^-ion is then
available again for hydrolyzing another ester bond. The reaction continues until the chemical equilibrium of the four
components is restored again.
In a pressure medium, free fatty acids represent the basic
material for chemical reactions. They react with metallic
abrasive particles contained in the fluid. From this reaction,
so-called metallic saponification agents arise, leading to a
possible functional i m p a i r m e n t of the hydraulic system.
Metallic saponification agents deposit on the surfaces of the
hydraulic components leading to a premature blockage of the
filters.
Aging
11: ENVIRONMENTALLY
FRIENDLY
OILS
281
11
i.
2
'1,75 bar
Z3
W
CO
oxidationstability
a.
TQ
copper coii
FIG. 31Rotary bomb test rig.
time [min] T,
282
HANDBOOK
test parameter
40
35
35
30
25
20
15
H 10
o
5
0
20
20
1
11
3
GS1
1
1
1
1
GS2
1
1
1
11
11
11
temperature:
1
1
II 1
t
20
1
1
GS3
t
0
0
150 iC
GS4
base oil
atmosphere:
6,25 bar
oxygen
limit:
1,75 bar
pressure
drop
catalyst:
^ g copper, 3m
S 1,5 mm
300'
!= 250!& 200-
1 150 | 100"
500-
267
220
tn
HLP
1
1
1
1
1
1
fr
213
1
T
temperature:
24
150iC
atmosphere:
/ * ^ 6,25 bar
\^Joxygen
70
limit:
^ T ^ 1,75 bar
^ ^ pressure
x^P^drop
catalyst:
SI
S2
nuid
S3
S4
^
^
copper, 3m
1,5 mm
FRIENDLY OILS
test Darameter
10000
i
1
GS1
temperature:
QS1
t.
variable
1 0 0 0 - ^^^^^^^=
atmosphere:
10"
1 -
90 j C
Z * ^ 6,25 bar
\jjl
oxygen
limit:
^H
^H
^^^^^1
^^^1
^ - 1 ^ 1 , 7 5 bar
^ S f j pressure
>_>'drop
1H H
120jC
temperature [\C]
catalyst:
^ p copper, 3m
^ ^ 1,5 mm
15C>iC
test parameter
150
temperature:
S1
-.125
E
110
>!ioo
75
64
1 50
a
"S
o
25
84
77
.a
150 iC
atmosphere:
RH
6,25 bar
oxygen
46
limit:
24
1,75 bar
pressure
drop
catalyst:
Cu
Fe
283
Cr
CrN
Ti
TiN
materials and coatings
without
^S variable
284
HANDBOOK
test parameter:
temperature:
variable
pressure:
S y\ variable
volume flow:
300 bar 300 bar 150 bar 300 bar 300 bar 150 bar
90C 60C eO-C 90C 60C 60C
GS1
GS1
GS1
S1
SI
20 l/min
water content:
^ < 0,03 %
4 HaO
test duration:
S1
1000 hrs
Test runs on the aging test bench confirmed the very good
oxidation stability of the more advanced fluids formulations
(Fig. 38). Fluid S3, in particular, exhibits an aging stability
comparable to mineral oils. The excellent stability is indicated by the constant viscosity throughout testing time.
A comparison of results of the formulated fluids with their
base fluids shows that the additives used and the base fluid
correlate well with each other. Additives increase the aging
resistance of the base fluid significantly.
Table 3 illustrates the effect of additional fluid characteristics. Variations of these characteristics are only of minor importance with respect to the aging performance. Therefore, a
graphical presentation is not shown.
CHAPTER
Aging
28
test parameter:
temperature:
90 C
viscx3sity
24
EBAN
5
X
IV.
g20
CO
12
>,
1^-
^g.
1 8
o_
FRIENDLY
O 00_
lOCM
1^
o
o"
S4
pressure:
300 bar
0)
volume flow:
(0
o>
c
I 4
z
<
20 l/min
water content:
^ <
0,03 %
H,0
test duration:
HLP
1000 hrs
FIG. 38AN and viscosity changes of different fluid generations after aging test runs.
Density
Viscosity
@40X
Viscosity
@ 100C
Viscosity
index
Pour-point
Flash-point
FZG-test
Vickers
pump test
AN
Corrosion
Steel
Alternative Test
Methods'"
ASTM^
ISC^
Unit
HEES 46
HLP 46
DIN
Standard"
kg/m3
nim2/s
ca. 920
ca. 880
46
51 757
51562T1
D 1298
D445
3104
7,1
51562T1
D445
3104
100
ISO 2909
D 2270
2909
-27
220
12
<120
<30
ISO 3016
ISO 2592
51 354 T2
51389T1
51 389 Tl
51 558
D 664
D92
D97
D5182
D 2882
3016
2592
14635
20763'*
D 974
D 664
D 5770
3371
6618
7537
46
mm2/5
["C]
[C]
Load level
[mg] ring
[mg] vane
[mg KOH/g]
9,3
184
-42
290
12
<120
<30
1.2
0,3
D 665A
7120
D665B
7120
1-100A3 1-100 A24
D130
2160
Copper
51759
"The DIN test procedures shown here were used to obtain the values shown.
* Although DIN test procedures were used for this work, equivalent ASTM tests may
also be used.
'' In some cases, the ASTM tests are not truly equivalent but the ASTM procedures
cited may be used.
'' This ISO Standard is still under development and has not yet been published.
0-A
OILS
285
Hydrolysis Stability
Laboratory
11: ENVIRONMENTALLY
0-A
51 585
286
HANDBOOK
test fluid
(150 g)
+
catalyst
(iron or copper)
+
fluid analysis
(variable)
3,0
test parameter:
^^^^1,5% iron |^
temperature:
32,5
Br 90C
2,0
E
ft. "I-5
en
c
n
u1.0
z
<
0.5
fluid:
GS1
test duration:
72hrs
catalyst:
0,0
0,0
0,2
0,4
0,6
0,8
1,0
water content [%]
1,2
1,4
1,6
^
p
iron,
1,5%
FIG. 40Hydroiytic stability of the GSI ester fluid vs. water content.
processes also occur since the reaction vessel was not purged
with nitrogen. Contrary to the oxidation tests reported earlier, the oxygen supply is very low since the container is only
filled with atmospheric pressure air.
Besides the determination of AN, deposit formation during
the tests was determined. This was done by SEM microscopy
to determine structure as shown in RBOT tests reported earlier, Fig. 42. The structure of the deposited particles differs
most with regard to particle size. The particle size of the deposits was significantly smaller. The medium particle size of
the contaminants measures about 10 ^i,m vs. about 60 /xm for
the iron test dust of the laboratory investigations.
After ultrasonification, there was no significant difference
in the particle size and amount between those generated in
the test rig cind those generated in the RBOT laboratory tests.
In addition, the compositions of the deposits from the two
tests were essentially the same. In addition to iron and copper, the deposits taken from the test rigs contained small
amounts of tin and zinc, which are alloying elements of the
non-porous materials used for construction of the test rig system components. The presence of phosphorous or sulfur.
CHAPTER
which would be attributable to the additives used for fluid
formulation, was not observed, which indicates that the data
obtained from the test rigs correlates well with results obtained from laboratory tests such as RBOT.
The analyses techniques, however, were unable to detect
hydrogen. Based on the chemical reactions occurring, the
presence of hydrogen would be expected, since metal
saponification occurs with the metal catalyzed hydrolysis.
Ester hydrolysis follows the reaction process described earlier. The faster hydrolytic reaction of iron vs. copper is due
to the stronger acidity of iron relative to copper.
Hydrolytic
Stability
Stands
Further assessment of the hydrolytic stability of different ester-based fluids was conducted using the test stand. These
5
X
04
11: ENVIRONMENTALLY
FRIENDLY
test parameter:
temperature:
variable
fluid:
GSi
0,8 % H2O
to O
O)
test duration
10
72lirs
^1
catalyst:
40
287
studies were performed with significantly lower loads relative to those used for the studies discussed previously to prolong the use lifetime of the hydraulic components used for
the test stand. Initially, the first generation of ester-based fluids (vegetable oils), were evaluated using varying water content u p to a maximum of 0.1%, which is the maximum allowable value r e c o m m e n d e d by VDMA (Association of
German Machine Manufacturers) [36,37]. (This is an empirical recommendation, which was not derived experimentally.)
For this work, the water contaminant was injected slowly
into the suction pipe of the p u m p on the test stand. Excellent
mixing of the fluid a n d water c o n t a m i n a n t was obtained
from the "whirling" action of the oil flow in the p u m p and the
subsequent turbulent motion of the fluid on the pressure re-
- C ^ 1,5% iron
-0 1,5% cxDpper
20
OILS
60
80
temperature [C]
100
120
140
variable
FIG. 41Hydrolytic stability influence of a catalyst on the hydrolysis of the GSI ester fluid.
ultra sonic
treatnmnt
latoratory
test
?m*
I
FIG. 42Hydrolytic splitting products.
':"|l
HANDBOOK
test parameter:
temperature:
60-0
I
0;
pressure:
150 bar
volume flow:
20 l/min
water content:
^ ^ variable
%0 see figure
0,03%
GS1
0,1%
GS1
0,5%
GS1
0,03%
SI
0,1%
SI
0,5%
SI
test duration:
1000 lirs
FIG. 43AN and viscosity changes after aging tests in the test rig with water contamination.
test parameter:
temperature:
60 C
pressure:
0-
isobar
volume flow:
20 l/min
water content:
GS1
GS2
GS3
S1
S2
S3
o.syoHjO
test duration:
1000 hrs
FIG. 44AN and viscosity changes after aging tests in the test rig with water contamination and using different generations of fluid development. The oldest was GSI and the most
recent fluid candidate is S3.
CHAPTER
of increased system pressure and reservoir temperature. In addition, it is also important to consider system component
compatibility. For example, water is soluble in the ester-based
fluid u p to 0.1% b.w. and 60%. Under these conditions no deleterious system effects were observed. However, water contents
of 0.5% b.w. are insoluble in the fluid and significant attack on
the system is observed. Although an oil-water emulsion is
formed initially, phase separation does subsequently occur depending on the demulsification properties of the fluid.
The extent of fluid hydrolysis was greatest with the GSI
fluid, which contained no additives. All of the fluid candidates contained emulsifies deposits at the b o t t o m of the
reservoir and the filter elements during the test run.
These deposits are formed due to the emulsification of the
fatty acids, which react with the corrosion metals from the
system components. This process may result in filter plugging even after only a few hours of operation during the test.
This occurs because the filter elements are equipped with a
by-pass valve that opens once a preset differential pressure is
exceeded at which time the fluid invades the system without
filtration. This results in an increase of solid abrasion particles (contamination) in the system.
The tests didn't show any impairment of the lubricating
properties of the fluids caused by the water as contaminant.
However, indirect consequence of water contamination is
that 3-body-abrasion causes increased wear on the hydraulic
components. The improved hydrolytic stability of more recently developed fluids produces smaller amounts of deposits
on the bottom of the reservoir.
A comparison of the composition of these deposits relative
to those found in laboratory tests was discussed earlier.
11: ENVIRONMENTALLY
FRIENDLY
OILS
289
viscosity of synthetic esters is considerably lower than mineral oil, providing a safe operation of a hydraulic system after changing over from a mineral oil to a synthetic ester of the
same viscosity class. At high temperatures, viscosity of the
same ISO viscosity class (ISO 3448, ASTM D 2422) is significantly higher, so that oil of the next lower viscosity class
might be used. Consequently, synthetic esters perform like a
multi-grade oil. ASTM D 6080 provides a procedure for esterbased hydraulic oil as a function of use temperature.
Crystallizing P r o c e s s e s With Slowly Decreasing
Temperatures
With very slowly decreasing temperatures a first formation of
crystals may occur at approximately - 2 0 C in synthetic esters. As experienced with vegetable oils, the degree of crystallization is dependent on time [8,23,26,32]. For the fluid GSI,
the completely crystallized condition is achieved after a four
day storage time at a temperature of 45C.
Consequently, the temperatures necessary for crystallization are about30C lower than those for rapeseed oils and
are below the temperatures where mineral oils are no longer
able to flow. Thus, a safe operation of hydraulic systems operated with synthetic esters instead of mineral oil is guaranteed at low temperatures.
From Fig. 46 the start of crystallization can be taken for
the generations of fluids for the fluids SI, S2, and S3, which
are branched, saturated diester-based fluids. Moreover, different filterability tests were conducted to assess the low
temperature performance. Good filtering properties of the
pressure media are a precondition for a safe operation of
the hydraulic system because if the fluid is excessively viscous, the p u m p will be starved for fluid and cavitation will
result. If the fluid viscosity is too low inadequate lubrication
will result. For the filterability tests the experimental system
shown in Fig. 47 was used that was developed at IFAS. The
fluid volume enclosed in the cylinder is pressed through a
membrane filter by means of compressed air at different
temperatures. Measures for filterability are either the time
necessary for a certain volume to pass the filter or the volu m e flow through the filter element in dependence of time.
The diagram shows the filterability properties of fluid GSI,
since no significant differences were found between the individual fluids based on synthetic esters. Compared to mineral
oil HLP 46, those fluids show a considerably better filterability. In the case of mineral oil, the filter m e m b r a n e clogs at
temperatures of 10C after a test time of only 60 s. The volu m e flow of fluid GSI through the filter element diminishes
within the same time by only 25%. However, when the SJTIthetic ester is contaminated with 0.5% water, the good filtering properties are lost, causing the filter element to clog after
a very short time. Since the water is no longer dissolved, but
finely dispersed in the Quid, ice crystals can form resulting in
clogged filter elements.
ECOLOGICALLY TOXIC PROPERTIES
Test Methods
For the investigation and development of environmentally
friendly, biologically fast degradable pressure media discussed above, various methods currently in use in Europe
'
^^\*-
'
'
'
'
''''
A.^
SN
VkV
m
\ ',
\^
KX
^
^3
GS1
S2
f-
GS3
P3
HLP46
fluid
^fe
? \ \
slope
1 i
3.34
S2
VI
^M WM i
^ in
80 .
^
%
63,550
40
31,5.
>
25 .
20
15,81
12,5-
^
\
in _
u
-W
^\
6 5-60
-zto
-2 0
(3
20
A0
60
80
100
-10
aging parameter:
temperature:
90 C
i Hi ni 11 Mq HI I I
MM nl I ! I 111
pressure:
/ * ^ 300 bar
volume flow:
water content:
/ ^ < 0,03 %
new fluid
1000 h aging
GS1
GS2
GS3
fluid
S1
20 l/min
W
S2
S3
H,0
aging time:
1000 h
FIG. 46Crystallization of esters at low temperatures. (Crystallization properties are determined by IFAS lab test procedure).
GS1
GS1 0,5% HP
X - -HLP46
20
~~~~-J
,,___^
-10 C
compressed air
(6 bar) "^
"i
5 10.
o
5=
-~
50
<
100
150
time [s]
200
ZO
filter [5|jm]
were employed. The examination of the toxicological properties of rapidly biodegradable fluids is a critically important
parameter in evaluation of the use-properties of these fluids.
This includes the self-classification of the test fluids into water hazard classes [40], since exclusively finished products
and no individual components were tested. These properties
were determined for this work using both new and used fluids. Aged fluids were evaluated to determine impact of aging
on biodegradability and toxicity. The VCI (Verband Chemischer Ingenieure) classification system [6,29,32] comprises
the tests shown in Fig. 48 and Table 4.
Test Results
Table 4 provides an insight into the test-substance specific investigations, results, and (preliminary) WGK-classifications
(WOK = water hazard class) [40].
ASTM International has developed various standards to
provide guidance in determining the biodegradability and
ecotoxicity properties of hydraulic fluids. A brief summary of
the slope of these tests will be provided here and more detailed discussion is provided in Chaper 34, Environmental
Characteristics of Fuels and Lubricants. Biodegadability is
one of three characteristics that are assessed when evaluating
the environmental impact of a hydraulic fluid. The other two
characteristics are ecotoxicity and bioaccumulation.
D 6006Guide for Assessing Biodegradability of
Hydraulic Fluids
This guide provides information to assist in planning a laboratory test or series of tests that would provide information
about the degradability of an unused fully formulated hydraulic fluid in its original form. Biodegradability may be
considered by type of environmental compartment: aerobic
fresh water, aerobic marine, aerobic soil, and anaerobic media. Test methods for aerobic fresh water, aerobic soil, and
WGK
classification
r
pre test
.
J'"flS'Ctlr,nV-,l
compulsory
i--.taxids-.i'J
daphni=<:>-.'*'/
mm^
test of
components
special case
additional
toxicidy tests
biodegradability
& mobility
Germ-toxic
Test method
Unit
GS2 Unused
GS2 1000 h Aging
S2 Unused
S2 1000 h Aging
DIN 38412 T 8
OECD 203
ECio [mg/L]
> 10.000
> 10.000
>10.000
> 10.000
LC50 [mg/L]
> 10.000
> 10.000
> 10.000
> 10.000
OECD 401
Limittest
LD50 [mg/L]
>2.000 78
>2.000 84
>2.000 89
>2.000 89
CEC L-33-A-93
Depletion [%]
N/A
N/A
76
64
BODIS ISO/DIN
10708
Depletion [%]
0
0
0
0
OH
complete
addrtive
package
strategy
- coatings
- eccological acceptable fluids
- data bases & simulation tools
- examinations on trSbological modells
- examinations on machines
Oil less
addrtivs
Biodegradability WGK
VCI-strategy
D 665
D 974
D 1298
D 15 3 3
D 2270
D 2422
D 2619
D 2882
D5182
D 5770
D 5864
D 6006
D 6046
D 6080
D 6158
D 6384
ASTM STANDARDS
No.
D 2272
D 92
D 95
D 97
D 130
D 445
D 664
Title
Standard Test Method for Oxidation Stability
of Steam Turbine Oils by Rotating Pressure
Vessel
S t a n d a r d Test Method for Flash a n d Fire
Points by Cleveland Open Cup Tester
Standard Test Method for Water in Petroleum
Products and Bituminous Materials by Distillation
S t a n d a r d Test Method for Pour Point of
Petroleum Products
Standard Test Method for Detection of Copper
Corrosion from Petroleum Products by the
Copper Strip Tarnish Test
Standard Test Method for BCinematic Viscosity
of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
S t a n d a r d Test Method for Acid N u m b e r of
Petroleum Products by Potentiometric Titration
E 203
OTHER STANDARDS
International Organization for Standardization
(ISO)
Title
Petroleum products; determination of flash and fire points: Cleveland open cup method
Petroleum products; determinaISO 3016
tion of pour point
Petroleum p r o d u c t s and bitumiISO 3733
nous materials; determination of
water, distillation method
ISO 6743/4 -1982 Part 4: Lubricants, industrial oils and related products (class L); classification. Family H (hydraulic systems)
No.
ISO 2592
294
MANUAL
HANDBOOK
DIN 51 381
DIN 51 502
DIN 51 561
DIN 51 566
DIN 51 569
DIN 51 585
DIN 51 587
DIN 51 592
DIN 51 599
DIN 51 757
Title
Testing of lubricants: mechanical testing of lubricants by the FZG gear test
rig method; gravimetric m e t h o d for
A/8, 3/90 lubricating oils
Testing of lubricants a n d hydraulic
fluids; d e t e r m i n a t i o n of air release
properties; impinger method
Testing of lubricants; mechanical testing of hydraulic fluids by the vanep u m p method: m e t h o d A for anhydrous hydraulic fluids
Lubricants a n d related materials;
designation of lubricants and marking
of lubricant containers, lubrication
equipment and lubrication points
Lubricants; lubricating oils; C lubricating oils; m i n i m u m requirements
Lubricants; ISO viscosity classes for industrial liquid lubricants
Pressure fluids; hydraulic oils; HL hydraulic oils: m i n i m u m requirements
Viscometry; determination of viscosity; general principles
Testing of mineral oils; determination
of neutralization number; color indicator titration
Testing of mineral oils, liquid fuels
and related liquids; measurement of
viscosity using the Vogel-Ossag viscometer: temperature range: approximately 10 to 1 50C
Viscometry; determination of kinematic viscosity using the standeird design Ubbelohde viscometer
(at present at the stage of draft) Testing of lubricating oils: determination
of foaming characteristics
Testing of mineral oils, liquid fuels
and related liquids; measurement of
viscosity using the Vogel-Ossag viscometer: t e m p e r a t u r e range: 55 to
approximately + 10C
Testing of lubricants; testing of corrosive effect of steam turbine oils and
hydraulic oils containing additives
Testing of lubricants: determination of
aging behavior of steam turbine oils
and hydraulic oils containing additives
(at present at the stage of draft) Testing
of lubricants; determination of the
content of u n dissolved matter in lubricating oils; membrane filter method
Testing of lubricating oils; determination of demulsification capacity by the
stirring method
Testing of petroleum products and related materials; determination of density
DIN 51 759
DIN 53 505
DIN 53521
REFERENCES
[1] Backe, W., The Present and Future of Fluid Power, Proceedings of
the Institution of Mechanical Engineers, Institution of Mechanical Engineers, Milwaulkee, WI, Dec. 1993.
[2] Backe, W. and Busch, C, "Biologisch Schnell Abbaubare Hydraulikflilssigkeiten," Tribologie + Schmierungstechnik, No. 1,
1995, pp. 30-35.
[3] Becker, R. and Knorr, A., "Antioxidantien fiir Pflanzliche Ole,"
Tribologie + Schmierungstechnik, No. 5, 1995, pp. 232-240.
[4] Bongardt, F., Einfluji der Chemischen Struktur aufdas Luftabscheidevermogen und die Hydrolytische Stahilitdt von Estem, Teil
1, Fat Science Technology, No. 12, 1990, pp. 607-613.
[5] Bongardt, F., Einfluji der Chemischen Struktur aufdas Luftabscheidevermogen und die Hydrolytische Stabilitat von Estem, Teil
2, Fat Sci. Technology, No. 12, 1990, pp. 614-619.
[6] Bongardt, F., "Native Ester: Basisole fiir leistungsfahige und
Umweltvertragliche Hydraulikfliissigkeiten," Tribologie 2000
Band 1, TAE, Esslingen, 1992.
[7] Busch, C, "Biologisch Schnell abbaubare Hydraulikfliissigkeiten," Tribologie und Schmierungstechnik, Vol. 41, No. 1,
1994, pp. 23-31.
[8] Busch, C, "Untersuchung und Analyse der Eigenschaften und
Eigenschaftsanderungen einer Rapsolbasischen Druckfliissigkeit in ihrer Funktion als Druckiibertragungsmittel," Dissertation RWTH Aachen, Aachen, Germany, 1995.
[9] Busch, C, Rapsol auf dem Priifstand - Alterungsstabilitat und
VerschleiySschutzvermogen, 10th AFK, Aachen, Germany, 1992.
[10] Dimming, T., Hartmann, J., Wunderwald, U., and Schafer, V.,
"Additivkomponenten auf Basis nativer Ole," Tribologie +
Schmierungstechnik, No. 6, 1994, pp. 375-380.
[11] Feldmann, D. G. and Remmelmann, A., Biologisch Schnell Abbaubare HydraulikfliissigkeitenErgebnisse von Priifstandstests
und Folgerungen fiir die Anwendung, 12th AFK, Aachen, Aachen,
Germany, 1996.
[12] Feldmsinn, D. G. and Hinrichs, J., Biologisch Schnell Abbaubare
Hydraulikfliissigkeitenein Neuartiges Konstruktionselement fiir
Hydrostatische Getriebe, Konstruktion, VDI Verlag, Dusseldorf,
Germany, 1995.
[13] Fessenbecker, A. and Korff, J., "Additive fiir Okologische Unbedenklichere Schmierstoffe," Tribologie + Schmierungstechnik,
No. 10, 1995, pp. 623-629.
[14] Mang, T., Umweltvertragliche Hydraulik, 12th AFK, Aachen,
Germany, 1996
[15] Fessenbecker, A., "New Additive for the Hydrolytic Stabilisation
[31] Spilker, M. and Bock, W., Die Umwelt als Ideologietrdger, FluidTechnik,No. 4, 1995.
[32] Vetter, J., "Synthetische u n d Nachwachsende GrundolkomponentenProduktsicherheit, Eigenschaften, Gesundheits- und
Umweltaspekte," Biologisch Schnell Abbaubare
Schmierstoffe
und Arbeitsfliissigkeiten, Technische Akademie Esslingen, Ostfildern, Germany, 1995.
[33] Wendorf, J., "Daueruntersuchung von Hydraulikolen auf Rapsolbasis in Mahdreschem und Selbstfahrenden Feldhackslem,"
Biologisch Schnell Abbaubare Schmierstoffe
und Arbeitsfliissigkeiten, Technische Akademie Esslingen, Ostfildern, Germany, 1995.
[34] Streitwieser, H. and Heathcock, J., Organische Chemie, 1. Auflage VCH-Verlag, Weinheim, Germany, 1990.
[35] DIN 51 524 T1-T4 Hydraulikole, Mindestanforderungen,
Deutsches Institut fur Normung e. V., Beuth Verlag, 06.1985,
Berlin, Germany.
[36] VDMA-Einheitsblatt 24 568: Biologisch Schnell Abbaubare HydraulikfliissigkeitenTechnische Mindestanforderungen, 3,
Beuth Verlag, Berlin, 1994.
[37] VDMA-Einheitsblatt 24 569: Biologisch Schnell Abbaubare HydraulikfliissigkeitenUmstellungsrichtlinien, Beuth Verlag,
Berlin, 1994.
[38] Bundes Imimissionsschutz-Gesetz, Law of the Federal Republic
of Germany, 1998.
[39] AbschluySbericht zum Forschungsvorhaben, "Synthetische Ester," VDMA, Frankfurt, Germany, 1997.
[40] KBwS: Bewertungsmuster zur Stoffeinstufung in Wassergefahrdungsklassen im Sinne von 19 Wasserhaushaltsgesetz;
Chemiereport VCI, 1989.
[41] OECD: Guidelines for Testing of Chemicals; OECD 203, OECD
401, Organization for Economic and Co-operation and Development, Paris 1981 (adopted 1983, 1984, 1986, 1987, 1989 und
1992).
[42] DIN 38412 T 8: Testverfahren mit Wasserorganismen L8,
Beuth-Verlag, Berlin, 1993.
[43] ISO/DIS 10708: Water QualityEvaluation in an Aqueous
Medium of the "Ultimate" Aerobic Biodegradability of Orgsinic
BondsMethod by Determining the Biochemical Oxygen Demand (two-phase closed bottle test). International Organization
for Standardization, Geneva, 1995.
[44] CEC L-33-A-93: Biodegradability of Two-Stroke Cycle Outboard
Engine Oils in Water; Commission for Environmental Cooperation, 1995.
[45] DIN 51828-2: B e s t i m m u n g der Schnellen Biologischen AbbaubarkeitInfrarotspektrometrisches Verfahren; Gelbdruck,
Beuth-Verlag, Berlin, 1995.
[46] UUmanns Enzyklopddie der Technischen Chemie, Vol. 11, Auflage Verlag Chemie, Weinheim, Germany, 1976.
MNL37-EB/Jun. 2003
the most radical changes it has seen in its relatively short history. The very conservative, slow moving industry dominated
by state utilities has, in the last ten years, seen a major transition for both political and commercial reasons. Many areas
of what used to be a highly regulated market have become
very competitive with the privatization of large, governmentowned power generators and a developing global energy market [1,2].
With the break-up of the state monopolies, smaller, independent power producers have appeared seeking to install
plant at the lowest cost and to make a rapid return on their
investment [3]. At the same time, intense competition in the
turbine industry has resulted in the development of equipment with substantially increased efficiency as the participants seek to increase their meirket share.
On the political front, apart from the decision to deregulate
the power industry, there has been environmental pressure to
halt the construction of, and even replace, nuclear power stations and to reduce the effect of emissions on global warming
by switching from coal and oil to gas and 'green' energy such
as wind power. In Europe, safety of machinery legislation [4]
has been introduced which, although not specifically directed at the p o w e r industry, nevertheless imposes constraints upon it.
As might be expected, such changes, while determining the
commercial shape of the industry well into the next century,
also have a major impact on its technical requirements. For
example, increased competition has driven improvements in
equipment efficiency. This, in turn, has resulted in turbines
operating at ever higher temperatures [5]. According to one
report, for each increase of 100F in firing temperatures of
gas turbines, the output is increased by 10-13% with a gain
of 2-4% in simple cycle efficiency [6]. This has the effect of
placing greater thermal stress on the system components
including the lubricantand an adverse impact on operating
life. Such pressures have forced the steam turbine builders to
consider technology previously used only in aero-derivative
gas turbines, w h i c h operate at the highest t e m p e r a t u r e s
found in the industry [7].
TURBINE TYPES
The source of the kinetic energy for conversion into power
depends on the turbine type. In a steam turbine it is the
rapid expansion of high-pressure steam, and in a gas turbine, the expansion of fuel combustion products. With wind
emd water turbines, the movement of a mass of air, or water under pressure, is the energy source. To convert the rotational energy into a more useful form of power, turbines
are coupled to alternators for electricity generation or to a
pump, compressor, or fan when used as a mechanical drive
[8]. Depending on the speed of the turbine rotation it may
be necessary to introduce a reduction gear between the turbine and driven equipment for steam, industrial gas, and
wind turbines.
Aero-engine gas turbines are not directly coupled to other
equipment, but instead the energy of the expanding gases is
used to provide forward motion, as in aviation usage, or to
drive a second turbine wheel, sometimes called a power turbine, which is independent of the power source and attached
to an alternator or compressor.
To summarize, turbines are manufactured in a wide variety of sizes and for several different applications as follows:
For power generation, where they may drive a generator,
either directly or indirectly via a gearbox.
As a direct mechanical drive for p u m p s and compressors.
As gas generators for propulsion (in the aircraft industry),
or when used with an independent power turbine, for driving p u m p s and compressors.
Steam Turbines
' Marketing and Technical Manager, Great Lakes Cliemical Corporation, Performance Additives and Fluids, Tenax Road, Trafford
Park, Manchester M17 IWT, England.
297
Copyright'
2003 by A S I M International
www.astm.org
298
HANDBOOK
CHAPTER
12: TURBINE
LUBRICATING
FLUIDS
299
Oil
purifier
Problems initially arose with the use of conventional turbine oils in t e r m s of reduced oil life, deposit formation,
micro-pitting and bearing failure and led to the use of polyalphaolefin (PAO)-based oils owing to their better high temperature stability. In spite of this the average life of the gearbox oil in the small units was still only about 1-2 ycctrs. The
oil life has increased since temperatures were reduced to
<70C but the problems of micro-pitting smd bearing failures
have not yet been totally eliminated. However, all new gear
oils for this application are required to pass an FZG micropitting test (FVA test 54/I-IV, Test Procedure for the investigation of the Micro-Pitting Capacity of Gear Lubricants).
Higher viscosity products (ISO VG 320) are also used in an
attempt to further minimize the problems. Even with these
changes, the current oil life expectations are, as yet, only 3-5
years. With additional research on the effects of oil cleanliness, moisture, and metal contamination, further improvements are thought possible.'^
As well as the operating problems mentioned above, other
factors have to be taken into consideration during operation,
for example the inaccessibility of the equipment in the event
of a failure (especially if located offshore). Power generation
without producing carbon dioxide can also have a higher
profit margin, so downtime losses/MW output are also higher
for this tjrpe of equipment.
As well as the gearbox, almost all wind turbines have a
small hydraulically operated braking system of 2-4 L capacity and working at about 100 bar pressure. Since conventional turbine oils are not used in wind turbines there will be
n o further discussion of this application.
- EXCITER
GRAVITY
DRAIN AND
GUARD PIPE
PRESSURIZED
OIL PIPES
OIL VAPOR EXTRACTOR
OIL RETURN
SCREENS
OIL
COOLERS
FIG. 2Shaft driven lubrication system of a steam turbine generator. Reproduced by permission of the Electric Power
Research Institute, Palo Alta, CA.
CHAPTER
12: TURBINE
(Eh
Fluid returns
>
'^-r
LUBRICATING
FLUIDS
301
4x}
-|J_yent
z
Fluid conditioning
^M%
Cooling water>
llling using
loling pump
C( Dllng water
-M-
Emptying>
illing using
^ s n ianual pump
creased safety and reduced downtime since 1958 and they are
now widely used in this application in North America [22]. In
the 1970s they were introduced for use in the control and lubrication systems of 70 MW sets for power generation [23]. A
t5rpical lubrication system for an industrial gas turbine is
shown diagrammatically in Fig. 4.
Aero-derivative gas turbines were introduced during the
Second World Weir and, while mineral oils were initially used
for lubrication, it was soon realized that both the low temperature properties and the high temperature stability of the
oils then available were inadequate for the more powerful engines that were being developed. Synthetic ester fluids were
therefore introduced a n d have remained the most widely
used type of fluid in this equipment for both aviation and industrial applications where they function as a combined hydraulic fluid and lubricant for the turbine [24]. Mineral oils
are still used in some of the older or smaller aero-engines for
military aviation, and in industrial applications where the
thermal/oxidative stresses are lower.
Where aero-derivative units are used for mechanical drive
applications, the hot exhaust gases drive a power turbine that
is attached to a compressor or a gearbox/generator, etc. In
this application, a synthetic ester product lubricates the engine, while the power turbine and the "driven" equipment are
normally lubricated with mineral oil in a separate system.
When used for pumping natural gas, the power turbine cind
compressor Eire often lubricated with a fire-resistant fluid.
302
HANDBOOK
IEGBO):
A
A
A
H
Mr
mm
MSuwIlF
DfMn
->
Q
)f>RESSUnE
'TRANSMITTEfl
TgwlflCSTiKfOMAt
FIG. 4Typical lubrication system for an Industrial gas turbine. Reproduced with permisson of Solar Turbines, Inc., San Diego, CA.
1940
1950
1960
303
bine oil lives, particularly for gas turbines, are now giving
cause for concern.
Since the thermal/oxidative stress on the oil or fluid is a
factor of temperature, time and the extent of air contact, the
faster the oil temperature (and the air content) can be reduced, the lower the amount of resulting fluid degradation. A
cooler in the return line is therefore preferred. The presence
of air depends to a large extent on tank design (including the
location of return lines, baffles, and sieves to remove entrained air), but it also depends on fluid circulation rates, the
level of fluid/oil in the tank, etc., Guidance on the basic system design parameters of turbine lubricating oil systems (including the use of suitable materials of construction; design
features of the reservoir and pump train; the appropriate use
and location of coolers, valves and filters, etc.) is available for
steam and industrial gas turbines when using conventional
turbine lubricating oil. This appears in such standards as
ASTM D 4241, Standard Practice for the Design of Gas Turbine Generator Lubricating Oil Systems, ASTM D 4248, Standard Practice for Design of Steam Turbine Generator Oil Systems, and the American Petroleum Institute (API) Standard
1970
Year
1980
1990
2000
304
MANUAL
HANDBOOK
i
i
305
System Property
Medium-Large Steam
(250-1500 MW)
Medium-Large
Industrial Gas
(30-300 MW)
19-115
5.5-10
60-65
70
1-3
17-21
50-70"
60-115
15-34
6-10
45-80"
55-85
Aeroderivative-Gas
Aviation
Industrial
(11 000-110 000 lb. thrust)
(31 MW)
0.006-0.02
60-240
60-70
120-130
0.9
5
ISO""
150-180
Marine
(4MW)
0.11
60
70
150
''The bulk fluid temperature In the tank may be similar to bearing return oil temperature if the cooler is placed on the pressure side of the pump. In this case
the bearing oil supply temperature will be significantly lower than that in the tank.
306
MANUAL
HANDBOOK
Type
n-paraffin
Viscosity index
Structure
high
^Ho
high
CH,
CH,
iso-paraffin
CH,
CHo
CH,
CH
naphthene
moderate
aromatic
low
^ - - ^
Dibenzothiophene
^"^^
1,7- phenanthrone
Viscosity
Index
Very High
High
Low
Low
Low
Pour Point
(High/Low)
High
Low
Low
Low
Low
Response to
Antioxidants
Good
Good
Good
Some poor
Poor
Oxidative Stability
Good
Good
Average
Average/poor
S is antioxidant; N and O
are pro-oxidants
Volatility
(High = Poor,
Low = Good)
Good
Good/average
Average
Poor
Poor
ReprintedfromHandbook for Hydraulic Fluid Technology, 2000, p. 716, courtesy of Marcel Dekker Inc., NY.
Crude oil
Dewaxing
Solvent extraction
Atmospheric/vacuum
distillation
Conventional
base oil
Gas oil
Wax
Extract
API Category
II
II
II
III
III
Description
I
Solvent
Refined
Solvent
Refined
Hydro-Cracked
Hydro-Cracked
Hydro-Cracked
Dewaxing
Solvent
Solvent
Solvent
Solvent
Iso-
Solvent
Iso-
25.7
20.8
27.9
24.9
0.7
46.5
29
25
31.7
14.2
0.1
54
23.7
30.8
39.1
6.4
0.0
54.5
21.6
32.8
37.6
8
0.0
54.4
30.2
30.5
35.3
4
0.0
60.7
32.6
34.2
32.9
0.6
76.1
14.7
9.2
66.7
90.8
Severely
Hydro-Cracked
Severely
Hydro-Cracked
Hydrocracked/Hydrotreated Basestocks
In view of the demand from industry for oils with better oxidation stability, as operating conditions become more severe,
attention has turned to processes that can remove yet more
308
MANUAL
HANDBOOK
This is, however, more than compensated for by better response to antioxidants when carefully selected [32,37]. The
loss of aromatics also results in reduced additive solvency necessitating a careful choice of stabilizers emd the continued
presence of small amounts of aromatics may be beneficial in
such cases [39]. The loss of sulfur also reduces the antiwear/extreme-pressure properties of these oils although these
can easily be improved by incorporating suitable additives.
These base materials vary in price from a level which is
comparable to that of solvent refined stocks to about three
times their price, depending on material type a n d local availability. As a result of the favorable price/performance characteristics it is likely that their use in conventional turbine oil
formulations will spread.
Polyalphaolefins (PAOs)
These synthetic fluids are normally m a n u f a c t u r e d by the
oligomerization of Eilpha-olefins, particularly a-decene, but
also by a-octene and a-dodecene and, until recently, were
available in a range of viscosities u p to the ISO 100 grade. The
latest development [40] reports the availability of very high
viscosity products ranging from 150-3000 cSt at 100C and
intended mainly as blending components for other hydrocarbon oils. They are currently more expensive than other hydrocarbon types.
PAOs are free of aromatic hydrocarbons, sulphur, oxygen,
and nitrogen compounds, and show excellent response to antioxidants [41], although they are now being challenged by
some of the severely hydro-cracked oils [42]. They also have
high viscosity indices (as assessed by ASTM D 2270, Standard Practice for Calculating Viscosity Index from Kinematic
H,
I
Atmospheric/vacuum
distillation
n.,,i
H2
I
- >
Ultra pure
base oils
Crude
oil
Atmospheric/vacuum
distillation
"Wax
HTU2
Hydro
Isomerization
309
TABLE 5A comparison of some physical properties of 6.0 cSt PAOs with solvent-refined and hydrocracked oils of similar viscosity.
Parameter
Test Method
API Group
Viscosity, cSt
at 100C
at 40C
at - 4 0 C
Viscosity Index
Pour Point (C)
Flash Point (C)
Evaporation Loss
(NOACK), %
ASTM
D445
ASTM D 97
ASTM D 92
DIN 51581
PAO
IV
5.98
30.9
7830
143
-64
235
6.1
160
Hydro-Treated
240
Neutral
200
Solvent Neutral
II
5.77
33.1
SoUd
116
-15
220
16.6
6.98
47.4
SoUd
103
-12
235
10.3
6.31
40.8
Solid
102
-6
212
18.8
5.9
NA
127
-12
225
6
NOTEReprintedfrom:Synthetic Lubricants and High Performance Functional Fluids, 1992, p. 13, courtesy of Marcel Dekker Inc., NY.
Viscosity at 40C and 100C) and flash points (by ASTM D 92,
Standard Test Method for Flash and Fire Points by Cleveland
Open Cup); very good low temperature viscosities (ASTM D
445, Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids) and p o u r points (ASTM D 97,
Standard Test Method for Pour Points of Petroleum Products), and a wide operating temperature range [42]. A comparison of the physical properties of PAOs with other hydrocarbon products of the same viscosity is given in Table 5 [43].
In view of the lack of aromaticity, additive solubility can be
a problem. PAOs also have limited dispersency and do not
penetrate rubber seals to cause swelling (as assessed by FEDSTD-791, methods 3604 and 3633, or by ISO 6072). As aresult,
it is necessary to blend PAOs with small a m o u n t s of a sealswelling agent (usually a carboxylate ester) to avoid leakage.
PAO-based gas turbine oils have been available for many
years [39] where the higher prices could be justified in terms
of smaller volume and better stability. They have not, as yet,
m a d e a n y significant penetration of the steam turbine oil
market [41].
Mineral
Lubricant
Oil
Ester
Oil
Kinematic viscosity
(cSt)at210F
2.5
3.3
-40F
3000
1700
-65F
25 000
11000
Viscosity Index
75
154
Pour Point ("F)
<-75
-80
Vapor Pressure
(psi) at
250F
0.15
350F
<0.01
1.3
400F
3.5
0.016
0.52
550F
Ryder gear machine
600
2000
failure load lb/in.
tooth face width
Flash point
295
430
(COC, ''F)
20.1
Solid
Solid
95
0
<0.01
0.065
-3000
485
Ester
7.5
12 000
Solid
150
-65
<0.01
0.28
3200
465
ROOC(CH2)nCOOR
diester
310
MANUAL
HANDBOOK
mercial applications for extended drain intervals necessitated the development of more stable products, and the socalled "polyol" or "hindered" esters were introduced at the
beginning of the 1960s [24]. These esters, based on the reaction products of neopentylglycol, trimethylolpropane, or
pentaerythritol with monobasic acids as shown in the reaction scheme below, have thermal degradation temperatures
about 40C higher than the diesters and are more oxidatively stable [46]. They have since been the basis for all commercial engine lubricants and an increasing proportion of
military requirements where low temperature limitations
permitted.
C2H5
I
C2H5
3RCOOH + HOH2CCCH2OH -^
I
I
RCOOH2C CCH2OOCR
CH2OH
I
CH2OOCR
monoacid
trimethylopropane
ester
CH2OH
I
CH2OOCR
4RCOOH + HOH2CCCH2OH +
I
I
RCOOH2CCCH2OOCR
CH2OH
I
monoacid
pentaerythritol
CH2OOCR
ester
where R = C5_^9
The continual pressure on equipment builders to increase
engine power in both military and civil applications has resulted in a need to periodically review and, where necessary,
improve the stability (oxidative and thermal) and deposition
performance of these oils. New versions of specifications, normally calling for improvements in these areas, have appeared
at intervals of a few years, particularly in the military arena.
That continual improvements in oil performance have been
possible is due to the skills of the formulators and the availability of more effective additives [47]. The impact of changes
in additive and basestock composition on oil stability is
shown in Fig. 11 [48]. In the oxidation test from which the
data has been taken, the B^^'^ temperature is the temperature
at which the insoluble content of the oil exceeds 0.5mg/g over
an 8-day test period when the oil is oxidized in the absence of
metals, and is used as a measure of bulk oil stability. The data
shows the initial performance level of diesters in the 1950s followed by improvements to the stabilizer package; the development of more stable fluids (the hindered or polyol esters)
followed by yet more additive developments. More information on the various additive t3^es in use and their function is
given in the following section.
Long chain polyol esters have also been promoted as "less
flammable" hydraulic fluids for steam turbine control systems on account of their relatively high flash and fire points.
The esters used in this application are normally reaction
products of trimethylolpropane and oleic acid (a C18 unsaturated monobasic acid) and in some respects, are significantly
different to the short-chain products used in aviation gas turbines oils. For example, they are far less stable due to the unsaturation (or the presence of double bonds) in the molecule
and their low temperature properties are inferior. When sold
Tiiaryl Phosphates
In common with the other two groups of fluids there are variations in the chemistry of triaryl phosphates that have led to
the commercial availability of different products. In this
case, however, it has been the past limitations on suitable
raw materials that has resulted in the diversity of products
available. Traditionally, phosphate esters were manufactured
from the distillation products of coal tar, which were mixtures of cresols and xylenols and known collectively as "cresylic acids." The phosphate esters produced from these feedstocks were referred to as "natural" products and were chiefly
tricresyl and trixylyl phosphate (TCP/TXP). When natural gas
became widely available, the distillation of coal tar rapidly
declined and attention turned to the production of phosphate
esters from synthetic feedstocks, specifically those based on
alkylated phenols [50]. The reaction scheme for the manufacture of triaryl phosphates, is given below:
ArOH +
POCls^
a phenol
phosphorus
oxychloride
(ArOsPO
3HC1
a triaryl
phosphate
The reaction of propylene or butylene with phenol produces mixtures of alkylated phenols and these became the
feedstocks for a range of "synthetic" phosphates with viscosities falling into ISO VGs 22-100. Since their introduction, the
raw material supply position for the production of the "naturcil" fluids has eased with the introduction of synthetic processes for the production of cresols and xylenols. As a result
the distinction between "natural" and "synthetic" phosphates
has become blurred but the terms are still used today to distinguish between TCP/TXP and the synthetic products based
on isopropylphenols and tertiarybutylphenols.
Although manufactured to the same viscosity level, commonly ISO VG 32 or 46, commercially available fluids do
have somewhat different levels of performance relative to one
another as indicated in Table 9. Therefore, depending on the
requirements of the application, one type of phosphate may
be preferred. For example, in steam turbines where contact
with water is most likely, the phosphate that is most hydrolytically stable, trixylyl phosphate, may be preferred. In
CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRA ULIC FLUIDS 311
Ester limit?
Additive effect
1950
1960
1970
1980
1990
2000
year
FIG. 11Developments In the stability of gas turbine lubricants. Reprinted with permission of B. Rayner, consultant.
TABLE 8^A comparison of the fire-resistance properties of mineral turbine oil, polyol ester, and phosphate ester fluids.
Phosphate Ester
Polyol Ester
Mineral Oil
Property
Test Method
ISO VG 46
ISO VG 68
ISO VG 46
270
258
ASTM D 92
220
Flash point-COC (C)
ASTM D 92
245
316
350
Fire point ( X )
ASTM D 2155
340
425
580
Autoignition temperature (C)
Hot manifold ignition (C)
AMS 3150C
350
430
>800
ISO 14935
Fail
Fail
Pass
Wick ignition
MIL-PERF-19457D
Compression ignition
-Ignition ratio
10
>42
Spray ignition
-Persistence of burning
F.M. Std 6930
Fail
Pass
Pass
Group 3 (worst)
Group 1-2
Group 1
F.M. Std 6930
- S p r a y Flammability Parameter
-Persistence of burning
ISO 15029-1
Fail
Pass
Pass
Class H (worst)
Class H
Class D/E
ISO 15029-2
-Ignitability Parameter
Fire
Resistance
Oxidation
Stability
Good
Good
Good
Moderate
Hydrolytic
StabiUty
Air Release
Excellent
Excellent
GoodExcellent
Poor
Moderate
Moderate
Moderate
Moderate
Antioxidants
The actual mode of oxidative decomposition of both hydrocarbon a n d synthetic oils is a complex process involving
many different mechanisms a n d a variety of intermediate
products depending largely on the temperature and the structure of the substrate. Fig. 12 [52] is a model of lubricant
breakdown at high temperatures, concisely illustrating the
different processes involved.
Antioxidants are chemicals that extend the life of the fluid
by interrupting the oxidation process, e.g., by decomposing
hydroperoxide intermediates (ROOH, where R is an alkyl
chain) and scavenging free radicals [52]. In the past the dominant stabilizer type for hydrocarbons in both automotive
H O / ( ^ V - R-S-R1
0.25%
0.25%
mw = 492
0.25%
HO/QV-CH3
0.05%
balance
Corrosion inhibitor
Mineral oil
Oxidation stability
TOST (ASTM D 943)
(95C; water, Fe and Cu catalysts; 3 L air/hour)
- t i m e to total acid n u m b e r of 2.0 mg KOH/g oil
-sludge (mg) (ASTM D 4310)
Basestock characteristics
ISOVG
CA (aromatic hydrocarbon)
Sulfur
4300
6
0.05%
balance
2400
39
0.25%
0.05%
balance
2200
28
hydrotreated
32
0
0
%
%
1100
47
solvent neutral
32
6.5
0.54
NOTEReprinted from: Chemistry and Technology of Lubricants, courtesy of Kluwer Academic Publishers, Dordrecht, The Netherlands.
volatile
hydrocarbon
fragmentsi
0.05%
balance
polycondensation
polymerisation
(with/without metal)
high molecular
products
polycondensation
polymerisation
sludge
314
HANDBOOK
and industrial oils has been a zinc dihydrocarbyl diphiophosphate (Fig. 13). This is a multi-functional additive in that
it also possesses antiwear/extreme pressure properties and
under certain conditions can provide protection against "yellow" metal corrosion. Different types of zinc dialkyldithiophosphates (or diaryl) are available depending on the alcohol
or phenol used in their manufacture, and the hydrocarbyl
group present strongly influences their activity; the greater
the thermal stability of the product, the lower the antioxidant
activity [33]. There is, however, a move away from this tj^e
of antioxidant in turbine oils and hydraulic oils as the thiophosphates are sensitive to moisture and the hydrolysis products, (zinc oxide and hydroxide), can precipitate. Some tur-
RO
OR
where R is typically C3 - Cg
\ .
Zn
OR
zinc dialkyldithiophosphate
O
CH2CH2C OR
where PL is Cg-Cig
where R is C4-C9
dialkyldiphenylamine
FIG. 13The structure of some common turbine oil antioxidants.
CHAPTER
12: TURBINE
Oxidation Stability
TOST (ASTM D 943)
(95C; water; Fa and Cu
catalyst 3 L air/h) time (h)
to total acid number of
2 mg KOH/g
sludge (mg) (ASTM D 4310)
Basestock characteristics
0.25%
0.05%
balance
0.25%
0.05%
balance
2000
200
0.2%
0.05%
0.05%
balance
3300
172
>5000
89
ISO VG 32
CA (aromatic carbon) = 6.5%
S = 0.54%
LUBRICATING
FLUIDS
315
to represent the materials of construction of the system, measurements are also made of the weight changes of the metal
specimens. Oxidation is accelerated by holding the fluid at a
high temperature in the presence of air, which is usually bubbled through the sample at a fixed rate. In some tests, particularly for steam turbine oils, water is also present to represent the effect of c o n t a m i n a t i o n t h a t is a fairly c o m m o n
occurrence in this application. The use of water can limit the
temperature of the test in order to avoid loss due to volatility.
It can also preferentially solubilize acids that are generated in
the oil on oxidation and, if present as a separate layer, may
remove t h e m from the oil so reducing their impact o n oil oxidation and acidity measurements. On the other hand the water will promote rusting and the generation of sludge and
may also result in the partition of some additives into the water layer.
The oxidation tests that are used to assess stability of turbine oils fall into two categories; those which use water to accelerate the testing and/or make the test more representative
of service, and those where the fluid is tested "dry." In spite
of the fact that gas turbine oils are used at higher temperatures than steam turbine oils and that service conditions are
generally drier, "wet" tests are also used for evaluating the
stability of these productsthough sometimes in combination with a dry test. The two principal tests used today for assessing the stability of inhibited turbine oils are indicated below.
1. ASTM D 2272, Standard Test Method for Oxidation Stability of Steam Turbine Oils by Rotating BombIn this
test (also known as the RBOT test), the fluid, water and a
copper catalyst are contained in a glass vessel. This is
placed in a pressure vessel equipped with a gauge or other
means of monitoring the change in internal pressure. The
"bomb" is charged with oxygen to a pressure of 6.2 bar (90
psi) and heated to 150C. The time taken for the pressure
to fall by 1.75 bar (25.4 psi) is monitored and recorded as
the life of the sample. Fig. 14 shows the b o m b and it's component parts while Fig. 15 shows a typical pressure chart
after a test. This is a highly accelerated test that is normally
completed well within 24 h. It does not represent what
happens in practice as the pressure prohibits the antioxidant (and water) from volatilizing. However, it is maintained that it shows good correlation with service [54]. It is
also widely used in fluid development as a screening test
for quality control purposes and in monitoring the stability of used fluid. Typical limits on mineral turbine oil
would be >350 m i n for ISO 32 or 46 grade products
(ASTM D 4304). Higher values, e.g., > 4 5 0 min are required
by some turbine builders.
2. ASTM D 943, Standard Test for Oxidation Characteristics
of Inhibited Mineral Oils, also known as the TOST (turbine
oil stability) test, is the second principal test for steam turbine oils. This involves heating the fluid together with water at 95C in the presence of iron and copper catalysts,
while air is passed through. At regular intervals the acid
n u m b e r in the fluid is measured and the test terminated
when the level reaches 2.0 mg KOH/g. In contrast to the
RBOT procedure, and depending on the base stock and activity of the stabilizers, this test can take several thousand
hours to complete. Minimum requirements for ISO 32/46
viscosity grades are normally 2000-2500 h. Fig. 16 shows
FIG. 14A view of the ASTM D 2272 pressure vessel, recorder, and sample container with catalyst.
317
The metal specimens used in the oxidation tests are normally (but not cJways) in electrical contact as this is how they
are found in the system and corrosion is frequently accelerated by bringing together metals of different electrical potential. The arrangement of the metal specimens in the FEDSTD-791, method 5308 and Alternative Procedure 2 in ASTM
D 4636 is shown in Fig. 17.
Mineral gas turbine oils are also tested by a modification of
the 5308 procedure. General Electric, for example, specifies
this method for its high temperature gas turbine oil specifi-
318
MANUAL
HANDBOOK
bine oils meeting ISO VGs 32 and 46. To increase the test
severity the duration was extended from 3-9 days for most
oils. This resulted in the mineral oils starting to degrade significantly.
FIG. 17Metal catalyst arrangement used in the FEDSTD-791 method 5308 oxidation test.
cations, GEK 32568 and GEK 101941, which call for a temperature of 175C while reducing the duration to three days.
Because of the importance of deposit formation in aircraft
lubricants, the accurate measurement of the amount of dirt
or sludge produced during the high temperature oxidation
tests is as important a feature of these tests as the generation
of acidity and increase in viscosity.
Oxidation test conditions for phosphate esters tend to fall
between those of mineral oil axid synthetic esters though, because of their tendency to hydrolyze, the tests specified are
dry tests. Typical test conditions are 164 h at 120C in the
presence of copper and iron catalysts (ISO 15595) or three
days at 175C (FED-STD-791, m e t h o d 5308 modified) as
found in b o t h ASTM D 4293, S t a n d a r d Specification for
Phosphate Ester Based Fluids for Turbine Lubrication and
the General Electric specification GEK 28136 for phosphate
ester fire-resistant gas turbine lubricants. Table 13 [27] compares the oxidation stability under stemdard and more severe
FED-STD-791 test conditions of uninhibited butylatedphenyl
phosphate esters and commercially available mineral gas tur-
319
TABLE 13--Comparison of the oxidation stability of mineral gas turbine oil with butylated phenyl phosphates
under extended FED-STD-791 test conditions.
Test
Duration
(days)
Viscosity
Increase
ISO VG 32 phosphate
(TBPP)
3
6
9
ISO VG 46 phosphate
(TBPP)
3
6
9
3
6
9
3
4.4
3.8
6
6.4
7.3
3.6
4.2
25
3
6
9
3
6
9
Fluid
3
6
3
3
(%)
18.3
24.3
49.5
23.4
28.6
80.6
13.4
21.2
- 5 to +15
- 5 to +20
Acidity
Increase
(mg KOH/g)
0.11
0.37
0.85
0.27
0.33
1
0.44
0.8
5.3
2.2
3.1
5
3
4.5
7
2
5.1
2.5 max
3.0 max
C12H22CH C O O H
Cu
Cd/Fe
Al
Mg
-0.11
0.02
-0.01
-0.01
0.11
-0.04
0.0
0.03
0.14
0.03
0.21
0.56
0.02
0.04
0.18
0.06
0.24
-0.17
0.04
0.1
-0.03
0.02
0.03
-0.01
0.17
0.18
-0.07
0.0
0.0
-0.11
0.08
-0.11
0.0
0.0
0.09
-0.03
0.02
-0.02
-0.02
0.13
0.07
where R, is
0.03
0.29
-0.02
0.02
0.04
0.01
0.08
0.13
0.04
-0.03
-0.1
-0.47
0.02
-0.13
0.05
-0.05
-11.7
0.03
0.03
0.05
0.01
0.03
0.06
0.06
0.07
0.33
0.02
0.01
0.04
-0.04
0.02
0.0
0.52
0.01
0.35
-0.04
0.02
-0.15
-0.1
0.07
0.96
0.05
0.02
0.32
+-CH2CH2O-J-H
I
CH2COOR1
C12H22CH C O O H
CH2CONHR2
FIG. 18Typical structures for turbine oils rust inhibitors.
can protect the metal from either type of attack by the formation of a protective layer of up to 5000A thick [55]. These
products, known as metal passivators are, for turbine oils
and fluids, chiefly of the triazole family (Fig. 19), and the effect of their activity is to substantially extend the life of fluids
in copper-catalyzed oxidation tests. Their effectiveness is
readily demonstrated in oxidation tests such as ASTM D 2272
and ASTM D 943. Apart from their performance in these and
other metal-catalyzed oxidation tests, the corrosive tendencies of oils towards copper is most frequently assessed by
ASTM D 130, Standard Method of Test for Detection of Copper Corrosion from Petroleum Products by the Copper Strip
Tarnish Test. In this test, a copper strip is normally immersed
in the oil for 3 h at lOO'C, but more severe conditions are also
used depending on the application. Following the immersion
period the strip is solvent cleaned cind visually rated for corrosion by comparing the surface color or tarnish with the
ASTM Copper Strip Corrosion Standards, which represent
increasing levels of tarnish axid corrosion. Normally turbine
oil specifications call for a maximum rating of lb, which is
slight tarnish.
Unfortunately, triazole derivatives titrate as acid and therefore contribute slightly to the acidity of the fresh fluid, a factor that has to be considered when meeting specification limits on fresh fluid.
Antiwear and Extreme-Pressure Additives
Antiwear additives are compounds added to an oil to reduce
the wear occurring between the surfaces in sliding contact.
They are normally effective at light to medium loads, for example in pump operation. These additives, of which neutral
triaryl phosphates are perhaps the most well known examples, initially form strongly adsorbed layers on the surface.
As the temperature increases due to the relative movement
of the surfaces, a chemical reaction takes place with the surface. The mechanism early suggested involved the formation
of a lower melting eutectic of iron and iron phosphide,
which flowed into the gaps between the asperities and therefore helping to provide a greater surface area to cany the
load. This idea was later rejected in favour of a metal phosphate layer that assisted lubrication [56]. The latest work,
HANDBOOK
methylene-bis-benzotriazole
tolutriazole
N
N
I
CH2NR2
N-alkylated benzotriazole
FIG. 19Structures of some metal passivators used in turbine oils and fluids.
however, suggests the formation of a self-regenerating
polyphosphate layer possibly in the presence of amorphous
carbon [57].
As the temperature increases still further a point is reached
where the phosphate film breaks down and cannot prevent
metcil to metal contact. In order to sustain even greater loads,
for example to provide adequate gear lubrication, it is necessary to generate higher melting films, which are normally
achieved by adding extreme pressure (EP) additives, particularly sulfur in the form of a sulphur carrier, e.g., ZDTP, sulfurized fats or olefins. Combinations of phosphorus and sulfur are also widely used and cover a wider temperature range
than each element individually, providing both antiwear
properties and EP performance over a wide range of applied
loads. Figure 20 shows the structures of some typical antiwear and extreme pressure additives.
Most specifications for hydrocarbon turbine oils do not require antiwear performance. There are also normally no
load-carrying requirements for steam turbine oils except for
extreme pressure steam turbine oils, e.g., in marine applications, but they do exist for gas turbine oils, and where the oil
is used for the lubrication of both a steam and gas turbine as
in some combined cycle applications. These requirements
are not particularly onerous, typically lying between FZG
failure load stage values of 5-8 while EP turbine oils require
a failure load stage of 12 + . Micro-pitting resistance may aJso
be required for this more severe application and is also ceirried out on the FZG gear rig using the Forschungsvereinigung Antriebstechnik (FVA) method 54/I-IV.
The other application to require gear testing is aero-engine
lubrication. These oils have traditionally required performance on the Ryder Gear Tester (ASTM 1947now discontinuedor FED-STD-791, method 6508). Increasingly, because of better precision, the test devised by the German
Forschungsinstitut fiir Zahnrad und Getriebe (FZG) is being
used and this method has been standardized by ASTM as D
5182, Standard Test Method for Evaluating the Scuffing
Load Capacity of Oils. Both the FED-STD 791 method and
the FZG procedure involve "a recirculating power loop principle, also known as a four square configuration, to provide a
fixed torque (load) to a pair of precision test gears." A
schematic is shown in Fig. 21. The drive gearbox and the test
gearbox are connected through two torsional shafts. Shaft 1
contains a load coupling used to apply the torque through the
use of known weights hung on the loading arm. The procedure involves operating the machine at a constant speed
(1450 rpm) and oil temperature (90C) for a fixed period at
successively increasing loads until the failure criteria are
reached. This is "when the summed total width of scuffing or
scoring damage from all 16 teeth is estimated to equal or exceed one gecir tooth width." The FVA micro-pitting test referred to above is in two parts. First, a load stage test is carried out in which the test oil is run at each load stage between
5 and 10 for a period of 16 h. This is followed by endurance
test involving 80 h at Load Stage 8 followed by 5 periods of 80
h at Load Stage 10. An assessment is made of the amount of
pitting or profile deviation on each tooth at the end of each
test period.
For aviation applications, the Ryder Gecir Test is still used
with the MIL-PRF-23699F specification in accordance with
Antifoams
The inhibition of foaming is essential to ensure the correct lubrication of pumps and bearings and, in hydraulic systems,
the transmission of power. Foam can also result in a rapid
loss in oxidation stability of the oil or fluid and, under the
worst conditions, can cause fluid loss from the tank. It is
therefore important that air is lost quickly from the fluid and
this can be assisted by the addition of very small quantities
(usually a few parts per million) of specific chemicals known
as antifoams that reduce the surface tension on the bubble
envelope [58]. The most widely used of these are the silicone
fluids. Chemically, these are polydimethylsiloxanes, which
triaryl phosphate
dialkyl phosphite
where R is C4-C8
triphenylphosphorothionate
RO^
OH.HNR'2
321
R'zNH.HO'
OH.HNR'2
amine phosphates
FIG. 20Structures of typical antlwear/extreme pressure additives used in turbine oils
and fluids.
322
MANUAL
HANDBOOK
1 != pinion
2 = gear wheel
3 = drive gears
4 = load clutch
diffusers produce bubbles of a known and consistent size. After passing air through the fluid for 5 min at 24C (TS^F), the
volume of foam (tendency) is noted immediately and then
also after 10 min (stability). The test is repeated at 93.5C
(200F) and then again at 24C to check if the foaming behavior has changed (possibly due to loss of cintifoam) as a result of the exposure to high temperature. The results are
quoted in terms of the tendency/stability values obtained at
each of the three temperatures. Values are normally much
lower at the higher temperature and hence limits under this
condition are more severe.
Because of the importance of foaming and its related topic,
air release, it is further discussed in the section on Performance Requirements, Their Significance and Evaluation.
The performance of the oil is usually retained as long as the
additives remain in solution a n d are not depleted owing to removal from the fluid as volatiles, by partitioning into any free
water, by precipitation, or by natural usage. If the additive is
removed by any of these means, the rate of degradation, for
example, can suddenly accelerate. If the oil monitoring is not
adequate it can result in the oil exceeding its operating limits
5 = locking pin
6 = lever arm iNWn weights
7 = torque measuring clutch
8 = temperature sensor
shaft 2
test gears
drive motor
drive gears
load clutch
shaft 1
FIG. 21Diagram of the FZG Test Rig.
Control system
Specific Application
Symbol ISO-L-
Typlcal Applications
Normal service
TSA
Special properties
TSC
Fire-resistant
TSD
High load-carrying
ability
TSE
Normal service
TGA
Higher temperature
service
TGB
Special properties
TGC
Fire-resistant
TGD
High load-carrying
ability
TGE
Fire-resistant
TCD
Aircraft^
Hydraulic"
TA
TH
o x i d a t i o n t e s t s (for e x a m p l e t h e A S T M D 9 4 3 o x i d a t i o n t e s t
referred to above) o r large-scale fire-resistance tests t h a t are
clearly impossible and/or u n n e c e s s a r y to evaluate on a b a t c h
p r o d u c t i o n b a s i s . A n e x c e p t i o n t o t h i s s i t u a t i o n is for m i l i t a r y
a v i a t i o n s p e c i f i c a t i o n s , e.g., M I L - P R F - 2 3 6 9 9 F w h e r e t h e Ryd e r G e a r T e s t is p e r f o r m e d o n t h e first b a t c h of e a c h c o n t r a c t
325
TABLE 15International and national specifications for turbine oils and hydraulic fluids.
International or
National Specifications
International Standards
Organisation
International Electrotechnical
Commission
European Standard
Canada
China
France
Germany
Japan
India
Russia
UK
USA
Steam Turbines
ISO 8068
Fire-Resistant
Hydraulic Fluid
Aero-Derivative Gas
ISO 8068
CD 10050
lEC 61221
EN61221
3-GP-357Mb
DL-571
DL/T 571-95
AIR 3514A AIR 3517
DIN 51515
nS-K-2213
IS 1012
Tp-22CTU 38.101821
Tp-22BTU 38.401-58
BS489
ASTM D 4304
ASTM D 4293
In preparation
JISK-2213
IS 1012
DIN 51518
COST 12245-66
COST 13076-86
ASTM D 4304
ASTM D 4293
TABLE 16Turbine builders and utility specifications for lubricating oils and hydraulic fluids.
Turbine Builder/Utility
Alstom Power
(France/UK)
Alstom Power Mannheim
(Germany)
Alstom Power (Switzerland)
Alstom Power (Sweden)
Steam Turbine
Oil Specification
Industrial Gas
Turbine Oil Specification
Aviation Gas
Turbine Oil Specification
NBAP50001A
SBVPRlOOl C
DIN 51515
H G T D 9 0 117V001Q
812101
812102
812106
812107
812101
812102
812106
812107
65/0027
QM44-101/B
IS 1012
HN 20-S-30
JISK-2213
GEK 46506D
QM44-100/B
602W917
ST 22007
HN20-S-41
Siemens TLV 9013.04
GEK 32568C
GEK 101941
GEK-28136A*
D50TF1-S4
Solar
Toshiba
Siemens Westinghouse
GEK 46357E
165A974CE
JISK-2213
GEK 4506D
JISK2213
769 45192
JISK2213
GEK 46357E
STM-1840
Fire-resistant Hydraulic
Fluid Specifications
Procurement Specification
207001, Part 9
521CTypell
TLV9013/04
TLV 9016 03/02
(hydraulic oil)
JISK-2213
55125Z3
TLV 9013/04
TLV:9012 01/05
ES 9-224
GEK 32568C
55125Z3
GEK 46357E
53740AL
326
MANUAL
HANDBOOK
Belgium
BN-PO-175A
Canada
France
3GP-357-Mb
STM 7220B
Italy
UK
MM-O-2001
Def Stan. 91-25/3
USA
MIL-L-17331H
Industrial Gas
Turbine Oil
Aviation Gas
Turbine Oil
BA-PO-lOeA"
BA-PO-115A
BA-PO-103B''
BA-PO-109C
AIR3514/A
AIR3515/A-B''
AIR3516/A"
Def. Stan 91-93
Def.Stan 91-94
Def.Stan 91-97/1"
Def.Stan 91-98/1
Def.Stan 91-99/1"
Def.Stan 91-100
Def.Stan 91-101
MIL-L-aOSlC
MIL-PRF-7808L
MIL-PRF-23699F
' Denotes a mineral oil-based product. The remainders are synthetic-based lubricants.
tures for measuring viscosity, the most widely-used temperatures are now 40C and 100C, and these are cJso the basis for
the determination of viscosity index and viscosity classifications (see below). The former temperatures, however, are still
frequently quoted and care is needed to avoid confusing the
different data. It is possible to measure viscosity over a wide
temperature retnge using this method and Fig. 24 illustrates
the viscosity/temperature relationships for the major fluids
TABLE 18A comparison of the technical requirements for turbine oils and fire-resistant hydraulic fluids.
Test Method
Property
Viscosity Grade
Appearance (20C)
Kinematic Viscosity (cSt)
at 40X
Steam/Industrial
Gas Turbine Oil
Aero-Derivative
Gas Turbine Oil
Fire-Resistant
Hydraulic Fluid
ASTM
32
Clear and bright
22
46
D2422
3448
D445
3104
28.8-35.2
41.4-50.6
-6
180
>23
4.9-5.4
13000
6
-54
246
D97
D92
3016
Report
1.0
100C
-40X
Vise. Change after 72 h at -40C (%)
Pour point (C)
Flash Point (X)
Density at 15C
Total Acid No (mg KOH/g)
max
mEix
max
min
max
max
-18
1.2
0.1
FED-STD-791 etc.
ISO etc.
3675
6619
D974
SAE ARP 5088
Foaming Tendency/Stability
Sequence 1
Sequence 11
Sequence 111
Air Release at 50C
Chlorine Content (mg/kg)
Water Content (%)
Volume Resistivity at 20C (Mfim)
60247
Emulsion Characteristics at 54C
min. to 3 ml emulsion
Evaporation Loss (%)
Rust Preventing Properties
Procedure A
Rubber Compatibility (% swell)
Corrosiveness to Copper Rating
Fluid Compatibility-sediment (mg/L)
Trace Metal Content (ppm)
Shear Stability-Viscosity Loss
at 100F (%)
Bearing Deposition-demerit rating
Thermal Stability & Corrosivity
at 274C
-Viscosity Change (%)
-Acid Number Change (mg KOH/g)
-Metal Weight Change (mg/cm^)
Oxidation Stability h to acid
number 2.0
Oxidation Stability-min. to
175kPa drop
Oxidation Stability
Viscosity change (%)
Total Acid Number Change
Sludge Content (mg/100 mL)
Wt. change (mg/cm^)-Fe
Wt. change (mg/cm^)-Cu
Wt. change (mg/cm^)-Ag
Wt. change (mg/cm^)-Mg
Wt. change (mg/cm^)-Ti
Wt. change (mg/cm^)-Al
Oxidation Stability
Acid number increase (mg KOH/g)
Wt. loss-Fe (mg)
Wt. loss-Cu (mg)
D892
max
max
max
mix
max
max
mm
6247
150/0
25/0
150/0
6
50
0.1
40
D3427
9120
15597
760
lEC
30
15
D 1401
6614
50/0
25/0
25/0
25/0
10
D972
D665
25-May
D6546
D 130
Pass
3604/3433
6072
3403
Atomic Emission
Spectr.
max
max
20
Various (1-11)
max
max
80
max
max
max
min
5.0
6.0
4.0
2000
D943
min
350
D2272
D2603
3410
3411
5308
max
max
max
max
max
max
max
max
max
max
max
max
- 5 to + 25
3.0
25/50
0.2
0.4
0.2
0.2
0.2
0.2
15595
1.5
1.0
2.0
328
HANDBOOK
TABLE 19A summary of the principal test methods for evaluating turbine oil properties.
Property
ASTM Method
ISO Procedure
Color
Kinematic Viscosity
Low Temperature Viscosity
and Viscosity Stability
Viscosity Index
Viscosity Classification
Density-hydrometer method
Density-digital density meter
Acid Number-Colorimetric
Potentiometric
D 1500
D445
D2532
3104
D2270
D2422
D1298
D4052
D974
D664
2909
3448
3675
12185
6618
6619
Water Content
D 1744
Pour Point
Evaporation Loss
Flash/Fire Points-Open Cup
Autoignition Temperature
Spray Ignition
D97
D972
D92
D2155/E659
760
12937
3016
D5306
D892
D3427
D 1401
D2711
D943
D2272
D5846
2592
3988
15029
20823
14935
6247
9120
6614
Others (FED-STD-791
Unless Specified)
102
305
307
9111
5105
5106
SAE ARP 5088
3253
201
351
1103
1152
Factory Mutual
Std. 6930
6053
3213
5307/5308
Hydrol5^ic Stability
s h e a r Stability-diesel injector
Shear Stability-sonic oscillator
Shear Stability-tapered bearing
Thermal Stability
Particle Contamination-optical
Particle Contamination-microscopic
Particle Contamination-gravimetric
Sizing particles
Trace Sediment
Copper Corrosion
Rust Preventing Characteristics
Corrosion prevention
Seal Compatibility
Fluid Compatibility
Electrical Resistance
4-Ball Wear Test
Vane P u m p Test
Gear Test-Ryder
Gear Test-FZG
Bearing Test
Deposition Test
D2619
15595
15596
CETOPRP 112H
D2603/D5621
D2070
F661
F313
D4898
D2273
D 130
D 665/D 3603
D 1748
CEC L-45-A-99
2508/3411
4402
4407/8
4405
4406
2160
4404
6072
D 1169
D4172
D2882
D 1947
D5182
3009
3004/3010
5325
4011
3604/3432
3403
lEC 60247
CETOP RP 67H
20763
14635
6508
DIN 51354
3410
5003
CHAPTER
12: TURBINE
(mm2/sec)
10 000
5000 Cavitation
X3
(0
>
,g
'Jam
ro
E
(D
C
7)
100
50
20
10
5
Low efficieaiey=
<D
O
O
a> 3
S 3
5' CD
3
Q.
CD
O.
3
CO
(D
Reduced volumetRelfticiency
-4i^3lv3Q0S
1
FIG. 23Significance of viscosity for tlie operation of a typical hydrostatic system. Reproduced from "Hydraulic Fluids,"
with kind permission of Butterworth-Helnemann, Oxford, UK.
LUBRICATING
FLUIDS
329
(0
o
.52
"c
<u
o
to
ou
CO
>
(U
200
10
20
40
55
65
75
85
degrees farenheit
FIG. 24Viscosity/temperature data for different turbine oil and fluid.
100
331
332
MANUAL
HANDBOOK
c
(D
Group 1
mineral
oil
Groups
mineral
oil
333
ISOVG32
polyol ester
ISOVG46
PAO
ISOVG46
phosphate ester
FIG. 26The effect of temperature on air release values for different turbine oils and
fluids.
334
MANUAL
HANDBOOK
Chlorine Content
Limits on chlorine content are required with phosphates in
order to avoid servo-valve erosion [63]. In fact it is the chloride ion (CI ) level that is critical and this can arise either
as a trace contaminant from the manufacturing process
(from the use of phosphorus oxychloride) or by air-bom
contamination. Another source is the incorrect use of chlorinated solvents for cleaning system components. Although
the chlorine in solvents is not initially present in ionic form
it is thought that the solvents break down thermally in the
system to release chloride ion. While limits are placed on
new fluid levels (normally 50 ppm), the content of chlorine
in fresh fluid is usually significantly lower (typically 20-30
p p m ) . In spite of the importance of the level of chloride ion
in the fluid, it is rarely specified for new fluid and the limits that have appeared in the past are at much lower levels,
e.g., 0.5-2 ppm.
The accurate measurement of very low levels of chlorine is
not easy and the standard b o m b calorimeter tests are not sufficiently accurate, as the combustion of phosphates by macro
techniques is usually incomplete. ASTM D 808, Standard
Test Method for Chlorine in New and Used Petroleum Products (Bomb Method), a typical bomb calorimeter process, for
example, is only valid for chlorine levels of 0.1-50%. Instead,
microcoulometry (e.g., IP proposed method AK99), a combustion process which uses very small amounts of sample is
preferred, or possibly X-ray fluorescence (ISO 15597). The
basis of all the calorimeter methods is the titration with silver nitrate of the chloride ion produced by combustion. Due
to the purity of phosphates in commercial production this
parameter is rarely a problem today and, as will be shown
later, is controlled in use by special filtration techniques.
Fire-resistance Tests
These properties are the most important requirements for the
phosphate esters and for the small quantities of polyol esters
that are supplied as hydraulic fluids into this application. The
origins of fires in turbines are divided almost equally between
the lubricant and hydraulic fluid [64] and are normally a re-
Tests
CHAPTER
12: TURBINE
LUBRICATING
FLUIDS
335
exhaust channel
anemometer
exhaust gas
thermocouple (Tp/Tex)
nozzle
\_
ambient air
thermocouple
atomising air
hydraulic fluid
FIG. 27Schematic representation of the test chamber used for the ISO 15029-2 Spray
Ignition Test. Reprinted with permission of the Health and Safety Laboratory, Sheffield,
UK.
der. Figures 27 and 28 are diagrammatic representations of
the equipment used to carry out the above tests.
Hot Surface
Tests
Although the latest spray ignition tests can indicate the relative fire resistance of fluids, the results tell us nothing about
the temperature at which the fluid would ignite on contact
with a hot surface. It is therefore important to obtain some
idea of this aspect from appropriate procedures. Currently
only one test is specified for turbine fluids, the determination
of autoignition or s p o n t a n e o u s ignition t e m p e r a t u r e , by
ASTM D 286 or D 2155 (both now obsolete) or by E 659, Standard Test Method for Autoignition Temperature of Liquid
Chemicals. In each of these procedures a small, measured
a m o u n t of the test fluid is inserted into a heated glass container (conical or round-bottomed flask). The temperature at
which the fluid ignites with the production of a visible flame
was the result recorded in the two earlier tests while the most
recent variant also observes the production of "cool flames,"
which occur at lower temperatures than conventional hot
flames.
The recent procedures have resulted from attempts to obtain a more even temperature distribution throughout the
container, while replacing the original molten lead bath,
which was a health hazard. Major differences are found between the results of the three tests with the trend towards
lower values with the later methods [66]. The reason for the
differences in results is mainly due to the increased size of
the container and therefore to the increased oxygen concentration present [67]. Unfortunately, the reduction in autoignition temperature values with recent methods has occasionally led the user to believe that an inferior product was
being supplied and as a result data is still quoted on the earlier methods, sometimes together with the figures from the
latest test. A further hot surface ignition method (The Hot
Manifold Test), based on FED-STD-791 Method 6053, is currently being developed by ISO as Standard 20823 and may be
preferred to autoignition temperature in the future as the
conditions more obviously simulate a n industrial hazard.
Wick Tests
The flammability behavior of the fluid when it is absorbed
into a substrate (or wick) can be assessed by ASTM D 5306,
336
HANDBOOK
fire products
collector
1.25 m
nozzle
^ y - / ^
flexible
^/connectors
1.4 m
propane
burner
floor
MdNn
'
sample
pressure
vessel
propane
load cell
/7777Z
FIG. 28Factory Mutual Research spray ignition test equipment. Reprinted with permission of Factory IVIutual Research, Norwood, MA.
by applying a vacuum to the fluid. Physical methods for drying used oil and fluid are practiced widely but currently the
use of chemical adsorbents is only found with fire-resistant
fluids.
Although the behavior of the fluid in use is more critical
due to the likely presence of contaminants and fluid degradation products, new fluid is tested to ensure that emulsification does not initially occur as a result of the use of surfaceactive products such as corrosion inhibitors.
The method most widely used to assess this aspect of performance is ASTM D 1401, Standard Test Method for Water
Separability of Petroleum Oils and Synthetic Fluids, (ISO
CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRA ULIC FLUIDS 337
ceramic
fibre cord
chart recorder
50 g weight
50 g weight
reservoir
wick
TF5^
burner position for
setting flame height
r
|l
|l
|l
burner may
be raised and
lowered in
clamp
stop bar
from propane
regulating valve
FIG. 30Equipment used for the ISO 14395 wicl( flame persistence test.
HANDBOOK
6614) where the fluid at 40C is stirred with an equal volume of water and the time taken for separation of the resulting emulsion (if formed), is noted. Typical limits for separation to a residue of 3 mL emulsion are 30 min maximum
(mineral oils) and 15 min maximum for phosphate esters.
Stability Characteristics
Oxidative Stability
All fluids are assessed for their oxidative stability as their service lives depend to a large extent on this property, and the effects of fluid degradation in terms of acidity generation, viscosity increase, and the production of deposits can have an
important impact on the system performance. The principal
methods used for evaluating oxidative stability were indicated earlier in the discussion on the testing of antioxidants.
These methods are additionally used to assess the effects of
other additives, e.g., rust inhibitors on oxidation stability and
assessing the performance of complete formulations.
In addition to the Universal Oxidation Test designed to
overcome the long test duration associated with the ASTM D
943 test, other approaches have been or are being evaluated.
These include a dry version of the TOST and, for research
and development, quality control and residual life assessments, high pressure differential scanning calorimetry
(ASTM D 6186, Standard Test Method for Oxidation Induction Time of Lubricating Oils by Pressure Differential Scan-
50
200
250
1-22
21
--20
--19
(^
o
18 b
To
178
' '
in
--16
-Lis
200
150
100
339
Hydrolytic Stability
This property assesses the fluid stability in the presence of
moisture. Normally the effect of water is to generate the acid
and alcohol (or phenol) from which the ester was originally
formed. All esters are sensitive in varying degrees to water
and, since hydrolysis is the normal mode of breakdown, it is
an important factor in determining the Hfe of both phosphates
and the polyol ester fluids used in hydraulic and aero-engine
lubricant applications. In steam turbine systems particularly,
water contamination of the hydraulic fluid and lubricant is often found and requires regular monitoring. As noted earlier
(Table 9) the structure of phosphates affects their hydrolytic
stability and may influence the selection of product for use in
steam (wet) or gas (dry) turbine applications.
The test procedure most commonly used for assessing hydrolytic stability is ASTMD 2619, Standard Test Method for
Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle
Method). In this test the fluid and water are mixed together
in a rotating sealed container for 48 h at 93C in the presence
of a solid copper catalyst, followed by measurement of the
acidity level in both the fluid and the water layers and the
metal weight change. Procedures are available for fluids that
are more or less dense than water and Fig. 32 shows the bottle with oil, water, and catalyst coupon.
n
li
340
HANDBOOK
injector nozzle set at a predetermined lifting pressure, for example 17.5 MPa (175 bar) for 30 cycles, (ASTM D 3945, Standard Test Method for Shear Stability of Polymer-Containing
Oils Using a Diesel Injector Nozzle). More recently, ASTM D
5275, Standard Test Method for Fuel Injector Shear Stability
for Polymer-Containing Fluids has been published. The latter
method was originally Procedure B of the D 3945 method but
was separated after tests showed that the two procedures in
the earlier method often gave different results. Although the
principle of the two methods is the same, the equipment differs and the latest test uses conditions of 20.7 MPa (207 bcir)
and 20 cycles. In both cases, reference fluids are required to
calibrate the equipment prior to evaluating the test samples.
A concern over the lack of field correlation with the results
from the diesel injector rig has recently led to the proposal in
Europe to use a tapered roller bearing as the means for shearing the fluid. This is Co-ordinating European Council (CEC)
method L-45-A-99, "Viscosity Shear Stability of Transmission Lubricants" that promises improved precision and better correlation with field data.
Rusting and Corrosion Behavior
The requirement for an oil or fluid to prevent rusting (of ferrous metals) and corrosion (of non-ferrous metals) is an existing part of nearly all hydrocarbon turbine oil specifications. While most rust tests are carried out at typical bulk
fluid temperatures of 35-60C, high temperature corrosion
performance requires evaluation either by oxidation/corrosion tests or by specific high temperature tests in non-oxidizing conditions such as those specified by the aviation turbine
builders. Some tests, e.g., gas turbine "hot end corrosion"
cannot be satisfactorily simulated in the laboratory and require evaluation in an engine test.
The most widely-used test for assessing rusting characteristics was reported earlier as ASTM D 665, Standard Test
Method for Rust Preventing Characteristics of Inhibited Mineral Oil in the Presence of Water. In spite of the title, the
method is also used for non-hydrocarbon oils and there is provision for the testing of products such as phosphate esters,
which are heavier than water. Although it may be difficult to
distinguish between the ratings for "moderate" and "heavy"
rusting in this test, this is largely academic, as specifications
normally call for a "Pass," that is, the absence of rust.
One of the limitations of the D 665 method is that it evaluates rusting on vertical surfaces only. In reality, horizontal
surfaces that can retain droplets of water are more prone to
rusting. A method has therefore been devised "to indicate the
ability of oils to prevent rusting and corrosion of all ferrous
surfaces in steam turbines." This is ASTM D 3603, Standard
Test Method for Rust-Preventing Characteristics of Steam
Turbine Oil in the Presence of Water (Horizontal Disk
Method). The test involves immersing a horizontal steel disk
and a vertical steel cylinder in a stirred mixture comprising
275 mL of the oil and 25 mL of distilled water for 6 h at 60C.
At the end of this period the specimens are washed and inspected for rust. The test is carried out in duplicate and no
rust must be seen in either of the two tests for the oil to be
considered a pass.
The above procedures only consider rusting in fluid contact with the metal surface whereas vapor-phase rusting is
CHAPTER
12: TURBINE
also possible, for example above the liquid layer in the tank.
This condition is simulated in ASTM D 5534, Standard Test
Method for Vapor-Phase Rust-Preventing Characteristics of
Hydraulic Fluids. With the exception of cin additional steel
specimen, which is located in the vapor space above the liquid, the apparatus and test conditions are identical to those
found in ASTM D 3603. The method is divided into two parts,
the first relating to fluids where water is the continuous
phase and the second to fluids where oil or other water-free
fluids (except phosphates) are in the continuous phase. In the
latter case the water necessary to cause corrosion is contained in a bcciker located below the specimen for assessing
vapor-phase corrosion. Results are reported as a pass or fail.
The introduction of a corrosion-inhibited grade of fluid in
the MIL-PRF-23699 specification has also resulted in the incorporation of a humidity cabinet test (ASTM D 1748, Standard Test Method for Rust Protection by Metal Preservatives
in the Humidity Cabinet.) This procedure involves immersing steel plates in the fluid, allowing them to drain and then
exposing t h e m to water vapor in the cabinet. The time tciken
for the production of rust is monitored.
In use, metals of different t3rpes may be in contact with one
another and the potential difference of the metal couple in
these conditions can influence gcJvanic corrosion, particularly with water-based fluids. An attempt to simulate this
condition for non-aqueous fluids is found in the CETOP
Method RP 48H, which is also being published as ISO 4404
Part 2. In this test, selected metal pairs in electrical contact,
after cleaning and pre-weighing, are half immersed in the
fluid for 28 days at 35C in a covered beaker. At the end of the
test period the weight change is measured and examination
made of the specimens for signs of corrosion, including the
surface above the liquid layer, which will indicate whether
vapor-phase corrosion has tciken place.
Hydraulic or lubricating oil systems containing phosphate
esters can be made from either mild or stainless steel and,
while rusting can occur with these fluids, it is not a common
occurrence and is normally limited to the area above the liquid layer in the tank where condensation occurs. If the tcink
interior is coated with phosphate, this forms a protective
layer and reduces the possibility of rusting. In cases where
the mild steel surface does not come into contact with the
fluid, condensation may be prevented by maintaining w a r m
fluid in the tank and/or passing dry air over the surface of the
liquid in the reservoir. As a result it is now standard practice
to leave the interior surfaces of hydraulic systems unpainted
when using phosphate esters. In the past, epoxy coatings
were recommended, but unless the coating can be cured in
position, the long-term resistance of this type of paint cannot
be guaranteed. However, due to the reduced risk of rusting
with these fluids in turbine applications, the frequent use of
stainless steel systems and the possible removal of inhibitors
by the adsorbent solids used in fluid conditioning to maintain low levels of acidity, there is normally no rusting requirement in the specification for this type of fluid.
With regard to non-ferrous metals, the corrosion of copper/brass as is found, for example, in turbine oil coolers, can
be a problem for all oil types, as the dissolution of this metal
will catalyze oil oxidation. The potential for oils to cause corrosion of copper and its alloys and the use of ASTM D 130 for
assessing this condition was mentioned above. While metal
LUBRICATING
341
Cleanliness
The importance of clean oil, to ensure that small orifices in
valves remain clear, that bcciring surfaces cire undamaged,
and that p u m p s and motors r u n smoothly, is now well accepted. Dirt can EJSO play a part in catalyzing oil and fluid
degradation by stabilizing foam and increasing oxidation. It
may also promote emulsification in the presence of water
and increase the conductivity of the fluid. Limits on cleanliness have therefore become steadily tighter over the years. At
the same time the variety Eind efficiency of filters has improved [53]. Today, turbine lubrication systems use 6 fim
(j8 = 200) filters while hydraulic systems generally have finer
filtration, typically 3 jam (jS = 200) filters to remove particles
as small as 3.0/im "absolute" in view of the use of fine toler-
342
HANDBOOK
3 lower balls
clamped
Thermocouple
A/V\AAAA^
Heater
343
344
MANUAL
HANDBOOK
to their lack of seal swelling and necessitate the use of a cocomponent (usually a carboxylate ester) as a seal-swelling
agent.
The high operating t e m p e r a t u r e s experienced in a n increasing n u m b e r of applications, for example aviation gas
turbine lubricants, place severe stress on conventional elastomers. Consequently, the use of fluorocarbon (and, to lesser
extent, perfluoroelastomer) seals is now widespread. Phosphates eire also very selective with regard to seals and paints,
but fortunately a suitable range of materials is now available.
Examples of suitable elastomers for turbine oils and fluids
are given in Table 20. A general procedure for testing for the
compatibility of seals in non-aerospace applications is detailed in ISO 6072, Hydraulic Fluid Power-Compatibility between fluids cind standard elastomeric materials, while the
aero-gas turbine oil specifications require performance
against FED-STD-791 methods 3604 and 3433 or procedures
listed by the equipment manufacturers. An ASTM standard
entitled "Standard Test Methods and Suggested Limits for
Determining the Compatibility of Elastomer Seals for Industrial Hydraulic Fluid Applications" is currently in development. Table 21 illustrates the conditions recommended for
testing different elastomers in the ISO 6072 standtird. The list
indicates the principal types of elastomers used with the different fluids, but is not exhaustive.
All the procedures involve suspending a rubber specimen
of known volume in the oil or fluid u n d e r fixed conditions of
temperature and test duration. This is followed at the end of
the test by a second measurement of the volume to determine
the percentage swell that has occurred. Additional measurements may be made of the chemges in elongation at break and
tensile strength. Depending on the rubber type and application, the test temperature may vary significantly. Fluorocarbon and perfluorocarbon rubbers are, for example, evaluated
at higher temperatures than nitrile and neoprene. However,
tests at high temperatures, e.g., 150C as currently appear in
the latest draft ISO 6072 standard, may not be representative
of practice since, at this temperature, the basestocks and additive packages may not be stable and could give erroneous
results.
Until recently, all methods specified relatively short periods of immersion, usually u p to one week. It is now accepted
that this period may be too short for the degree of swell to
have stabilized, and in the latest version of ISO 6072, tests of
1000 h in length are now proposed in addition to the shorterterm exposure.
No s t a n d a r d m e t h o d s in turbine oil specifications are
known for evaluating paint compatibility and this aspect is
generally left to the paint manufacturers w h o u n d e r t a k e
long-term tests.
The aspects of compatibility discussed above relate only to
the fluid/constructional material interface. There is EJSO the
aspect of the compatibility of different oils and fluids with
each other. Should fluids from different manufacturers be
mixed? This aspect is viewed differently by different industries. On the one h a n d it is a condition of militciry aviation oil
specifications that all approved products should be compatible with one another. If this were not the case it could impair
the combat readiness of aircraft. In the industrial power generation market some equipment builders specify that a new
fluid must be compatible with the residue of the previous
charge without any adverse effect on the new oil. However,
FIG. 34A general view of the test equipment for measuring d.c. resistivity.
345
090
1
1 = inner elecrode
2 = outer etecrode
3 = guard ring
4 = inner elecrode
5 = silica washer
6 = silica washer
7 = minimum level
of liquid
the builder had investigated the compatibility of the two fluids cmd/or the user had accepted the risk associated with mixing. In some cases oils can be mixed without problems but
laboratory tests are advisable to check the effects of physical
and chemical (in)compatibility, e.g., the impact on stability
and the surface active properties (e.g., foaming and air release). The test used by the aviation turbine oil industry,
FED-STD-791 method 3403, Compatibility of Turbine Lubricating Oils, involves checking the miscibility with reference
ester-based lubricants. Mixtures of the test oil and the reference lubricants at three concentrations are heated in an oven
346
HANDBOOK
Polyol
Ester
Yes
Yes
Yes
No
No
Yes''
No
Yes"
Yes
Yes
No
No
No
Yes
Yes
Yes
No
No
Yes"
Yes
Yes*
Yes
Yes
No
No
No
No
Yes
Yes
Yes
TABLE 21Conditions recommended for testing the compatibility of elastomers with different turbine fluids.
Suitable
Temperature
ISO
Duration of
Test Elastomer
C 1
Test" h 2
Fluid
Classification
HH, HL
HM, HR
HV
NBRl, 2
HNBRl
FKM2
100
130
150
HFDR
FKM2
EPDMl
Polyol esters
HFDU
Mineral oils
Synthetic hydrocarbon
HEPR
168
1000
150
130
168
1000
NBRl, 2
HNBRl
FKM2
100
168
1000
HNBRl
FKM2
130
150
168
1000
"The test duration of 1000 h is recommended for evaluation of elastomer compatibility with highly critical fluids.
NBR = nitrile (acrylonitrile butadiene)
HNBR = hydrogenated nitrile
EPDM = ethylene propylene
FKM = fluorocarbon
Reprinted courtesy of the International Organization for Standardization, Geneva, Switzerland.
347
or not the system is being commissioned, and if operational problems are being experienced. Using the data produced to establish trends in performance can assist in identifying the source of problems and when action may be
needed [80].
Unlike the extensive range of specifications available on
fresh oil or fluid, the situation with regard to the used oil is
less complicated. Many, but not all, of the turbine builders incorporate used oil requirements into their new oil specifications. A few have separate standards and some of the oil or
fluid suppliers offer guidance in the absence of information
from the turbine manufacturers. Where no builder recommendations exist, guidance is also available from national/international standards. For mineral turbine oils there are
ASTM D 4378, Standard Practice for In-service Monitoring of
Mineral Turbine Oils for Steam and Gas Turbines; the lEC
Standard 60962, Maintenance and Use Guide for Petroleum
Lubricating Oils for Steam Turbines; and the very detailed
EPRI report referred to earlier [79]. For fire-resistant hydraulic fluids, lEC 60978 and ISO 7745, Hydraulic Fluid
Power-Fire-resistant Fluids-Guidelines for Use, are available, while for aero-engine oils there are recommended limits on acidity and viscosity increase from the turbine
builders, but otherwise no published requirements. The
rapid rate of top-up of oil in this applicationeven in industrial applicationsmeans it is unlikely that the physical
changes in fluid quality would normally reach values of concern.
The above industry guides are comprehensive documents
which typically examine the reasons for fluid degradation
and its impact on fluid performance, identify fluid sampling
techniques, give appropriate tests for monitoring both new
and used oil behavior, as well as a proposed schedule for
their use. Table 22, which is taken from ASTM D 4378, identifies the turbine properties of gas and steam turbine oils
that are monitored in service, their warning limits and appropriate action to be taken in the event that these limits are
exceeded. Quite a wide range of tests can be used to monitor
fluid degradation, etc. These can be divided into primary
tests that check for specific degradants or contaminants and
secondary tests, the results of which are influenced by the
degradant or contaminant. An example would be the measurement of water, which can be determined directly and in
esters, its presence may be implied from a reduction in viscosity or a rapid increase in acid number.
Acidity is probably the most important property monitored on a regular basis, but is the parameter most frequently disputed. As indicated earlier, of the two techniques
used for determining the acid number of both new and aged
fluid or lubricant, only the potentiometric method is really
suitable for aged fluid [81]. This is because the fluid darkens
on ageing and it becomes more difficult to estimate the endpoint in the colorimetric method. Some fire-resistant fluids
are also dyed to ensure that they are not confused with mineral oils and for such fluids this technique is also unsuitable,
particularly when new.
Other important properties that are routinely measured
for all Quids include viscosity, water content, and particulate
levels. In addition, rapid changes in color and appearance
can be indicative of developing problems. A measure of the
residual life or stability of the product may also be advanta-
Test
TABLE 22Interpretation of test data and recommended action for mineral turbine oils.
Steam (S)
Oil Life
Warning Limit
or Gas (G)
(Running Hours)
Interpretation
Action Steps
up to 20 000 h
up to 3000 h
Investigate cause.
Increase frequency of
testingcompare with
RBOT data.
Consult with oil supplier for
possible reinhibition.
0.3-0.4 mg KOH/g
S, G
at any time
during life of
oil charge
RBOT
up to 20 000 h
Investigate cause.
Increase frequency of testing.
RBOT
up to 3000 h
Investigate cause.
Increase frequency of testing.
RBOT
less than 2 5 % of
original oil
S, G
at any time
Water content
exceeds 0 . 1 %
at any time
Oil contaminated.
Potential water leak.
Cleanliness
exceeds accepted
limits"
at any time
light fail
up to 20 000 h
light fail
S, G
after 20 000 h
Appearance
hazy
S, G
at any time
solids or both
Color
S, G
at any time
Viscosity
5% from original
oil viscosity
S, G
at any time
a) Oil is contaminated,
b) oil is severely degraded, or
c) higher or lower viscosity
oil added.
Flash point
S, G
at any time
Probably contamination.
exceeds following
limits
tendency: 450
stability: 10
S, G
at any time
Possibly contamination or
antifoam depletion. In new
turbines residual rust
preventatives absorbed by
oil may cause problems
Acid no.
Increase over
new oil
0.1-0.2 m g K O H / g
Acid no.
Increase over
new oil
Sequence 1
S, G
CHAPTER
12: TURBINE
FUTURE TRENDS
Many of the developments discussed in the course of this
chapter will continue to influence the development and availability of turbine lubricating oils. Some of t h e m were the subject of presentations at an ASTM Symposium entitled "Turbine Lubrication in the 21st Century." The papers presented
are now published and serve as a useful reference to the subject [82].
Where possible, the turbine builders will continue in their
sccirch for higher operating efficiencies that will result in even
higher operating temperatures and greater thermal and oxidative stress on the lubricant. This, in turn, will accelerate the
move from solvent refined oils towards severely hydrocracked
oils and synthetic hydrocarbons. It may also accelerate a
move toward fire-resistant lubricants particularly as the dcingerous "cocktail" of higher temperatures and reduced staffing
could result in an increase in the frequency of oil fires.
The d e m a n d for greater e q u i p m e n t availability and reduced outages in order to improve the financial returns to the
IPPs will also result in a demand for longer oil/fluid lives. The
increase in operational severity will place even greater emphasis on stability, but the advent of in-service monitoring of
stabilizer levels, re-inhibition of the existing charge, the possibility of in situ reclamation by better filtration, and removal
of developed acidity by by-pass treatment will extend oil life
still further.
As a result of the anticipated longer oil life there will be increased competition for the initial fill. This will substantially
LUBRICATING
FLUIDS
349
reduce the operating margins for new business cind encourage the suppliers to provide "cradle-to-the-grave" service
agreements whereby they maintain the fluid throughout its
life, supply top-up material as needed, and eventually dispose
of the degraded product. The development of in situ condition-monitoring techniques will assist station staff in determining the level and timing of necessary fluid maintenance.
The trend to environmentally friendly fluids, where required, may also develop^particularly for water turbine applications, where some experience has been obtained with
biodegradable fluids [83].
One recent development not previously mentioned that
may have a future impact on the lubrication of gas turbines
has been the successful evaluation in a static engine test of a
vapor-phase lubricant based on a tertiarybutylphenyl phosphate [84,85]. Very small amounts of the lubricant are vaporized and react with the metal surface of a ceramic bearing
to form a polymeric film that can sustain a load. The immediate interest appears to be for missiles and other unmanned
aero-space vehicles because of the reduced weight penedty
with the smaller volume of liquid required, b u t wider use in
the longer term may be possible.
Acknowledgments
The author gratefully acknowledges the kind assistance (and
patience) of R. Coombes and G. N. Kay of Alstom Power, M.
Dennis of Rolls Royce, D. Irvine of Petro-Canada Lubricants,
G. Jones of G.E. Energy, E. Letterman of General Electric
Power Systems, H. Moeller of Elsam, M. Morris, Consultant,
Dr. T. Okada of ExxonMobil, Dr. L. Quick of Siemens A. G.,
J. Pankowiecki of Siemens Westinghouse a n d B. Rayner,
Consultant. Lastly, thanks are cJso due to Alan Holt of Great
Lakes Chemical Corp. for the photographs and to Alan Watson for editorial assistance.
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[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
Future," Supplement to Proceedings of the 12''' International Tribology Colloquium, Esslingen, Germany, Jan 2000, pp. 41-53.
"Engine Oil Licensing and Certification System," American
Petroleum Institute Publication 1509, 14* ed.. Appendix E, Section E.1.3, Washington, D.C., Dec 1996.
Ashman, T., "Advantages of Turbine Oils Blended with Hydrotreated Base Oils," Presented at the 54"' Annual STLE Meeting, Las Vegas, May 1999.
Galiano-Roth, A. S. and Page, N. M., "Effect of Hydroprocessing
o n Lubricant Base Stock Composition a n d P r o d u c t Performance," Lubrication Engineering, Vol. 50, No. 8, pp. 659-664.
Deckman, D. E., Lohuis, J. R., and Murphy, W. R., "HDP for Industrial Lubricants," Hart's Lubricants World, September 1997,
pp. 20-26.
Zielinski, J., "Supersyn Polyalphaolefins-a New Generation of
Synthetic Fluids," Presented at the 54"' Annual STLE Meeting,
Las Vegas, May, 1999.
Benda, R., BuUen, J, V., and Plomer, A., "Polyalphaolefins-Base
Fluids for High Performance Lubricants," Journal of Synthetic
Lubrication, Vol. 13, No. 1, 1996, pp. 41-57.
Fefer, M., Henderson, H. E., Legzdins, A., and Ruo, T., "Oxidation of Polyalphaolefins and Severely Hydro-Cracked : Kinetics
of Peroxide Formation-Part III," presented at the 54''' Annual
STLE Meeting, Las Vegas, May, 1999.
Rudnick, L. R. and Shubkin, R. L., "Poly(a-olefins)," Synthetic
Lubricants and High Performance Functional Fluids, L. R. Rudnick and R. L. Shubkin, Eds., Marcel Dekker Inc., NY, 1999.
Randies, S. J., "Esters," Synthetic Lubricants and High-Performance Functional Fluids, L. R. Rudnick and R. L. Shubkin, Msircel Dekker, NY, 1999, pp. 63-101.
Fowler, B. T., "Diesters as High Temperature Lubricants," Wear,
Vol. 15, 1970, pp. 97-104.
"Aviation Gas Turbine Lubricants-Military and Civil Aspects,"
SAE Special Publication 633, Proceedings of the Aerospace Technology Conference, California, October 1985, Society of Automotive Engineers, Warrendale, PA.
Markson, A. J., "Future Gas Turbine Lubrication-A Formulators
View," Proceedings of the 10th International Tribology Colloquium, Esslingen, Germany, January 1996.
Rayner, B. R., Private presentation to Rolls-Royce pic, Derby,
UK, 17 May 2000.
Phillips, W. D., "A Comparison of Fire-resistant Hydraulic Fluids for Hazardous Industrial Environments -Part 1," Journal of
Synthetic Lubrication, Vol. 14, No. 3, 1998, p p . 211-235.
Phillips, W. D., "Phosphate Esters," Handbook of Hydraulic
Fluid Technology, G. E. Totten, Ed., Marcel Dekker, NY, 1999,
pp. 1025-1093.
Marino, M. P. and Placek, D. J., "Phosphate Esters," CRC Handbook of Lubrication and Tribology, Vol III, Monitoring, Materials, Synthetic Lubricants and Applications, E. R. Booser, Ed.,
CRC Press Inc., Boca Raton, FL, 1994, pp. 269-285.
Rasberger, M., "Oxidative Degradation and Stabilisation of Mineral Oil Based Lubricants," Chemistry and Technology of Lubricants, R. M. Mortier and S. T.Orszulik, Eds., Kluwer Academic
Publishers, Dordrecht, The Netherlands, 1997, pp. 98-142.
Graham, J. and Leonhardt, H., "Development of Lubricating
Oils for Combined Cycle Applications," Proceedings, 11''' International Tribological Colloquium, Technische Akademie Esslingen, Germany, January 1998, p p . 1487-1500.
"Lubricating Oil Recommendations for Gas Turbines with Bearing Ambients Above 500F (260 C)," General Electric Specification GEK 32568C, July 1993.
Chadwick, D. and Hashemi, T., "Adsorbed Corrosion Inhibitors
Studied by Electron Spectroscopy; Benzotriazole on Copper
and Copper Alloys," Corrosion Science, Vol. 18, 1978, p p . 39-51.
Godfrey, D., "The Lubrication Mechanism of Tricresyl Phosphate on Steel," ASLE Preprint 64 LC-1, Park Ridge, IL, 1964.
MNL37-EB/Jun. 2003
Hydraulic Fluids
W. A. Givens^ and Paul W. Michael^
Where:
K = Bulk modulus
Vo = Original volume
AP = Pressure change
Ay = Change in volume
transfer
power. The concept of fluid power is based on a principle articulated by Blaise Pascal, which is usually given as follows:
"Pressure applied to an enclosed fluid is transmitted undiminished to every portion of that fluid and the walls of the
containing vessel" [1]. Within the context of fluid power,
pressure is related to the force acting on a confined fluid as
illustrated in Fig. 1 [2]. This principle has given rise to mode m hydraulics, which entails highly engineered systems for
efficiently controlling fluid flow to transfer energy and accomplish work.
The heart of any hydraulic system is the pump, which pulls
in fluid from a reservoir by creating a vacuum at its inlet and
then forces the fluid through its outlet, usually against pressure created by flow controllers and/or actuators downstream of the p u m p . Pumps, actuators, and other system
components have surfaces that move relative to each other,
often at high speeds, pressures, and temperatures. These
components require cooling and lubrication for efficient performance and durability. Consequently, hydraulic fluids not
only must transmit power, they serve critical functions as lubricant and heat transfer medium.
Heat Transfer
Heat is generated as a by-product of normal operation of a
hydraulic circuit. Friction between the moving parts of a
p u m p or hydraulic motor, as well as friction between the
fluid and surfaces of valves, pipes, and other circuit devices
generates heat. In addition, heat is generated in a hydraulic
system as a result of the dissipation of the potential energy of
pressurized fluid [8]. As a hydraulic fluid is circulated
through a system, heat is transferred from high temperature
areas to coolers, reservoirs, and other regions of the circuit
where it is dissipated. As can be seen in Table 1, typical specific heat and thermal conductivity values for hydraulic oils
are a fraction of that of water [4]. These factors are an important consideration in sizing hydraulic system coolers because the inherent cooling efficiency of petroleum based hydraulic fluid is less than that of water. ASTM D 2717, Test
Method for Thermal Conductivity of Liquids and ASTM D
2766, Test Method for Specific Heat of Liquids and Solids are
used to determine these properties of fluids.
P o w e r Transfer
To transfer power efficiently, a hydraulic fluid must exhibit
minimal compressibility. Low compressibility allows all of
the pressure applied to the fluid to be available for direct
and effective transmission to system components such as
motors, cylinders, or other actuators. The compressibility of
a fluid is generally discussed in terms of its "bulk modulus,"
which describes the change in fluid volume as a result of applied pressure [3]. The bulk modulus of a fluid, which is the
reciproccd of compressibility, is described by Eq 1. There
are a n u m b e r of m e t h o d s available for estimating the
isothermal secant bulk modulus of a fluid based upon its
viscosity and density characteristics [4,5]. As depicted in
Fig. 2, the bulk modulus for oil also varies with temperature
[6]. For petroleum oils, compressibility is often assumed to
be 0.5% for each 1000 psi pressure increase u p to 4000 psi
[7].
Bulk modulus {K) = -Vo
(\PI\V)
Lubrication
The durability of hydraulic equipment depends to a large extent upon the lubricating properties of the fluid. As a lubricant, the key function of the hydraulic fluid is to reduce friction between contact surfaces. A reduction in friction lowers
contact t e m p e r a t u r e s a n d wear. This is accomplished
through a combination of hydrodjoiamic and boundary lubrication mechanisms. The hydrodynamic lubricating properties of a fluid are governed by its physical properties while
boundciry lubrication is a function of fluid chemistry. A discussion of hydraulic fluid wear testing is presented in the
Wear Protection section of this chapter.
(1)
TRENDS
* Exxon Mobil Research & Engineering, Paulsboro Technical Center, 600 Billingsport Rd., Paulsboro, NJ 08066.
^ Benz Oil, 2724 West Hampton Avenue, Milwaukee, WI 53209.
A brief outline of major trends in the motion control industry, particularly with respect to hydraulic equipment design
and fluid requirements, is presented as a backdrop for the
discussion of hydraulic fluids test methods. As motion con-
353
Copyright'
2003 by A S I M International
www.astm.org
Force
Area
F = force in pounds
p = pressure in pounds / sq. incli (psi)
A = sq. in.
FIG. 1Relationship of force, pressure, and area in fluid power. Any one of the parameters equals the other two in the relationship depicted by the triangle.
TABLE 1Thermal conductivity and specific
heat values for oil and water.
40
30
M
Q.
Oil
Water
z
CO
Thermal
Conductivity
Btu/h/ft^/F/Ft
@ 212F
Thermal
Conductivity
W/m-K
@373K
Specific
Heat
BTU/lbF
@68F
Specific
Heat
J/kg K
@293K
0.08
0.39
0.14
0.67
0.47
1.0
1966
4184
20
I
10
3
m
100
200
300
trol technology advances, there is a trend towards higher performance and efficiency. For hydraulic equipment, this
translates into a concentration of horsepower in smaller
components. There are a n u m b e r of reasons for such a trend.
Equipment manufacturers are looking for ways to minimize
raw material usage and cost. Users of the equipment demand
smaller systems for better space utilization in industrial environments cind compact multifunctional capabilities in mobile equipment. These advancements in mechanical design
along with e n c r o a c h m e n t of environmental, health, and
safety regulations fuel the following trends:
Hydraulic equipment builders will continue to push comp o n e n t manufacturers to design parts to a c c o m m o d a t e
high pressures a n d t e m p e r a t u r e s . F o r example, hoses,
valves, and other fittings will continue to evolve in terms of
materials used as well as actual functional design.
Smaller c o m p o n e n t s will m e a n smaller p u m p displacements [cubic inches or cc per p u m p revolution]. To maintain flow rates at present or higher levels, p u m p speeds will
be increased [cubic inches/minute = displacement X speed
(rpm)]. Smaller reservoir sizes will mean shorter fluid residence times and will therefore dictate use of hydraulic fluids with improved air release characteristics.
Smaller dimensional clearances will be required. These
smaller clearances will dictate more stringent fluid cleanliness requirements to prevent abrasive wear from particulate c o n t a m i n a n t s a n d failure of servo or proportional
valves.
Fluid cleanliness will increasingly be emphasized as an effective way of increasing equipment durability and controlling warranty costs. As a result, users will move to finer
filtration and specify pre-filtered hydraulic fluids [9]. Consequently, the filterability of the hydraulic fluid will continue to grow in significance. (Filterability is described in
section 4.6.)
Quieter hydraulic systems will be required in order to meet
workplace noise restrictions and compete with electric motors. Reduction of noise levels in hydraulic equipment has
been attained by the insulation that absorbs the noise. This
insulation results in higher system temperatures, as heat is
not as readily dissipated.
Components and actuators, such as cylinders, will be designed with tighter seals to increase efficiency and reduce
CHAPTER
13: HYDRAULIC
FLUIDS
355
Solvent refining yields base oils that fall into Group I while
hydroisomerization and deep hydrogenation processes yield
low sulfur, high paraffin content Group II a n d Group III
base stocks. Because of their lower aromatic and sulfur content, hydraulic fluids formulated from Group II and Group
III base stocks typically have superior oxidation stability.
However, more highly refined stocks tend to be less effective
at dissolving additives. Not only is additive solubility a concern, additive chemistries and their functional mechanisms
may be b o t h synergistic a n d antagonistic. Thus, additive
chemistry must be ceirefully balanced to achieve optimum
performance. In the following section, test methods for evaluating key fluid properties such as oxidation stability, wear
prevention, and corrosion inhibition are discussed. These
methods have been developed to measure characteristics of
hydraulic fluids that are thought to correlate to performance
in "real-life" applications as well as gage additive response
for the fluid formulator. In order to provide a link between
fluid tests and additive chemistry, a description of the generally accepted functional mechanisms of additives is also
included.
Composition
< 9 0 % Saturates or
> 1 0 % aromatics
9 0 % Saturates or
< 1 0 % aromatics
> 9 0 % Saturates or
< 1 0 % aromatics
All polyalphaolefins (PAO)
All others not included in
Groups 1,11, m or IV
Suli^ir
>0.03%
Viscosity
Index
80-120
<0.03%
80-120
<0.03%
>120
356
MANUAL
High Temperature/Oxidation
HANDBOOK
Tests
OXYGEN
DELIVERY
TUBE
CATALYST
COILS
Fluid Type
Hours to TAN of
2.0 by D 943 Method
65
300
2016
5040
5500
>10,000
Initiation
RH
Propagation
R + O2
ROO*
Peroxy radical
ROO + RH
ROOH + R*
Hydroperoxide
ROOH
-*
RO + OH
Alkoxy radical
RO + RH
->
ROH + R
Alcohol
OH + RH
->
H2O + R
Water
Branching
Termination
Alkyl radical
R + ROO
Alcohols
RO + ROO
Aldehydes
ROO + ROO
Ketones
RO + R
Acids
R + R
Longer chain
hydrocarbons
Hydraulic Oil
RO
RO
SZnS
OR
OR
Base Oil
(Paraffinic)
and
Additives
Machines
and Outside
Environment
T
Reaction withi
Thermal P^''^^
Deterioration
Degradation
witii Water
ZnSq
RO
Decomposition
Oxidation
Reaction with
l\^etai Ions
Polyphosphates
0
OR
0- -Zn0
OR
\ ^
RO
Oxidation
Products
and
Metal Soaps
Wear Particles,
Dust, Rust, Water
andOtliers
Sludge
FIG. 5Mechanism of sludge formation by zinc dialkyldithiophosphate.
Requirement
No discoloration
3.5 mg maximum
1.0 mg maximum
5 rating maximum
10.0 mg maximum
5% change maximum
25 mg/100 mL max
50 % maximum
species react with oxygen and non-oxidized oil to form additional free radicals, which propagate the oxidation process.
This generally accepted mechanism is described as free radical chain reaction and is illustrated by the steps shown in
Fig. 4.
Antioxidants interrupt this chain reaction and thus, reduce
the rate of oxidation and the resulting viscosity increase and
acid and deposit formation. There are two general mechanisms by which these additives inhibit oxidation. The antioxidants are therefore categorized as primary or secondary, depending u p o n the m e c h a n i s m of oxidation inhibition.
Primary antioxidants, commonly referred to as "free radical
scavengers," react with the peroxy radicals and hydroperoxides to form inactive compounds (Fig. 6) [21]. Examples of
primary antioxidants include hindered phenols and aromatic
amines. Secondary antioxidants, commonly referred to as
"peroxide decomposers," react with hydroperoxides or peroxy radicals to form less reactive compounds. Examples of
secondary antioxidants include sulfur a n d / o r p h o s p h o r u s
c o m p o u n d s a n d metal dithiophosphates (Fig. 7). Antioxidants genereilly function in the bulk lubricant and are consumed as they do their job [22].
Detergents
IDispersants
(R0)3P?-0O3
(R0)3P + R'OOH
H
(R0)3P=0 + HOR'
FIG. 7Secondary antioxidants such as the phosphite compound depicted above inhibit oxidation by decomposing hydroperoxides. This prevents the oxidation process from progressing beyond the branching stage In the reaction
mechanism.
o
+ R00
ROO^^R
FIG. 6Reaction scheme for primary antioxidants. Primary or freeradical trapping antioxidants work by donating a hydrogen radical H* to
the peroxy radical formed during mineral oil oxidation. Due to steric hindrance, the antioxidant radical does not attack mineral oil molecules,
i.e., R-H bonds. Consequently, the radical chain is terminated.
the TOW for straight grade mineral oil based hydraulic fluids. The viscosity grade indicated in the TOW corresponds to
ASTM D 2422, Classification of Industrial Fluid Lubricants
by Viscosity System. For example, ISO 32 hydraulic oil generally will provide satisfactory performance in a temperature
window of - 8 to 64C.
There are several methods for measuring the viscosity of
hydraulic fluid. The most widely utilized method is the ASTM
D 445, Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids. In this test, the time is
measured for a fixed volume of liquid to flow under gravity
through the capillary of a calibrated viscometer at a closely
controlled temperature. The kinematic viscosity is the product of the measured flow time and the calibration constant of
the viscometer. Based upon D 2442 and ISO 3448, the standard temperature for measuring hydraulic fluid viscosity is
40C [26]. Typically, the viscosity of a hydraulic fluid is 15-68
mm^/s (centistokes) at 40C. ASTM D 446, Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers, describes more than 15 types of viscometers that may be employed in performing a D 445 viscosity
test. With the exception of invert-emulsion type fluids, hydraulic fluids are generally transparent. Consequently, a tube
suitable for transparent liquids such as the popular CannonFenske viscometer may be used. For opaque liquids, a reverse-flow tube is required because it is difficult to see the
meniscus as the fluid flows by the timing marks on a standard viscometer. Cannon-Fenske tubes for viscosity measurement of transparent and opaque liquids are depicted in
Fig. 10.
1
MIXFn FN M
LUBRICA-|ON
B OUNDARY
LIJBRICATION
0.1
c
o
o
c
g>
o
0.01
^
O
o
0.001
0.001
0.01
359
0.1
hULL-hlLM
LUBRICATION
1
1
10
212
90
94 194
80
o
<D
176
84
70
158 LL.
140
73
60
64
5 50
-I
55
122
104 CO
CD
86 O.
44
I" 30
32
j5^20
CO
+10
10
+4
-2
-23
-4
-30 3 3
-22
-40
10
50
14
-15
-20
E
.<!>
32
-8
-10
CD
V
15
22
32
46
68
100
-40
FIG. 10Cannon-Fenske standard and reverse flow kinematic viscosity tubes, respectively.
CHAPTER
make contact, resulting in friction and weeir. In most cases,
mixed-film lubrication takes place and some hydrodynamic
lubrication occurs, even as "asperity contact" creates boundary conditions. Depending upon the extent of asperity contact, scuffing or adhesive wear may occur. A schematic description of the various wear processes specific to hydraulic
p u m p s is shown in Fig. 11. When cavitation, corrosion, or
scuffing wear processes generate particles that are the same
approximate size as p u m p clearances, synergistic wear may
take place. Sjmergistic wear ultimately leads to failure that
may appear to be abrasive in origin [28].
Wear protection under conditions of boundary lubrication
may be enhanced through the use of additives that interact
with surfaces to form protective chemical films. (See the Antiwear Performance Testing section for description of the
boundary lubrication additives utilized in hydraulic applications.) These chemical films reduce friction by decreasing the
shear strength of the surface relative to the underlying material. Thus, surface interaction under boundary lubrication
conditions is primarily between the low-shear strength chemical films rather than the metal substrate. Good wear protection and friction reduction result in enhanced equipment
durability, reduced heat generation, improved energy conservation, and many other operational advemtages.
Antiwear
Performance
13: HYDRAULIC
FLUIDS
Testing
The majority of hydraulic fluids are formulated with antiwear additives because surface loads associated with highpressure p u m p operation necessitate the use of fluids with
enhanced wear protection. There are a variety of test methods available for assessing the antiwear performance of hydraulic fluids. These tests may either be bench-top or fullscale tests employing high-pressure piston and vane pumps.
Bench tests are generally less expensive to perform t h a n
p u m p tests. However, translating bench test data into realworld performance can be problematic because of the complexity involved in simulating all of the materials, velocities.
(a)
FIG. 12The four-ball test:
(a) perspective view, (b) plan view.
EXTEERNAL
PAR"riCLE
INGREESSION
\Air:Ap
CAVITATION JElr
ASPERITY
CONTACT
FATIGUE
WEAR
ADHESIVE
WEAR
VVtArl
DEBRIS
WEAR
DEBRIS1
>
ABRASIVE
WEAR
TOTAL
WEAR
ELECTROLYTE
(WATER)
361
CORROSIVE
WEAR
WEAR
WEAR DEBRI S
DFRRI.q
FIG. 11Synergistic view of pump wear process. Fatigue, adhesive, and corrosive wear
can be triggered Independently. Resulting wear debris generation leads to abrasive wear.
362
MANUAL
HANDBOOK
CHAPTER
D 6158, Standard Specification for Mineral Hydraulic Oils,
less than 50 mg of total wear is expected from properly formulated petroleum based antiwear hydraulic oil. For invertemulsion type fluids, higher wear rates in the 100-200 mg
range are c o m m o n while water glycol fluids routinely generate less than 50 mg wear in the D 2882 test.
While the D2882 test is a popular benchmark for evaluating hydraulic fluids, this method is not without its problems.
First of all, Vickers has discontinued production of the
V104C p u m p . This will ultimately necessitate the use of substitute hardware or abandonment of the test procedure. Second, rotor and bushing failures are common in the first few
hours of the test. This may be due to the fact that the p u m p
was originally designed for a m a x i m u m pressure of 1000
psig. Fluid performance in the V104C p u m p is evaluated at
1000 psi using the ASTM D 2271, Standard Test Method for
Preliminary Examination of Hydraulic Fluids (Wear Test). In
this procedure, the p u m p stand is operated for 1000 h, which
provides an extended evaluation of p u m p wear behavior under normal operating conditions. Xie et al. provide a detailed
discussion of the D 2882 Test Method in the Handbook of Hydraulic Fluid Technology [36].
For higher pressure a n d mobile applications Vickers
prefers their 35VQ25 vane p u m p for screening hydraulic
fluid wear performance (Table 5). In the 35VQ25 test, three
50-hour tests are conducted on the same charge of test oil.
For each 50-hour test a new p u m p cartridge is used. The test
rig is operated at 3000 psi and 200F with a p u m p speed of
2400 rpm. Vickers limits the amount of wear on each test kit
to 90 mg: 75 mg ring, 15 mg vanes. In addition there must be
no sign of scuffing on the cam ring.
The Denison T6C vane p u m p test is a variable pressure
vane p u m p test. In this test, a Denison T6CSH 020 p u m p cycles between 7 b a r (100 psi) and 250 bar (3600 psi) at onesecond intervals for 300 h [37]. The p u m p speed is nominally
1700 r/min a n d fluid t e m p e r a t u r e is m a i n t a i n e d at 80C
(176F) for mineral oil based fluids a n d 45C (113F) for
those based on water. The test is r u n in two 305-hour sequences. Each 305-hour test consists of a 5-hour break-in period followed by 300 h of high pressure cycling. After the first
305-hour test, the p u m p cartridge is removed for inspection
and a new cartridge is installed for the second sequence. The
second 305-hour sequence is r u n with 1% distilled water
added to the fluid. The first stage of the T6C test serves as an
aging mechanism and increases the susceptibility of the fluid
to the deleterious effects of water contamination. After the
second 305-hour sequence the p u m p cartridge is again removed for inspection. As with the 35VQ25 test, weight loss of
cam ring and vanes, vane tip profile, and visual appearance
of all components are all reported. In addition, a wet filterability test is performed on the fluid to determine if water
contamination will lead to filter blinding. (See the Filterability section for a discussion of filterability tests.)
Although the V104C and 35VQ25 vane p u m p tests have
served the industry well for many years, these tests are not
sufficient to screen hydraulic fluids that will be used in highpressure piston p u m p s applications [38]. Thus, piston p u m p
tests have been to qualify the antiwear capabilities of hydraulic fluids. Komatsu, Rexroth, and S u n d s t r a n d piston
p u m p tests are described below.
K o m a t s u developed a piston p u m p test to evaluate
13: HYDRAULIC
FLUIDS
363
and Extreme
Pressure
(EP)
Additives
Denison HF-0
Vickers
Requirements
Requirements
6 M LS-2
Cincinnati iWachine
.
P68
32
P70
46
P69
68
35.2
28.8
50.6
41.4
74.8
61.2
188
215
196
218
196
218
LH-02
22
LH-03
32
LH-04
46
LH-06
68
300
24.2
19.8
4.1
175
420
35.2
28.8
5
190
780
50.6
41.4
6.1
190
1400
74.8
61.2
7.8
195
-21
-18
-15
-12
10
10
19/16/13
0.84 - 0.90
<1.S>
Pses
Pass
Pass
Pass
<1b>
<1500>
5
<:50/0>
<SO/0>
<50/0>
Timeto40/40)(O/W/E)
<30>
<10>
-10
-/O
-10
90
100
<90>
Oto-7
Oto-7
Oto-6
OtolS
0to12
<95>
0to12
OtolO
<5>
<50>
Record
< 25 mg. /100ml >
<10>
<5>
<5>
<50>
100
10
Report
Oto-8
<1.5>
2
200
50
SO
(1)
0.2
4.0
<0.2>
<4>
I-2S6-S
SO
M-2950^
15
75
Satisfactory
Satisfactoiy
600
2xdry
< 50 >
(2)
<10>
<50>
no smear, scratch, etc
< 0.01 >
No distress
<600>
< 2 X dry >
365
may be registered either potentiometricly or by color indication. Although this method has the capability to be more accurate than distillation or centrifuge techniques, the Karl
Fisher Test is susceptible to chemical interference. Calcium
sulfonate, magnesium sulfonate, ZDTP and other oil additives react with iodine and have been known to interfere with
the titration [43].
Hydrolytic Stability Testing
Hydrolytic stability refers to the lubricant's resistance to
chemical interactions with water that result in undesirable
changes to fluid properties. Certain chemical components
may react with water to decompose or form undesirable
byproducts of hydrolysis. Heat and catalysts such as copper
can accelerate the process of hydrolysis. Hydrolytically unstable oils form insoluble contaminants and acidic compounds that create hydraulic system malfunctions similar to
those produced by oxidation and thermal degradation of fluids. Furthermore, antiwear additives and corrosion preventatives that are susceptible to hydrolysis are likely to lose their
ability to perform their critical functions in the presence of
heat and water.
ASTM D 2619, Standard Test Method for Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle Method) is used to
measure this fluid property. In this test, 75 g of fluid and 25
g of water are sealed in a beverage bottle with a copper strip.
The test bottie is rotated in an oven for 48 h at 93C (200F).
At the end of the test, the oil and water layers are separated
FIG. 14The Karl Fisher apparatus (a) titrant solution, (b) burette, (c) titration cell with
electrode, (d) solvent, (e) waste.
366
MANUAL
HANDBOOK
Testing
levels, entrained air is visible to the h u m a n eye as larger bubbles and can cause the oil to become cloudy. Uncontrolled air
contamination results in a n u m b e r of undesirable consequences. Entrained air increases the compressibility of the
fluid and can adversely affect its response to hydraulic control mechanisms or devices, especially in high-pressure systems. Dissolved or entrained air expands into larger bubbles
as its solubility in the fluid decreases as a result of exposure
to vacuum conditions at the p u m p inlet. This leads to noise
and cavitation, which is the dynamic process of gas cavity
growth a n d collapse in a liquid [47]. Several studies of this
p h e n o m e n o n have suggested theoretical m e c h a n i s m s a n d
documented experimental evidence of wear a n d increased
oxidation due to cavitation [48].
Foaming is very much rooted in the fundamentcJ problem
of air contamination and consequently, results in many of the
same negative effects of air entrainment. It is characterized
by the formation of a mass of relatively large bubbles on the
surface of the fluid and is usually brought about by turbulent
return of oil to the reservoir or migration of entrained air to
the surface. It is desirable to have fluids with a low tendency
to form foam in the first place a n d have the foam collapse
quickly once formed. For effective foam control, the rate of
foam collapse must be faster t h a n the rate at which entrained
air migrates to the surface to form the foam. Otherwise, the
foam layer will continue to increase and air may eventually
be re-dispersed in the bulk fluid [49]. In severe cases, oil that
produces a significant amount of foam may bubble out of hydraulic reservoir breathers, creating a fluid spill.
The speed at which water is separated from oil and the tendency of an oil to form a cuff of emulsified oil at the interface
between the oil and water phases may be measured by ASTM
D 1401, S t a n d a r d Test Method for W a t e r Separability of
Petroleum Oils and Synthetic Fluids. In this test, a 40 ml sample of oil a n d 40 ml of distilled water are stirred for 5 min at
54C (130F) in a graduated cylinder. The time required for
the emulsion to separate into water a n d oil phases is
recorded. An oil with good demulsibility will completely separate in 30 m i n or less without a "cuff' of emulsified oil between the phases [45].
Demulsifiers
Because of the importance of properly managing air contamination in hydraulic fluids, there are a n u m b e r of standardized test methods for evaluating this feature of fluid performance. The foaming tendency a n d stability of oil may be
measured by ASTM D 892, Standard Test Method for Foaming Characteristics of Lubricating Oils. In this test, an oil
sample is equilibrated at 24C (75F). Air is bubbled through
oil for 5 min, and then the oil is allowed to settle for 10 minutes. The volume of foam is measured at the end of both periods. The test is repeated at 93.5C (200F) and again at 24C
(75F) after the foam breaks. Various levels of foaming tendency are permitted by industry standards, but stable foam is
generally not tolerated [50,51].
Not only must a hydraulic fluid resist the tendency to form
stable foam, it also must allow air to rapidly rise and separate
from the fluid. The Waring blender test is one test method
that may be used to measure the air release properties of fluids [52]. In ASTM D 3519, Standard Test Method for Foam in
Aqueous Media (Blender Test), 200 ml of the fluid is stirred
Aeration a n d Foam
Under normal conditions there is always air present in a hydraulic fluid. By volume, it is present at about 7-9% at room
temperature a n d atmospheric pressure [46]. In this state, it is
not visible to the h u m a n eye and thus referred to as dissolved
air. Higher temperatures and/or lower pressures (such as vacu u m conditions) lead to lower dissolved air levels. (See chapter on compressor lubricants for detailed discussion on gas
solubility and methods of measuring gas solubility.)
Fluid circulation through hydraulic systems and reservoirs
may cause mecheinical introduction of air into hydraulic fluids, particularly if reservoir size or design does not allow sufficient residence time for air separation to occur. At elevated
Tests
CHAPTER
at an agitation rate of 4000 to 13000 r p m for 30 s. The meixim u m total height at zero time, at 5 m i n a n d 10 m i n is
recorded in order to assess the foaming and aeration tendency of a fluid under high shear conditions.
Air release properties of a hydraulic fluid may also be
quantified by IP 313, DIN 51381 or ASTM D 3427, Standard
Test Method for Air Release Properties of Petroleum Oils. In
these tests, the time in minutes for finely dispersed air in oil
to decrease to 0.2% under standard test conditions is measured using a density balance. Air release times and specifications typically vary with oil viscosity.
Defoamants
Antifoam additives, generally referred to as defoamers or defoamants, are materials that destabilize the liquid film that
surrounds air bubbles. The most commonly used defoamants
are silicone polymers (particularly polydimethylsiloxanes),
which function as finely dispersed marginally soluble liquid
particles. Since silicon defoamants have very low surface tensions, they tend to accumulate at air/oil interfaces. When the
larger bubbles rise to the surface and join other bubbles to
form foam with only very thin films separating them, silicone
defoamants cause these films to rupture, thus accelerating
collapse of the foam. While silicone defoamants reduce the
foaming tendency of a fluid, they may also tend to increase
air entrainment (Fig. 15) [53].
Besides affecting air entrainment in hydraulic fluids, silicone defoamants tend to have poor filterability and storage
stability due to their marginal solubility in oil. Non-silicone
defoamants are increasingly used to address these disadvantages. Polyalkylacrylate additives are the most common class
of non-silicone defoamants recognized in the industry. Although they do not possess the disadvantages of the silicone
types, these polyalkylacrylates must be used at higher concentrations to deliver equivalent performance.
13: HYDRAULIC
Tests
Due to the likelihood of water contamination in many hydraulic systems and its potential impact on fluids, most of the
filterability tests are designed to r u n dry and wet (with water
added). Hydraulic fluid filterability tests generally consist of
filtering a specified quantity of fluid t h r o u g h a standard
medium while monitoring changes in flow rate (Table 6). The
results are tj^pically reported in terms of a ratio between flow
rates with and without water added to the fluid. This approach attempts to account for changes in filterability behavior independent of viscosity. In Denison TP 02100 the
time required for complete flow of a standard volume of fluid
through a specified filter is evaluated. In the Pall Filterability
Test the differential pressure across a specified filter assembly is monitored over the duration of the test and cin appropriate limit is established to discriminate between fluids with
good and poor filterability behavior. While key equipment
OIL WITH
SILICONES
O
O
eg
<
h-
SETTLING OR
"TRANQUIL PHASE"
BLOWING OR
TURBULENT PHASE"
367
Filterability
VOLUME OF AIR
BLOW IN
FLUIDS
>
TIME
FIG. 15Impact of silicone defoamer on foaming tendency and air release. Silicone defoamer decreases the tendency of the oil to generate foam while increasing the tendency
of the fluid to retain air below its surface.
368
MANUAL
Method
HANDBOOK
Denison
3/LiM
1.0
24 h
70C
1.2 ^M
2.0
None
25C
"Parkhurst, H., Pall Filterability Index Test for Paper Machine Oils, SLS Report No. 5669, April 1995.
Additives
From a formulation standpoint, identifying and replacing additives with potential filterability problems (i.e., filter material incompatibility, gel-forming tendency, hydrolytic instability, etc.) has been the primary method of improving fluid
filterability. Recently, dispersants have been identified that
enhance filterability by preventing agglomeration of insoluble species present in the fluid. These dispersants are typically alkyphenol-based or alkyl succinimide polymers of
varying molecular weights.
Corrosion Protection
Chemical contaminants and corrosive by-products of fluid
degradation can cause surface attack of metallic hydraulic
system components. Ferrous metal corrosion in a hydraulic
system is most often caused by water contamination, while
copper and its alloys are susceptible to attack by the products
of high temperature fluid degradation. Rusting of ferrous
metal is an electrochemical reaction that occurs between the
parent metal and the thin oxide layer on the metal surface
formed as a result of exposure to the atmosphere [20]. Rust,
which is hydrated iron oxide, compromises the integrity of
the metaJ surface and adversely affects other important fluid
properties w h e n it contaminates the bulk fluid. Ferrous
metal corrosion protection in hydraulic systems is usually accomplished by incorporating surface-active additives such as
rust inhibitors. There are several ASTM methods for evaluating the corrosion inhibition properties of hydraulic fluids.
Corrosion
and Rust
Testing
369
mulated with water. Such fluids have entirely different corrosion inhibition requirements. For instance, water glycol
hydraulic fluids must prevent corrosion in the vapor phase
above the liquid due to evaporation. Thus they are formulated with vapor phase corrosion inhibitors such as morpholine. Typical classes of rust inhibitors include metallic sulfonates, amine phosphates, simple fatty acids, and succinic
acid esters. Triazoles, or derivatives thereof, are commonly
used metal passivators.
370
MANUAL
HANDBOOK
Designation
la
Slight tarnish
lb
2a
2b
2c
Slight tarnish
Moderate tarnish
Moderate tarnish
Moderate tarnish
2d
2e
3a
3b
Moderate tarnish
Moderate tarnish
Dark tarnish
Dark tarnish
4a
Corrosion
4b
4c
Corrosion
Corrosion
Seal Compatibility
Very critical to the successful operation of a hydraulic system
is the ability to prevent leakage and accidents that are a result
of failed seals. Leaks can lead to contamination, loss of pressure, loss of lubricating fluid, and environmental damage depending on the severity of the spill. In extreme temperature
and pressure operations, sudden failure of seeds may have life
threatening consequences, considering the potential for explosions, fires, etc. [57]. Hydraulic fluids and elastomeric
seals are composed of complex chemical components that
can interact as they come into contact. Depending on the
chemistries involved, time, t e m p e r a t u r e , a n d mechanical
stresses cause fluid interactions with the seal material, resulting in swelling or shrinkage of the elastomer compound.
It is desirable to select seal materials that exhibit minimal
change in hardness, volume, tensile strength etc. in service.
Slight swelling of seals is preferable to shrinkage as indicated
in Table 8. This is because a reduction in seal volume may result in leakage of fluid due to failure of the seal to fill the
gland that retains it in place.
Seal Compatibility
Description
Testing
Maximum
Volume
Swell,
Time in
Hours
24
70
100
250
500
1000
Seal Swell
Maximum
Vol.
Shrinkage,
Hardness
Change,
Shore A
Points
15
15
15
15
20
20
-3
-3
-3
-4
-4
-5
7
7
8
8
10
10
Maximum
Tensile
Strength
Change, %
-20
-20
-20
-20
-25
-30
Agents
Separability
Testing
A standard industry test method for assessing lubricant compatibility with coolants has not yet been established. However, some Icirge industrial manufacturers and lubricant suppliers do have in-house test procedures designed to simulate
oil contamination by a low percentage of coolant, as well as
coolant contamination by a low percentage of oil (typically
referred to as tramp oil). In general, these procedures consist
of mixing the lubricant with the coolant at a specified ratio
a n d t e m p e r a t u r e for a s t a n d a r d duration. The fluid container, t5^ically a graduated cylinder, is then allowed to sit
while the degree of separation between the coolant and the
lubricant is observed at specific time intervals. Properties
such as additive leaching and foam stability may also be ob-
CHAPTER
served. Rapid separation, implying absence of a stable emulsion or cuff (the layer between way oil and coolant) at the interface, is very desirable (Fig. 18).
Shear Stability
Mobile hydraulic equipment such as excavators, farm tractors, cranes, and timber harvesters frequently are required to
operate under extreme high and low temperature conditions.
To accommodate wide-ranging environmental conditions,
hydraulic fluids with enhanced viscosity - temperature properties are often employed. These fluids t3^ically contain viscosity index improving polymers that thicken oil at high temperatures, while having little impact u p o n their low
temperature fluidity. Viscosity index (VI) is a common means
for expressing the variation of viscosity with temperature.
The viscosity index of an oil is calculated from the measured
viscosity of the fluid at 40 and lOOX using ASTM Method D
2270, Standard Practice for Calculating Viscosity Index from
Kinematic Viscosity at 40 and 100C. A high VI indicates less
relative change in viscosity for a given change in temperature. Vl-improved oils are commonly referred to as multigrade oils, because they meet both the low temperature requirements of low viscosity oils and the high temperature
requirements of higher viscosity oils. Conceptually, an SAE
Good
13: HYDRAULIC
FLUIDS
371
lOW-30 multigrade oil consists of a lOW base oil and sufficient polymer to thicken the oil at 100C to a viscosity equal
to that of an SAE 30 weight oil (Fig. 19).
Viscosity Index Improvers are typically subjected to mechanical degradation due to shearing of the molecules in high
stress areas such as between gear teeth in gear pumps and
vane-ring interface in vane p u m p s . High pressures generated
in hydraulic systems subject fluids to shear rates up to 10^ s~'
[60]. Not only does hydraulic shear cause fluid temperature
to rise in a hydraulic system, but shear may bring about permanent viscosity loss in hydraulic fluids [61]. Permanent viscosity loss results from mechanical scission of polymer
molecules in multigrade hydraulic fluids and often occurs after a relatively short period of time (<24 hours of operation).
The polymer (as opposed to the base oil) is susceptible to mechanical shear because it has a higher molecular weight and
therefore a larger molecular volume. As a result, with polymer-containing multigrade hydraulic fluids, the functional
viscosity of an oil may differ from that predicted from kinematic viscosity measurements of new oil [62].
Shear Stability
Tests
Fair
Poor
HANDBOOK
Multigrade Oils
100,000
10,000
1,000
2-i
-40
.
^40
100
150
Temperature, C
FIG. 19Impact of VI improver on lubricant viscosity.
-20
designed to stress multigrade oils so that they produce a permanent viscosity loss such as would take place in service. The
two methods generally used are mechanical shearing with a
Bosch diesel fiiel injection pump and sonic shearing with a
high frequency sonic oscillator. In ASTM D 6278, Test Method
for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus, the polymer-containing
fluid is passed through a diesel injector nozzle at a shear rate
that causes polymer molecules to degrade. Under standard
test conditions, the kinematic viscosity of the fluid is measured after 30 to 250 cycles through the injector pump to determine the extent of permanent viscosity loss that has taken
place. In ASTM D 5621, Standard Test Method for Sonic
Shear Stability of Hydraulic Fluid, the polymer-containing oil
is irradiated with a sonic oscillator for 40 min and changes in
kinematic viscosity are measured. Based upon data from
Kopko and Stambaugh, the Fuel Injector Shear Stability Test
lacks the necessary severity to predict permanent viscosity
loss produced by hydraulic equipment [62]. However, 40 min
of irradiation with a high frequency sonic oscillator produced
viscosity changes that closely correlate to that experienced in
the ASTM D 2882 Vane Pump Test. Consequently, this test
method has become the basis for ASTM D 6080, Practice for
Defining the Viscosity Characteristics of Hydraulic Fluids.
Viscosity Index Improvers
Viscosity Index Improvers (also referred to as viscosity modifiers) are high molecular weight poljTuers that reduce the
magnitude of viscosity change as a function of temperature.
They function by enabling the oil to retain thickness at higher
temperatures while having minimal impact on viscosity at
lower temperatures. In general. Viscosity Index Improvers
are oil-soluble organic polymers with molecular weights
ranging from about 10000 to 1 million. The oil temperature
controls coiling of the polymer molecules, which in turn controls the degree to which the polymer increases viscosity. The
higher the temperature, the less the coiling and the greater
the "thickening" effect of the polymer. Therefore, as temperature increases, there is less thinning of the lubricant compared to non-polymer-containing oils.
The performance of VI Improvers is also described in terms
Reversible/
Orientation of Coil
Under Shear Forces
Temperature
Viscosity Loss
sNonreversible
Rapture of Coil and
Subsequent Orientation
Under Shear Forces
Permanent
Viscosity Loss
Min.
Max.
L5
L7
LIO
L15
L22
L32
L46
L68
-49
-41
-32
-22
-14
-7
-1
-50
-42
-33
-23
-15
-8
-2
4
Depressants
Pour point depressants are additives designed to reduce formation of rigid wax crystals in the lubricant at low temperatures. Conventionally refined mineral oils typically require
the use of pour point depressants because they contain wax
HVDRMjuc mxs
Pelrolaum 8al
R&OlfWbHed
SynlHtBc Ba9Cl
AnCweartAW)
MuBgrade
Witer Baaed
PoW/'}
EMere
Phosphale Eaan
SMeones
PololEgre
Rapwwed
Polyalphaolat>i8(PAO)
wsot 0 ^
Polyaloxarwa
EWare
HatoaanalKl Cemiiounds
Polyetherg
Aryieftera
ScBean
SynHiellc SoluUon
Water-h-QI (hvBrt)
O U n - W W f ;So>i>le OB
Ghlorinatad Hydrocarbons
Raflutor
Silanas
FluowEstere
V 9 a * f c b 0 1 Based
Mcra Emulalm
374
MANUAL
HANDBOOK
Classification
HH
HL
HM
HV
Commercial
Designation
Straight base oils
R&O oils
Antiwear oils
Multigrade oils
CHAPTER
13: HYDRAULIC
FLUIDS
375
ISO 11158
ASTM
Properties
ISOVG
Kinematic Viscosity, cSt
D445
40'C max.
40C min.
D92
Flash Point, C min.
Flash Point, C min.
093
Brookfield Vis < 750 cP, Max
D2983
D97
Pour Point, C, max
Visual
Appearance
D1744
Water Content, wt%
01298
Density @1SC
TAN, ma KOH/g, max
0664 or 0974
D665A
Rust Test A
Rust Test B (Salt Water)
06658
Cu Rating (3 hr, 100C), max. 0130
TOST Oxidation, hours
0943
AN after 1000h, max.
Air Release @ 50C, minutes
D3427
(max)
Foam tendency/stability
0892
Seql
max
max
SeqII
max
SeqIII
Demulsibility @ 54C
01401
Minutes to 37 mL water .
0 5182
FZG Fail Stage
Ctiange in Hardness
0 471
NBR1,168 hrs @ 100C
ISO 7619
Change in Volume (%)
NBR1,168hrs@100C
Viscosity Index, min
0 2270
CM Thermal Stab.
02070A
Sludge, mg/100 ml max
Copper rod appearwice, rating (max.)
0 4310
Oxidation (1000 h)
AN, mgKOH/g max
Total sludge, mg max.
Total Metals in oil/water/sludge
Vickers 104C mg. wear max.
0 2882
HM (Antiwear)
32
46
22
S8
22
68
24.2
19.8
165
35.2
28.8
175
50.6
41.4
185
74.8
61.2
195
24.2
19.8
165
35.2
28.8
175
50.6
41.4
185
74.8
61.2
195
-18
-15
< Report >
-12
-12
-21
-18
-15
-12
-15
-21
-8
-18
<C&B>
-2
-15
4
-12
2
1000
2
1000
2
1000
10
13
30
30
Oto-7
Oto-6
<-ao5->
10
13
10
10
<15Qro>
<7SI0>
<i5ao>
<75/Q>
<150)>
30
10
<15C/0>
<70>
<150)>
<i5oro>
30
10
30
10
30
10
40
40
10
40
10
60
10
Oto-8
Oto-7
Oto-7
Oto-6
0to15
0to12
0to12
OtolO
2
< Report >
HFAE
Commercial
Descriptions
Soluble oils
High water based
fluids
Invert emulsions
Water-glycols
Phosphate esters
Polyol esters
30
30
0to12
<-90->
0to12
OtolO
25
5
25
5
25
5
200
200
< Report >
50
200
200
50
50
: Report >
Classification
HFDU
HM (Antiwear)
32
46
74.8
61.2
180
168
Symbol
HFDR
22
50.6
41.4
180
168
HFC
68
35.2
28.8
160
148
Fire resistant hydraulic fluids are used in the basic metals industry, die casting, military, and foundry applications. They
may be found in any application where a ruptured hydraulic
line presents a potential fire hazard. Fire resistant hydraulic
fluids are formulated with materials that have a lower BTU
content than mineral oils, such as polyol esters, phosphate esters, and water-glycol solutions. As a result, they b u m with
less heat generation than mineral hydraulic oils. As with mineral hydraulic fluids, the International Organization for Standardization has established a classification system for fire resistant fluids based upon composition. Table 12 provides a list
HFB
ASTM D6158
24.2
19.8
140
128
HFAS
Requirements
32
46
50
376
MANUAL
HANDBOOK
Antiwear Hyd.
Oil
Invert
Emulsion
Water
Glycol
Phosphate
Ester
Polyol
Ester
HM
29.1 kJ/g
650
150F
0.001 @ 50C
0.85-0.88
32-68
0.05%
HF-B
16.3 kJ/g
830
120F
NA
0.91-0.93
80-100
43%
HF-C
5.3 kJ/g
830
120F
80 @ 50C
1.05-1.10
40
43%
HF-DR
19.0 kJ/g
1100-H
150F
< 1 @ 150C
1.02-1.16
22-100
0.05%
HF-DU
21.1 kJ/g
750"
150F
NA
0.91-0.96
46-68
0.1%
100%
Buna-N, Viton
33%
Nitroxyl, Buna-N
67%
Buna-N
67%
Butyl, EPR
100%
Viton, Buna-N
"Roberts and Brooks Flammability Data, NFPA T2.13.8-1997, a calculated estimate was used for HFDU.
CHAPTER
combustion of phosphate esters are endothermic. Thus,
phosphate esters generate less heat when burned relative to
other HFD fluids. In addition, because their Are resistance
is not dependent upon the presence of water or mist suppressing additives, the fire resistance of HFDR fluids does
not degrade in service.
HFDR fluids have been used in hydraulic applications for
more than forty years and are known for excellent inherent
lubricating properties [77]. In fact, aryl phosphate esters
serve as antiwear additives in mineral oil based hydraulic fluids [78]. However, phosphate esters have a steep viscosity
temperature curve, which makes their temperature operating
window rather narrow [79]. Hydrolysis is the most c o m m o n
form of degradation in HFDR fluid, and can occur in the
presence of a small amount of water and heat. When hydrolysis takes place, phosphate esters break down into their constituent acids and alcohols. Due to the frequent presence of
water in hydraulic applications, the sensitivity of phosphate
esters to water has limited their use and significantly reduced
their service life.
Phosphate esters are compatible with all common metals
except aluminum. Phosphate esters do not "wet" the surface
of aluminum and thus aluminum should not be used in tribological contacts such as bearings [80]. Phosphate esters
should never be added to systems containing mineral oil or
water-based fire resistant fluids. Not only are these materials
chemically incompatible with each other, in all probability
preexisting gaskets, seals, hoses, and coatings are also incompatible. Special precautions also are required in the selection of filter construction materials and plumbing of
p u m p inlets. Thus, it is necessary to work closely with fluid
and component suppliers when utilizing HFD fluids.
HFDU fluids typically are composed of polyol esters although other materials such as polyalkylene glycols are included in the HFDU category. Trimethylol propane oleate,
neopentyl glycol oleate, and pentaerythritol esters are the
most c o m m o n of the synthetic polyol esters. Triglycerides
derived from soybeans, sunflower, and rapeseed plants are
naturally occurring polyol esters that also are used in HFDU
fluids. Polyol esters derive their fire resistance from a combination of factors. First, polyol esters have a relatively high
flash, fire, and autoignition point. Second, they b u m with
less energy than oil because of the presence of oxygen in the
molecule. And finally, polyol ester fire resistant fluids employ antimist additives that enhance their spray-flammability resistance [81]. Depending upon the shear stability of the
polymer, the fire resistance of the fluid may deteriorate in
service.
Like phosphate esters, polyol esters have excellent lubricating properties but are prone to hydrolysis in the presence
of water [82]. In addition, they are vulnerable to oxidation because of unsaturation irl the fatty acid portion of the ester.
These factors tend to limit their service life relative to mineral
oils. Most common metals used in hydraulic applications are
compatible with polyol ester hydraulic fluids, with the exception of lead, zinc, and cadmium. Unlike other fire resistant
fluids, polyol esters performance is satisfactory with comm o n filter construction materials and system designs. Thus it
is relatively easy to convert a hydraulic system that operates
on mineral oil based hydraulic fluids to HFDU fluids.
13: HYDRAULIC
FLUIDS
377
Classification
Commercial Designation
HETG
HEES
HEPG
HEPR
Polyglycol types
Polyalphaolefln types
ASTM STANDARDS
No.
D 92
D 95
D 96
D 97
D 130
CONCLUSIONS
A well formulated hydraulic oil consists of a properly selected
base fluid and the appropriate balance of additives, optimized to provide the best possible overall performance required for the targeted application. The versatility of hydraulics makes fluid power advantageous in a wide variety of
industrial and mobile applications. With this versatility
comes the challenge of developing fluids that function appropriately in a wide range of conditions, even as environmental health and safety requirements become more and
more stringent. New fluid technologies continue to emerge to
meet these challenges.
D 287
D 445
D 446
D 471
D 664
Title
Test Method for Flash and Fire Points by Cleveland
Open Cup
Test Method for Water in Petroleum Products and
Bituminous Materials by Distillation
Test Method for Water and Sediment in Crude Oil
by Centrifuge Method
Test Method for Pour Point of Petroleum Products
Test Method for Determination of Copper Corrosion from Petroleum Products by the Copper Strip
Tarnish Test
Test Method for API Gravity of Crude Petroleum
and Petroleum Products (Hydrometer Method)
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
Specifications and Operating Instructions for Glass
Capillary Kinematic Viscometers
Test Method for Rubber Property-Effect of Liquids
Test Method for Acid Number of Petroleum Products by Potentiometric Titration
Polypropylene glycols
I Mininnum
Maximum
Mineral oils
Hydro-treated
mineral oils
Polyethylene glycols
1 Vegetable oils
Synthetic esters
20
40
60
80
100%
CHAPTER
D 665
D 892
D 943
D 974
D 1298
D 1401
D 1744
D 2070
D 2270
D 2271
D 2272
D 2422
D 2619
D 2717
D 2766
D 2783
D 2882
D 2983
D 3339
D 3427
D 3519
D 3603
D 3707
D 3709
D 4172
D 4310
D 4684
D 5133
D 5182
D 5306
D 5534
D 5621
D 6006
D 6046
D 6080
D 6158
D 6278
D 6351
D 6546
D 6547
13: HYDRAULIC
FLUIDS
379
OTHER STANDARDS
AFNOR NF E48-690: Hydraulic Fluid Power. Fluids. Measurement of Filtrability of Mineral Oils
AFNOR NF E48-691: Hydraulic Fluid Power. Fluids. Measurement of Filtrability of Minerals Oils in the Presence of
Water
ANSI/(NFPA) S t a n d a r d T2.13.7R1-1996: Hydraulic Fluid
Power - Petroleum Fluids - Prediction of Bulk Moduli
ISO 6743/4 Part 4: Family H (Hydraulic Systems), Lubricants, Industrial Oils and Related Products (Class L ) : Classification Part 4: Family H (Hydraulic Systems)
ISO 12922: Lubricants, Industrial Oils, and Related Products
(Class L)Family H (Hydraulic systems)Specifications
for categories HFAE, HFAS, HFB, HFC, HFDR and HFDU
ISO/DIS 15380: Lubricants, Industrial Fluids and Related
Procedures (Class L), Family H (Hydraulic Systems)-Specifications for Catagories HETG, HEPG, HEES and HEPR
REFERENCES
[1] Halliday, D. and Resnick, R. Physics, 3rd ed., John Wiley &
Sons, NY, 1978, p. 376.
[2] Henke, R., Diesel Progress, Fluid Power Buyer's Guide, Diesel
and Gas Turbine Publications, Waukesha, WI, 1994, p. 4.
[3] Vickers Industrial Hydraulics Manual, Ch. 3, Vickers, Inc.,
Rochester Hills, MI, 1992, p. 3-1.
[4] Booser, E. R., Handbook of Lubrication, Volume II Theory and
Design, CRC Press, Boca Raton, FL, 1987, pp. 242-244.
[5] NFPA Standard T2.13.7R1 - 1997: Hydraulic Fluid Power Petroleum Fluids - Prediction of Bulk Moduli, National Fluid
Power Association, Milwaukee, WI, 1997.
[6] Lightening Reference Handbook, 7th ed., Paul-Munroe Hydraulics, Whittier, CA, 1990, p.l22.
[7] Totten, G. E., Webster, G. M., and Yeaple, F. D., "Physical Prop-
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
[64]
[65]
[66]
MNL37-EB/Jun. 2003
Compressor Lubricants
Desh Garg, ^ George E. Totten, ^
and Glenn M. Webster^
II
V2
T2
In addition, if the temperature of a gas increases as the pressure increases when the volume is held constant then Amonton's Law states that:
Pi_
P2
T2
DISCUSSION
Charle's Law and Boyle's Law are combined to form the wellknown Ideal Gas Law which states:
Gas Laws
PxV,
P2V2
Ty
T2
Avogadro's Law states that the equal volumes of gases at the
same temperature and pressure contain the same number of
molecules:
PV = nRT
PiFi = P2V2
When performing these calculations, the reference value used
to determine the pressure must be indicated. If the reference
value is a vacuum, then the pressure is absolute {Pa) However,
if the reference level is atmospheric pressure {Patm), then it is
called gauge {Pg) pressure. They are related by:
Where n is the number of moles, R is the so-called gas constant that is selected to be consistent with the units of temperature, pressure, and volume used in the calculation (see
Table 1).
Dalton's Law states that the total pressure (Py) of a mixture
is the sum of the partial pressures of the constituent gases
(a,b,c,
) in the mixture:
PT = Pa + Pb + Pc+
383
Copyright'
2003 by A S I M International
www.astm.org
P2V2
T2Z2
Values for the compressibility factor are obtained from reference charts called general compressibility charts such as
those available in Ref. 4.
Pd
-J,-;
IJJ
Isothermal versus Adiahatic Operation
Theoretically, there are two ways that a positive displacement compressor can be operated; either isothermally or adiabatically. These modes of operation are illustrated using a
WORK
-h ;:v.
'"^"/t-i-'i-r'
Ps
P2V'2
VOLUME INCREASES
X l O V gs/deg mole
joules/d eg mole
cal/deg mole
cc atm/deg mole
Gas
Methane
Ethane
Propane
i-Butane
n-Butane
i-Pentane
n-Pentane
Hexane
Carbon Dioxide
Hydrogen Sulfide
Nitrogen
Oxygen
Chemical
Formula
CH4
C2H6
CjHg
C4H10
C4H10
C5H12
C5H12
CeHn
CO2
H2S
N2
O2
Critical
Temperature
(R)
344
550
666
735
766
830
846
915
548
673
227
278
Critical
Pressure
(psia)
673
708
617
529
531
483
489
440
1073
1306
492
732
Molecular
Weight
(g/mole)
16
30
44
58
58
72
72
86
44
34
28
32
Density @
60F, 14.7 psia
Specific
Gravity
Air= 1.0
Lbs/ft^
0.554
1.038
1.523
2.007
2.007
2.491
2.491
2.975
1.519
1.176
0.967
1.105
0.0424
0.0799
0.1180
0.1578
0.1581
0.190
0.190
0.227
0.1166
0.0897
0.0738
0.0843
Specific Heat @
60F, 14.7 psia
Cp
Cv
BTU/lb/F
BTU/lb/F
0.527
0.410
0.388
0.387
0.387
0.383
0.388
0.386
0.199
0.238
0.248
0.219
0.403
0.344
0.343
0.353
0.353
0.355
0.361
0.363
0.154
0.180
0.177
0.157
Cp/Cv
1.308
1.192
1.131
1.097
1.097
1.078
1.076
1.063
1.293
1.325
1.400
1.346
AB - ADIABATIC
AC - POLYTROPIC
AD - ISOTHERMAL
.
\
[4]:
THEORETICAL
NO CLEARANCE
0}
W
Ul
DC
where R is the compression ratio which is defined as the absolute discharge pressure divided by the absolute inlet pressure of a compressor and C is the cylinder clearance (%). This
is a theoretical value and equation must be modified to account for inefficiencies such as internal leakage, gas friction,
pressure drops through valves, etc. This is done by introducing the factor "L."
Q.
..A
VOLUME
Ti
385
D CB
UJ
LUBRICANTS
Pi
(B)
Piston Displacement-
FIG. 4Illustration of the determination of volumetric efficiency from the PV diagram using piston displacement and actual capacity
Compression Ratio
Very high
High
Moderate
Low
144
33000 \ k - 1
Compressors
Reciprocating compressors compress gas by physiccilly reducing the volume of gas contained in a cylinder using a piston. As
the gas volume is decreased, there is a corresponding increasing in its pressure (as indicated by the gas laws discussed earlier). Therefore, this type of compressor is also referred to as a
positive displacement type. An illustration of a reciprocating
Clearance
Clearance principally
Balanced
Valving
(k-l/k)
R - 1
(PsVs)
300
O
2 200
E
<a
\-
100
1
50
1
100
1
150
200
LUBRICANTS
To consider the lubrication process, it is convenient to divide the parts that need to be lubricated into two categories;
namely cylinder parts and running parts. Cylinder parts include pistons, piston rings, cylinder liners, cylinder packing,
and valves. All parts associated with the driving end (i.e., the
crankcase end), cross-head guides, main bearing and wristpin, crankpin, and cross-head pin bearings are running parts.
An equation recommended by Scales for estimating the
amount of oil to inject into a cylinder for lubrication is [3]:
Q
BXSXNX
62.8
10 000 000
COMPRESSOR TYPES
RECIPROCATING
ROTATING
FIG. 6Classification of compressor types. Reprinted with permission from Universal Compression,
Inc.
Cylinder
Liner
Crosshead
Guide
Crosshead
Piston Rod
pamnq
Water Jacketed
Cylinder
Variable VOIURK
Clearance Pocket
FE 6501
Piston
Rod
Valve
Frame
Crankshaft
387
Connecting
Counter
Wght
FIG. 7Cross section of a reciprocating compressor. Reprinted with permission from Universal Compression, Inc.
Compressors
Rotary compressors are further classified as positive displacement or djTiamic type compressors. A positive displacement type of compressor utilizes gas volume reduction to increase gas pressure. Examples of this type of compressor
include: rotary screw, lobe, and vane compressors that are illustrated in Fig. 8 [10,12,14], Fig. 9 [9] and Fig. 10 [9].
The rotary screw compressor illustrated in Fig. 8 consists
of two intermeshing "screws" or rotors that trap gas between
the rotors and the compressor case [13]. One rotor is the male
rotor and is driven by the motor. The outer rotor is the female
rotor and is driven by the male rotor. Both rotors are encased
in a housing provided with gas inlet and outlet ports. Gas is
drawn through the inlet port into the voids between the rotors. As the rotors rotate, the volume of trapped gas is successively reduced and compressed by the rotors coming into
mesh.
These compressors are available as dry or wet (oilflooded) screw types. For the dry-screw type, the rotors run
inside of a stator without a lubricant (or coolant). The heat
of compression is removed outside of the compressor, limiting it to a single-stage operation. For oil-flooded screw
type compressors, the lubricant is injected into the gas that
is trapped inside of the stator. The functions of the lubricant include cooling, sealing, and lubrication. The gas is removed from the compressed gas-lubricant mixture in a separator. As opposed to reciprocating compressors, which are
once through processes, rotary compressors, such as the
screw compressor, continuously recirculate (1-8 times a
min) the lubricant-gas mixture to facilitate gas cooling and
separation [13].
In a rotary screw compressor, the lubricant is injected into
the compressor housing. The rotors are therefore exposed to
a mixture of the gas and lubricant. In addition to providing a
CHAPTER
.y Impeller^
Labyrinth Seal-,
Oil Pump
14: COMPRESSOR
LUBRICANTS
389
Impeller
'Roller
Bearing
Timing
Gears
(a)
(b)
FIG. 9Cross section of a rotary straight lobe compressor.
i INLET
DISCHARGE
-THRUST PIN
SLOT
VANE
PACKING
STRIP
ROTOR
lobes and then discharged. The bearings and timing gears are
lubricated using a pressurized lubricating system.
A rotary vane compressor schematically illustrated in Fig.
10 [9]. Rotary cane compressors consist of a rotor with multiple sliding vanes that are mounted eccentrically in a casing.
As the rotor rotates, gas is drawn into areas of increasing volu m e (A) and discharged as compressed gas from areas of
small volume (B).
As with reciprocating compressors, lubrication of rotary
vane compressors is also a once through operation. The lubricant is injected into the compressor casing and it exits
with the compressed gas and is usually not recirculated. The
lubricant provides a thin film between the compressor casing
and the sliding vanes and also provides lubrication within the
slots in the rotor for the vanes. The sliding motion of the
vanes along the surface of the compressor housing requires a
lubricant that can withstand the high pressures within the
compressor system.
A dynamic compressor, such as the centrifugal compressor
shown in Fig. 12 [9], operates on a totally different principle.
Energy from a set of blades rotating a high speed is transferred to a gas that is then discharged to a diffuser where the
gas velocity is reduced and its kinetic energy converted to
static pressure. One of the advantages of this type of compressor is the potential to handle large volumes of gases.
In a centrifugal, the lubricant and gas do not come into
contact with each other which is a major distinction from reciprocating, rotary screw and rotary vane compressors. The
lubricant requirements are therefore simpler and usually a
good rust and oxidation-inhibited oil will provide satisfactory
lubrication of the bearings, gears and seals.
Compressor Lubricants
Performance
Demands
390
HANDBOOK
-AIR
DISCHARGE
BACKPLATE
DIFFUSER
PACKING BOXLABRINTH
SEAL
SLEEVE
BEARING
pressed, the degree of compression and the final outlet temperature. Piston compressors provide the highest gas pressures and are among the most difficult from the standpoint
of cylinder lubrication. Rotary compressors with final pressures below 1 MPa are less difficult to lubricate. Because of
the potential for vane-on-ring contact, rotary vane compressors require the use of an antiwear oil [17], whereas an R &
O oil is often sufficient for the crankcase splash lubrication
391
TABLE 5ISO 6743-Part 3A: Family D-Compressor lubricant classification oil-lubricated air compressors.
Particular Application
Positive
displacement
air compressors
with oil-lubricated
compression
chambers
More Specific
Application
Reciprocating
(crosshead and
trunk pistons or
Rotary drip feed
(vane)
Rotary oil-flooded
(vane and screw
compressors
Positive displacement
air compressors with
oil-free compression
chambers
Dynamic compressors
Symbol ISO-L
DAA
Typical
Applications
Light duty
Continuous operation
DAB
Medium duty
Intermittent operation
DAC
Heavy duty
Intermittent or
continuous operation
DAG
Light duty
DAH
Medium duty
DAJ
Heavy duty
Liquid ring
compressors
and w a t e r flooded vane
and screw
compressors
Reciprocating oilfree compressors
Rotary oil-free
compressors
Radial and axial
turbo
compressors
'Under favorable conditions, light-duty oil may be used at discharge pressures higher than 800 kPa (8 bar).
Remarks
Sufficient time to allow cooling
between periods of operation
Compressor stop and start
Variable discharge capacity
a. discharge pressure >10^kPa
(lobar)
discharge temperature >160C
stage pressure ratio >3:1 or
b. discharge pressure >10^ kPa
(lobar)
discharge temperature >140C
stage pressure ratio >3:1
Sufficient time to allow cooling
between periods of operation
a. discharge pressure >10^kPa
(lobar)
discharge temperature >160C
or
c. discharge pressure > 10^ kPa
(lobar)
discharge temperature >140''C
or stage pressure ratio >3:1
As for "medium," when
conditions a, b, or c above are
fulfilled and where severe coke
formation in a discharge
system might be anticipated as
a result of previous experience
with a medium-duty oil.
Air and air/oil discharge
temperature <90C
Discharge pressure
<800 k P a ' ( < 8 bar)
Air and air/oil discharge
temperature <100C
Discharge pressure
800-1500 kPa (8-15 bar)
or
Air and air/oil discharge
temperature 100-110C
Discharge pressure
<800 k P a ' ( < 8 bar)
Air and air/oil discharge
temperature > 100C
Discharge pressure
<800 k P a ' ( < 8 bar)
or
Air and air/oil discharge
temperature f l O O X
Discharge pressure
800-1500 k P a ' ( 8 - 1 5 bar)
or
Discharge pressure
> 1500 b a r (>15 bar)
Lubricants suitable for gears,
bearings and transmissions
392
MANUAL
HANDBOOK
Basestocks
32
395
84.14
17.74
66.40
(24.46)
(15.24)
(9.10)
(10.58)
(4.67)
(2.35)
14.37
(10.49)
(2.60)
(0.48)
(0.13)
(0.67)
0.19
1.30
500
30
Solvent
Refined
Naphthenic
32
330
58.22
12.22
45.00
(15.69)
(12.82)
(8.21)
(6.01)
(2.45)
(0.82)
31.06
(12.28)
(12.58)
(2.72)
(2.28)
(1.20)
9.09
1.64
13,400
160
Two-Stage
Hydrotreated
32
405
99.97
32.60
67.37
(30.81)
(19.52)
(8.87)
(4.75)
(2.56)
(0.86)
0.03
(0.03)
Nil
Nil
Nil
Nil
Nil
Nil
2
1
LUBRICANTS
393
350r
100
200
300
PRESSURE (bar)
FIG. 13Recommended guideline for the use of mineral oil lubricants for air compressors.
Phosphate Ester
- _ ^ Phosphate Ester
_
w/ Iron Oxides
Polyol Ester
Diester, 100ISO
Polyalphaolefin
Mineral Oil #1
Mineral Oil #2
Mineral Oil #2
w/ Iron Oxides
90
120 150 180
PRESSURE (PSIG)
FIG. 14Autoignition of various synthetic and mineral oils compared
to discharge pressures and temperatures. A. single stage, B. two stage,
and C. three stage.
moved using a flash still unit such as the one shown schematically in Fig. 15 [19].
PAG polymers exhibit excellent viscosity-temperature behavior (high viscosity index) as shown in Fig. 16 [ 14] and they
may usually be used up to compression temperatures of
200C [16] However, they have been reported to degrade at
compression temperatures of 230C which would make them
unsuitable for high temperature air compressor applications
[23]. Other reported advantages include low pour point, high
flash point, and low vapor pressure. PAG-based compressor
lubricants have been used with success in natural gas, nitrogen, carbon dioxide, hydrogen, and helium compression [29].
Ethylene compression for low-density polyethylene (up to
50000 psig) has also been reported [29].
Blends of PAGs with other basestocks have been reported
to offer properties superior to either basestock itself. For ex-
394
HANDBOOK
COMPRESSED
-GAS
DISCHARGE
Gas
Refrigerant
r0cCOOLER
MOTOR
OMPRESSOR
1 I LUBE
Gas + Lube +
i r SEPARATOR
H.C. Condensibles Z
Condensibles
_F;
fe 3
(fn
Lube + H.C.
Condensibles
Recycle Stream^<^ 1
H.C. Vapors
IFILTER
SUCTION
TANK
-Or
HEATER
FLASH
DISTILLER
LUBE
PUMP
COOLER
FIG. 15Flooded rotary screw gas compressor system equipped with a flash still unit.
100,000
20,000
(0
u
E
CO
O
1,000
300
75
40
15
PAG
PAO
Semi-Synfhetic
Mineral Oil
>
-30
50
100
150 200
TEMPERATURE (F)
-17.8
37.7
93.9
148.9
TEMPERATURE (C)
FIG. 16Comparative viscosity-temperature relationships
for different compressor lubricants.
100
90
80
9
3
X
UJ
>
UJ
in
Polyalphaolefin
"Fluid
70
60
/C
50
DIester
Fluid
403020
10-
'
500
Jt-L
1000
- 1 ^iOO
2000
2500
3000
3500
CHAPTER
"0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
WEEKS
FIG. 18Comparison of the oxidative stability of a food
grade Poly(Alphaolefin) (PAO) with a hydrocarbon white oil.
in the
Lubricant
14: COMPRESSOR
LUBRICANTS
395
300
j f
<
Q^ 200
LU
DC
i/>
Uj 100
a:
crfSs-
^5^=^
Q.
10
20
30
% GAS
FIG. 19Hydrocarbon gas solubility in an ISO 220 polypropylene oxide at constant temperature.
396
HANDBOOK
o
o
>
2000
3000
4000
PRESSURE (PSIA)
500
1000
500i
5000
20
40
60
80 100
TEMPERATURE (C)
FIG. 20Effect of hydrocarbon gas dilution on viscosity with
increasing temperature of a hydrocarbon gas in an ISO 220
polypropylene oxide fluid.
"0
1000
2000
3000
4000
Pressure (PSIA)
FIG. 24Hydrogen solubility comparison in a PAG.
2000
3000
PRESSURE (PSIA)
FIG. 21Methane gas solubility comparisons for a polyalkylene glycol, Poly(Alphaolefin) and petroleum oil at 50C.
2000
3000
PRESSURE (PSI)
LUBRICANTS
397
^ 0.5
(
lU 0.4t
>
CD 0.3
0.2
^ ^ s * ^ ^
0.1 -{"4f
1000
2000
(a)
3000
4000
5000
PRESSURE (PSIA)
6000
7000
(O
(
l
i""-i
1
i S J PAG
t
10
20
30
40
50
60
70
80
TEMPERATURE C O
FIG. 27Solubility of carbon dioxide in a PAG at SOX.
1000
(b)
3000
4000
5000
PRESSURE (PSIA)
6000
7000
-^ 0.5
o
E 0.4
.^.PJAG
^ 0.3
5 0.2
O
0.1
48
i
!
60
72
84
TEMPERATURE (C)
i
96
108
is also an important fluid maintenance procedure and is useful for comparison with the viscosity of a fresh fluid. Viscosity measurement by various tests, including Test Method D
445, is discussed in detail in Chapter 32Flow Properties
and Shear Stability, and will not be discussed further here.
The viscosity-temperature relationship (viscosity index) of
a compressor fluid is another important physical property
that may be determined according to ASTM D 2270.
398
MANUAL
HANDBOOK
^ ^ 2 0 0 est PAG
a.
O 40
OT 30
o
o
W 20
hOGAS
ATMOSPHER C PRE
URE
340 bar N,
SATURATED WITH
METHANE
FIG. 28Effect of pressure and gas dilution on the viscosity of a mineral oil and a PAG cylinder lubricant.
Stability
(Test Method
2619)
Some compressor lubricants hydrolyze in the presence of water at elevated temperature such as those based on ester basestocks [8]. Therefore, it may be important to determine the
hydrolytic sensitivity of a compressor fluid to water. Conducting Test Method D 2619, the Beverage Bottle Method,
can do this.
Test Method D 2619 covers the determination of the hydrolytic stability of synthetic or petroleum-base hydraulic
fluids b u t is as applicable to compressor fluids. In this
method, 75 g of the compressor fluid and 25 g of water and a
copper test specimen are sealed in a pressure-type bottle. The
bottle is rotated, end for end, for 48 h in an oven at 93C
(200F). Layers are separated, and insolubles are weighed.
The weight change of copper is measured. Viscosity and acid
numbers and the acidity of the water layer are determined.
This method differentiates the relative stability of compressor lubricants in the presence of water under the conditions of the test. Hydrolytically unstable fluids form acidic
and insoluble contaminants, which may cause compressor
system malfunctions such as corrosion, valve sticking, or
change of viscosity of the fluid.
Foaming
Tendency
(Test Method
D 892)
Air Release
(Test Method
3427)
(Test Method
4310)
CHAPTER
[10,11,25,26,31,32,34,35]. The flash point is the lowest temperature, corrected to a barometric pressure of 101.3 kPa
(760 m m Hg), at which the application of an ignition source
causes the vapors of a fluid being tested to ignite under the
specified conditions of the test. The test usually cited for
compressor fluids is the so-called Cleveland Open-Cup flash
point. This test procedure is described in detail in Chapter
25Volatility.
The fire point is the lowest temperature, corrected to a
barometric pressure of 101.3 kPa (760 m m Hg), at which the
application of an ignition source causes the vapors of a fluid
being tested to ignite and continue to b u m for 5 s under the
specified conditions of the test.
Autoignition
(Test Method
E 659)
Compressor fluids should not be used above their autoignition temperature. Autoignition temperature is the temperature at which the fluid will ignite spontaneously in contact
with air and may be determined by Test Method E 659. No
sparks or open flame need be present. Hydrocarbon fluids
absorbed on porous surfaces can ignite at temperatures more
t h a n 50C (approximately 100F) lower t h a n indicated by
Test Methods E 659.
Evaporation
Increasing volatility of the compressor fluid will result in increasing carbon build-up in the discharge system of a compressor [27]. This will occur if the oil fractions are sufficiently volatile to r e m a i n in the vapor state of the hot
discharge zone where the oil can break down into carbon.
Evaporation Loss (Test Method D 972)Oil volatility can be
measured by Test Method D 972. In this test, a weighed sample of the compressor oil is placed in a bath maintained at the
desired test temperature, typically 100-150C (210-300F).
Heated air is passed over its surface for 22 h. The evaporation
loss is calculated from the loss of mass of the sample.
NOACK Evaporation Loss (Test Methods D 5800 and D
6375)The NOACK test method is a method of measuring
evaporative loss of an engine oil during use, but can be related to any set of conditions. It was recently applied to measuring the evaporative loss of compressor fluids [35]. This
test is conducted using the NOACK Evaporative Tester illustrated in Fig. 29. In this test, a measured quantity of the compressor fluid is placed in an evaporation crucible, which is
then heated to the desired temperature with a constant flow
of air drawn through it for 60 min. The loss in mass of the oil
is determined. In this test, Wood's metal, which contains
lead, bismuth, antimony, a n d cadmium, is used. These components have been found to be health hazards. Therefore, if
it is possible. Test Method D 6375 should be used (see following discussion).
An automated, smaller scale variant of Test Method D 5800
is Test Method D 6375, the "TGA NOACK Method." This
method is applicable to lubrication oils that exhibit NOACK
evaporative losses of 0-30%. In this test, a sample of the desired compressor fluid to be tested is placed in an appropriate Thermogravimetric Analyzer (TGA) specimen pan. The
pan is placed on the TGA p a n holder and quickly heated to
between 247-249C under a stream of air and then held for
an appropriate time. Throughout the process, the TGA monitors and records the mass loss experienced by the specimen
14: COMPRESSOR
LUBRICANTS
399
due to evaporation. The NOACK evaporation loss is subsequently determined from the specimen weight percent loss
versus time curve (TG Curve) as the mass percent lost by the
specimen at the NOACK reference time determined under
the same TGA conditions. This procedure requires m u c h
smaller test specimens and is m u c h faster when multiple
samples are sequentially analyzed; it is also safer than the
NOACK Test Method D 5800.
Carbon
Residue
One of the greatest problems encountered when using a compressor fluid is the formation and accumulation of sludge,
which can lead to a safety problem, possibly even an explosive situation if coupled with overheating. This will occur if
sufficient quantities of c a r b o n a n d sludge are formed to
cause the valves to stick open (Reference ISO 5388 part
6.6.1). Therefore, it is desirable to determine the sludgeforming potential of a compressor fluid.
Conradson Carbon Residue (Test Method D189)One method
of quantifying the sludge-forming potential of a compressor
fluid involves determination of the Conradson carbon residue
(Test Method D189) [31 ], which measures the amount of polymeric material remaining in the oil after heating to elevated
temperatures in the absence of sufficient oxygen to burn off
all of the organic compounds present. The Conradson carbon
residue is determined by placing a weighed sample in an iron
crucible. The crucible is heated with a Meeker-type gas burner
to a sufficiently high temperature to evaporate and b u m the
oil. The sample is further heated until the bottom and sides of
the crucible are cherry red and is held at this temperature for
30 min. The crucible is then cooled and weighed. The amount
of tar remaining in the crucible relative to the original amount
of the oil define the Conradson carbon residue value. Test
Method D 189 may be affected by some additives used to formulate the compressor fluid.
Ramsbottom Carbon Residue (Test Method D 524)Another
test that is used to determine the tendency for a compressor
lubricant to form carbonaceous residues is Test Method D
524, the Ramsbottom Carbon Residue test [15]. In this test,
the sample, after being weighed into a special glass bulb, is
placed in a metal furnace and heated to 550C. In this way,
the sample is quickly heated to the point where all volatile
material is evaporated out of the bulb, with or without decomposition, while the remaining residue undergoes cracking and coking reactions. After the test, the bulb is cooled and
weighed. The residue remaining is reported as % of original
sample and is called the Ramsbottom Carbon Residue.
"Micro Method" for Carbon Residue (Test Method D 4530)In
the "micro method," a weighed sample of the fluid is heated
in a 2 mL glass vial at 500C under an inert atmosphere (nitrogen) in a controlled manner for a specific time. The sample undergoes coking reactions a n d the volatiles that are
formed are swept away by the nitrogen. The carbonaceous
residue formed is reported as % of original sample as "carbon
residue (micro)." This test method is reported to be equivalent to the Conradson Carbon Residue.
Precipitation
Number
(Test Method
D 91)
400
HANDBOOK
~N
Manometer
Thermometer
j ~ To Pump
FIG. 29Schematic illustration of the NOACK Evaporative Tester (ASTM Test Method D 5800).
CHAPTER
in the presence of an iron-copper catalyst at 95C. The test is
continued until the measured acid n u m b e r is 2.0 mg KOH/g
or above. The n u m b e r of hours required for the test fluid to
reach 2.0 mg KOH/g is the "oxidation lifetime." Sugiura,
however, utilized a m u c h lower critical AN value of 0.4 mg
KOH/g since his work indicated that the oxidation rate of the
compressor oils he examined increased dramatically above
0.4 mg KOH/g [22].
Rotating Bomb Oxidation Test-RBOT (Test Method D 2272)
Various workers have reported the use of RBOT as an accelerated test to evaluate compressor fluid lifetime [11,23,26].
This test m e t h o d utilizes an oxygen-pressurized vessel to
evaluate oxidation stability of new and used compressor fluids in the presence of water and a copper catalyst at 150C.
For this test, the compressor fluid, water, and copper catalyst
coil, contained in a covered glass container, are placed in a
vessel equipped with a pressure gauge. The vessel is charged
with oxygen to a gauge pressure of 620 kPa (90 psig, 6.2 bar),
placed in a constant-temperature oil bath set at 150C, and
rotated axially at 100 r p m at an angle of 30 from horizontal.
The n u m b e r of minutes required to reach a specific drop in
gauge pressure is the oxidation stability of the fluid.
Indiana Stirring Oxidation Test-ISOT (Test Method JIS K
2514)~The ISOT, although developed in the U.S., has only
been standardized in Japan as JIS K 2514 and has been reported to provide superior correlation with actual results for
actual industrial compressor use [22,26]. This test cell for
this method is illustrated in Fig. 3 1 . This modified version of
14: COMPRESSOR
LUBRICANTS
401
Washing
Wash-Off
402
MANUAL
HANDBOOK
Dry Air
10 1 Mir.
fr
Oil Bath
Temperature = 170 "C
4-5Sample
4J.44
^ ^
Dimensions in miilimeters (mm)
Liquid Heptane
Wasiiing Test
then the plates are dipped into a bath of heptane for 5 s. After
ten dipping cycles, the steel plates are suspended in air to allow the h e p t a n e to evaporate and then the plates are
reweighed to determine the a m o u n t of oil film removed. An illustration of the relative weight loss of two different compressor oils subjected to this test is provided in Fig. 32 [8].
Antiwear
Properties
If possible, it is desirable to determine the lubrication properties of every compressor oil in every compressor. However,
in addition to being prohibitively expensive and requiring
enormous amounts of time, industrial equipment is not designed with the precision required for ideal laboratory test instruments. Therefore smaller scale lubrication testing is performed as a laboratory fluid development tool and while very
useful, these data must, at some point, be confirmed by infield testing in actual compressor units and processes where
the use of the fluid is contemplated. Although any test could
conceivably be used if properly correlated with compressor
operation, there are two bench tests that are encountered
most often in the published literature: FZG [23,32,35] and 4ball [8,15,25]. These tests will be discussed here.
4-BaU EP and Wear Test (Test Methods D 2783, D 4172 and IP
239)Test Method D 4172 is used to measure the relative
wear preventive properties of lubricating fluids under sliding
contact conditions using a Four-Ball EP and Wear Test Machine. Although Test Method D 4172 calls for test loads of 15
or 40 kgf at 1200 r p m and 75C, any load condition can be
used, if more appropriate. Some test conditions that have
been reported include: 1 h at 40 kgf, 1800 rpm and 54.4C
Cycles
FIG. 32Comparison of the liquid heptane
wash-off results for a 200 cSt PAG and a mineral
oil compressor lubricant.
403
7.5 k W
Speed
Maximum oil deliveiy pressure
Oil capacity
Free air delivered
Air discharge temperature
825 rpm
10bar(150psig)
4.5 L
15.2L/sat lOOpsig
MANUAL REGULATING
VALVE
CONDENSATE DRAIN
300-325C
404
HANDBOOK
<i>
LP AIR T O
ATMOSPHERE
<I>
C/W RETURN
"mERMOCOUPLE
(STAGE 4)
Sr^ ^-
RECIRCULAtORY
COOLING WATER - FLOW
H.P.AIR
<i>'
^-^
&
REAVELL VHP15
4 STAGE AIR
COMPRESSOR
10
DRIVE
MOTOR
22 Kw
CONDENSATE
DRAINS
22 kW
Speed
Maximum delivery pressure
Free air delivery rate
Sump oil capacity 23.1 L
1450 r p m
350 b a r (5000 psig)
13.3 L/s
3.1
140
19.6
179
84.5
146
310
180
405
Test 1
Compressor
Fluid
A
B
C
D
Field
Rating
(1 = Best)
3
4
1
2
Air Flow
ON Flow
Alr/OII Flow
Water Flow
5M
Air
Filter
Differential
Pressure
Gauge
5-10 M
Air
Filter
Motor
Oil Cooler
Drain Valve
FIG. 35Schematic illustration of compressor test circuit used for coalescer blocking tendency test.
406
MANUAL
HANDBOOK
100
-SO
90
L = 0.300 exp
Where T =
for a liquid
273 K for a
ent density
o.639m;^
/H3.333LO
(P-Pv)L
0.224
TEMPERATURE,-F
200
30O
100
tSO
200
eso
T E M P E R ATURE.'C
r - 288 - 2
CHAPTER
TABLE 12Ostwald coefficients at 0C for
petroleum liquids with d = 0.85.
Gas
Ostwald
Coefficient (LQ)
Helium
Neon
Hydrogen
Nitrogen
Air
Carbon monoxide
Oxygen
Argon
Methane
Krypton
Carbon dioxide
Ammonia
Xenon
Ethylene
Hydrogen sulfide
0.012
0.018
0.040
0.069
0.098
0.12
0.16
0.18
Use Fig. 36"
0.60
1.45"
1.7"
3.3
Use Fig. 36"
5.0"
// =
IlD
B = 2697
r-288.2
Alternatively, the density may be determined experimentally by Test Method D 1298 or it may be obtained from the
fluid supplier. Another method of density temperature correction is to use the value dp/dT from Table 13 and calculate as follows:
MG
407
Step 2Obtain the value of the equivalent solubility parameter of the gas, S2, (MPa)''^ from Table 14.
Step 3Calculate the Ostwald coefficient (L) for a lubricant from:
L = exp[(0.0395 (Si - 82)^ - 2.66) - 3.03Si
- 0.0241 (17.60 - 82^ + 5.731]
To calculate the Ostwald coefficient for a distillate fuel or
a halogenated liquid, multiply by the fuel factor from Table
14.
Step 4Calculate the Bunsen coefficient (B) as follows:
PT-
X= 10"
LUBRICANTS
Si = 8.63 2 + 0.96
14: COMPRESSOR
p^ = p-(T-
288.2) - ^
Di-2-ethylhexyl adipate
Di-2-ethylhexyl sebacate
Trimethylolpropane
pelargonate
Pentaerythritol caprate
Di-2-ethylhexyl phthalate
Diphenoxy diphenylene
ether
Diphenoxy triphenylene
ether
Polychlorotrifluroethylene
Polychlorotrifluroethylene
Polychlorotrifluroethylene
Dimethyl silicone
Methyl phenyl silicone
Perfluoro polyglycol
Tri-2-ethylhexyl phosphate
Tricresyl phosphate
S,
dp/dT
M,
18.05
17.94
18.48
370
427
459
0.928
0.916
0.962
0.00075
0.00073
0.00070
18.95
18.97
23.24
540
390
440
1.002
0.986
1.178
0.00065
0.00075
0.00079
23.67
520
1.205
0.00076
15.47
15.55
15.71
15.14
18.41
14.30
18.27
18.82
600
700
1000
10000
5000
1000
467
368
1.925
1.942
1.998
0.969
1.063
1.914
0.923
1.158
0.00166
0.00154
0.00152
0.00093
0.00080
0.00180
0.00090
0.00090
408
MANUAL
HANDBOOK
He
Ne
H2
N2
Air
CO
O2
Ar
CH4
Kr
CO2
M,
52 at 298 K
Fuel Factor
4
20
2
28
29
28
32
40
16
84
44
3.35
3.87
5.52
6.04
6.67
7.47
7.75
7.71
9.10
10.34
14.81
1.27
1.37
1.27
1.70
1.44
1.37
1.28
1.37
1.42
1.37
1.14
M2
and gas at the desired temperature. Gas is typically transferred to the Parr reactor from a gas-charging vessel. The lubricant is stirred to obtain equilibrium as indicated by reaching a constant pressure. Viscosity of saturated lubricant at
final pressure is measured with a viscosity probe and it's associated electronics. Gas solubility can be calculated from
initial and final pressures using gas laws and compressibility
factors. It can also be obtained by weighing the gas-charging
vessel before and after equilibrium.
Absorption of the Lubricant into the Gas PhaseThis is the
test procedure published previously by Matthews, which was
performed to determine the amount of lubricant lost into the
gas being compressed [8]. The test is conducted by weighing
the test oil into a small aluminum container of about 25 m m
diameter which was then placed into a 50 mL stainless steel,
high pressure reactor which was then heated to 100C. The
test gas is then pressurized to 400 bar and fed through stainless steel tubing into the stainless steel reactor containing the
test oil. The pressure is maintained by releasing the gas
through a needle valve and the total volume of the gas being
discharged is metered. At the end of the test, the aluminum
container is re-weighed and the weight loss is recorded.
Heat Transfer
Efficiency
Gos Inlet
g.
>v
Gas Outlet
1000-ml Seporotory
Funnel (peor-shopedl
Control
ThecTnocouple
Test Liquid
Healing Mantle
Ts" \
,
Cos Dispersion
Element
PTFE Stopcock A
Boll Joint B
i 12/2
FIG. 37Schematic illustration of an ainblent pressure saturator.
CHAPTER
14: COMPRESSOR
LUBRICANTS
409
Pressure Goge
Tube Connection
A"
Elastomeric
Seals Compatibility
(Test Method
D 471)
Seals may degrade in use. As an oil deteriorates in service, additional tests may be required to assure that seals remain
compatible with the degraded oil. Mills et. al, have reported
the determination of seal compatibility by a short term test
by immersion of 50 m m X 25 m m X 2 m m test specimens of
the elastomer (most often a nitrile rubber) into the compressor fluid of interest at 120''C for 168 h [32]. Volume swell was
d e t e r m i n e d according to the procedures outlined in Test
Method D 471 and the hardness was determined according to
Test Method D 1415. The authors recommended setting the
volume swell limits at 5 to -1-15% and the change in hardness to -t-20%. Although an accelerated test may be performed, it is preferable that the temperature ranges of the
tests should correspond to temperatures to which seals will
be exposed in service and the tests should be conducted for at
least 1000 h.
Thermocouple
2500-ml
Stainless
Steel \fe$sel
Thermostotic
Control
Jacket
Paint Compatibility
Test
[32]
To Condenser K
14/35
Solid Broce
stopcocks
L,M,N, ore
2-woy
'^E-0.5 mm Cleoronce
60mn(i 0.0.
SOmmO.D.
Lewting
Bulb
(Mercury)
Co pillory
Monometer
(Opin-Endl
(a)
Boiler-1
To Leveling
BulbH-
J 12/2
to Boiler I
FIG. 39Gas extraction system: A. schematic illustration of the entire apparatus and B: Illustration of the gas extraction chamber.
(b)
410
MANUAL
HANDBOOK
paint a small steel test specimen with the paint of interest and
let it dry [32]. The painted surface is then scratched in the
form of a cross and then immersed into the compressor fluid
at 120C for 168 h. If the paint is lifted or removed by the
fluid, it fails the test.
D 445
D 471
D 524
Test
[32]
D 664
D 665
D 892
D 943
D 972
D 974
SUMMARY
In this chapter, an overview of basic compressor fluid technology has been provided. This discussion included a description of the gas laws and how they applied to gas compression. Also provided was a short tutorial on how c o m m o n
types of compressors operate. This was followed by a summary of the properties of the most common classes of compressor fluids in current use in the market place. Finally,
there includes an extensive listing of various test procedures
that have been applied to the analysis of the expected performance of compressor fluids such as water content, oxidative
stability, carbon and sludge formation, gas solubility and lubrication properties.
However, it is must be realized that there is no one single
bench test that will best predict the performance of a particular compressor fluid, in a given compressor, in a given industrial process. This is illustrated in Table 10, which shows
that no one single test predicts the actual relative performance of a compressor fluid in an industrial process. It is
therefore recommended that groups of tests be performed
and overall ranking be used. Of course, whatever the bench
tests indicate, whether individually or collectively, final compressor machine performance validation is necessary.
ASTM STANDARDS
No.
D 91
D 92
D 95
D 97
D 130
D 189
D 287
Title
Test Method for Precipitation Number of Lubricating Oils
Test Method for Flash and Fire Points by Cleveland Open Cup
Test Method for Water in Petroleum Products and
Bituminous Materials by Distillation
Test Method for Pour Point of Petroleum Products
Test Method for Determination of Copper Corrosion from Petroleum Products by the Copper
Strip Tarnish Test
Test Method for Conradson Carbon Residue of
Petroleum Products
Test Method for API Gravity of Crude Petroleum
and Petroleum Products (Hydrometer Method)
D 1298
D 1401
A 1415
D 1744
D 2270
D 2272
D 2502
D 2503
D 2619
D 2711
D 2717
D 2766
D 2779
D 2780
D 2783
D 3427
D 3827
D 4007
D 4172
D 4530
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
Test Method for Rubber Property-Effect of Liquids
Test Method for Ramsbottom Carbon Residue of
Petroleum Products
Test Method for Acid N u m b e r of Petroleum Products by Potentiometric Titration
Test Method of Rust-Preventing Characteristics
of Inhibited Mineral Oil in the Presence of Water
Test Method for Foaming Characteristics of Lubricating Oils
Test Method for Oxidation Characteristics of Inhibited Mineral Oils
Test Method for Evaporation Loss of Lubricating
Greases and Oils
Test Method for Acid and Base Number by ColorIndicator Titration
Test Method for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum
Products by Hydrometer Method
Test Method for Water Separability of Petroleum
Oils and Synthetic Fuels
Test Method for Rubber Property-International
Hardness
Test Method for Determination of Water in Liquid Petroleum Products by Karl Fischer Reagent
Practice for Calculating Viscosity Index from
Kinematic Viscosity at 40C and 100C
Test Method for Oxidation Stability of Steam Turbine Oils by Rotating Pressure Vessel
Test Method for Estimation of Molecular Weight
(Relative Molecular Mass) of Petroleum Oils from
Viscosity Measurements
Test Method for Relative Molecular Mass (Molecular Weight) of Hydrocarbons by Thermoelectric
Measurement of Vapor Pressure
Test Method for Hydrolytic Stability of Hydraulic
Fluids (Beverage Bottle Method)
Test Method for Demulsibity Characteristics of
Lubricating Oils
Test Method for Thermal Conductivity of Liquids
Test Method for Specific Heat of Liquids and
Solids
Test Method for Estimation of Solubility of Gases
in Petroleum Liquids
Test Method for Solubility of Fixed Gases in Liquids
Test Method for Measurement of Extreme-Pressure Properties of Lubricating Fluids (Four-Ball
Method)
Test Method for Air Release of Petroleum Oils
Test Method for Estimation of Solubility of Gases
in Petroleum and Other Organic Liquids
Test Method for Water and Sediment in Crude Oil
by the Centrifuge Method (Laboratory Procedure)
Test Method for Wear Preventive Cheiracteristics
of Lubricating Fluid (Four-Ball Method)
Test Method for Determination of Carbon
Residue (Micro Method)
E 659
OTHER STANDARDS
No.
DIN 51352
DIN 51352
IP 239
ISO 5388
I S O 6743-3A
JIS K 2514
Title
P a r t 1 D e t e r m i n a t i o n of A g i n g C h a r a c t e r i s t i c s
of L u b r i c a t i n g O i l s . I n c r e a s e i n C o n r a d s o n
c a r b o n residue after aging by passing air
t h r o u g h t h e l u b r i c a t i n g oil.
P a r t 2 D e t e r m i n a t i o n of A g i n g C h a r a c t e r i s t i c s
of L u b r i c a t i n g O i l s . I n c r e a s e i n C o n r a d s o n
c a r b o n residue after aging by passing air
t h r o u g h t h e l u b r i c a t i n g oil i n t h e p r e s e n c e of
iron(III) oxide.
D e t e r m i n a t i o n of E x t r e m e P r e s s u r e a n d Antiw e a r P r o p e r t i e s of L u b r i c a n t s - F o u r Ball M a chine Method
Stationary air compressors-Safety rules a n d
c o d e of p r a c t i c e
L u b r i c a n t s , i n d u s t r i a l oils, a n d r e l a t e d p r o d u c t s (Class L ) - C l a s s i f i c a t i o n - P a r t 3A: F a m i l y
D (Compressors)
T e s t i n g M e t h o d of O x i d a t i o n C h a r a c t e r i s t i c s
of E n g i n e Oils
REFERENCES
[1] Lilje, K. C , Short G. D., and Miller, J. W., "Compressors and
Pumps," Ch. 4, Synthetic Lubricants and
High-Performance
Functional Fluids, 2"'' ed., L. R. Rudnick and R. L. Shubkin,
Eds., Marcel Dekker Inc., NY, 1999, pp. 539-558.
[2] Patzau S. and Szchawnicka, E., "Oils for Air and Technical Gas
Compressors," Trybologia, Vol. 20, No. 4, 1989, pp. 18-21.
[3] Scales, W., "Air Compressor Lubrication," Ch. 19, Tribology
Data Handbook, E. R. Booser, Ed., CRC Press, Boca Raton, FL,
1997, pp. 242-247.
[4] Bloch, H. P., A Practical Guide to Compressor Technology, McGraw-Hill Inc., NY, 1996.
[5] "Unit Course 2-For Natural Gas Compressors-Considerations
for Sizing a Reciprocating Gas Compressor Package," Weatherford Compression, Corpus Christi, TX.
[6] Istvan, V., "Interplant Tests of Chemical Plant Lubricants: - Part
2-Compressor Oils and Heating System Oils and Their Application: Grease Lubrication," Magyar Kemikasok Lapja, Vol. 53,
No. 3, 1998, pp. 139-144.
[7] "Unit Course 1-For Natural Gas Compressors-An Introduction
to the Basic Function and Components of a Gas Compressor
Package," Weatherford Compression, Corpus Christi, TX.
[8] Matthews, P. H. D., "Lubrication of Reciprocating Compressors," Journal of Synthetic Lubricants, Vol. 6, No. 4, 1990, pp.
292-317.
[9] Wills, J. G., "Compressors," Ch. 14, Lubrication
Fundamentals,
Marcel Dekker, Inc., NY, 1980, pp. 365-394.
411
[10] Short, G. D., "Development of Synthetic Lubricants for Extended Life in Rotary-Screw Compressors," Lubrication Engineering, Vol. 40, No. 8, 1983, pp. 463-470.
[11] Carswell, R., McGraw, P. W., and Ward, E. L., "A Blend of a
Polyglycol and a Trtra Ester as a Lubricant for Rotary Screw Air
Compressors," Lubrication Engineering, Vol. 39, No. 11, 1982,
pp. 684-689.
[12] Miller, J. W., "Synthetic and HVI Compressor Lubricants," Journal of Synthetic Lubricants, Vol. 6, No. 2, 1989, pp. 107-122.
[13] Kist, K. R. and Doperalski, E . J . "Brief Introduction to the Screw
Compressor," Paper 68E, AIChE 8 6 * National Meeting, 1979.
[14] Tolfa, J. C , "Synthetic Lubricants Suitable for Use in Process
and Hydrocarbon Gas Compressors," Lubrication
Engineering,
Vol. 47, No. 4, 1990, pp. 289-295.
[15] Cohen, S. C , "Development of a "Synthetic" Compressor Oil
Based on Two-Stage Hydrotreated Petroleum Basestocks," Lubrication Engineering, Vol. 44, No. 3, 1987, pp. 230-238.
[16] Kajdas, C , "Industrial Lubricants," Ch. 8, Chemistry and Technology of Lubricants, 1992, pp. 196-222.
[17] Arbocus, G., "Synthetic Compressor Lubricants-State of the
Art," Lubrication Engineering, Vol. 34, No. 7, 1977, pp. 372-374.
[18] Chen, C.-I., "Typical Lubricating Oil Properties," Tribology Data
Book, E. R. Booser, Ed. CRC Press, Boca Raton, FL, 1997, pp. 333.
[19] Miller, J. W., "Synthetic Lubricants and their Industrial Applications," Journal of Synthetic Lubricants, Vol. 1, No. 2, 1984, pp.
136-152.
[20] Klamann, D., Ullmann's Encyclopedia of Industrial
Chemistry,
5"" ed.. Vol. A15, VCH Verlagsges mbH, 1990, pp. 423-518.
[21] Randies, S. J., "Esters," Ch. 3, Synthetic Lubricants and HighPerformance Functional Fluids, 2"^ ed., L. R. Rudnick and R. L.
Shubkin, Eds., Marcel Dekker Inc., NY, 1999, pp. 63-102
[22] Sugiura, K., Miyagawa, T. and Nakano, H., "Laboratory Evaluation and Field Performance of Oil-Flooded Rotary Compressor
Oils," Lubrication Engineering, Vol. 38, No. 8, 1982, pp. 510518.
[23] Matthews, P. H. D., Walkden, R. H., and Williams, G. C , "Current and Future Developments of Lubricants for Industrial Air
Compressors," Paper N u m b e r C477/023/94, ImechE Conference, Proceedings of the Institute of Mechanical Engineers, 1994,
pp. 175-183.
[24] Van Ormer, H. P., "Trim Compressed Air Cost with Synthetic
Lubricants," Power, 1987, pp. 43-45.
[25] Miller, J. W., "New Synthetic Food-Grade Rotary-Screw Compressor Lubricant," Lubrication Engineering, Vol. 40, No. 7,
1983, pp. 433-436.
[26] Takashima, H., "Gas Compressor Oils," Toraiborojisuto, Vol. 38,
1993, pp. 135-139.
[27] Hampson, D. F. G., "Reducing the Risk of Fires in Large Reciprocating Air Compressor Systems," Wear, Vol. 34, 1975, pp. 399407.
[28] McCoy, C. S. and Hanly, F. J. "Fire-Resistant Lubes Reduce
Danger of Refinery Explosions," The Oil and Gas Journal,
November 10, 1975, pp. 191-197.
[29] Garg, D. R., "Polyalkylene Glycol-Based Compressor Lubricants," presented at the Sixth Annual Reciprocating Compressor
Conference, Salt Lake City, UT, 23-26 Sept. 1991.
[30] Oberle J. and Rajewski, T., "The Development of Lubricants for
Ammonia Refrigeration Systems," presented at the 11AR 19'*'
Annual Meeting, 23-26 March 1997, New Orleans, LA.
[31] Whiting, R., "Monitoring Energy Savings of Diester Compressor
Oils," 6 * International Colloquium, Technische Akademie Essligen, 1998, pp. 14.41-14.43.
[32] Mills, A. J., Tempest, M. A., and Thomas, A. S., "Performance
Testing of Rotary Screw Air Compressor Fluids in Europe," Lubrication Engineering, Vol. 42, No. 5, 1986, pp. 278-286.
[33] Blackwell, J. W., BuUen, J. V., and Shubkin, R. L., "Current and
, Future Polyalphaolefins," Proceedings of the Conference on Syn-
MNL37-EB/Jun. 2003
A further consideration for proper choice of lubricant depends on whether the system is of the hermetically sealed
type, such as that found in window rack or other portable A/C
installations, or is designed to be serviced periodically, such
as outdoor residential and commercial units. In hermetically
sealed systems, the motor windings are exposed to the refrigerant/lubricant mixture. This mixture must have both good
electric insulating properties a n d chemical compatibility
with seals, materials of construction, and residual contaminants. A hermetically sealed system is charged with refrigerant and lubricant and sealed only once, with an expected
maintenance-free life of fifteen years or more. The older lubricants, such as mineral oil or synthetic alkylbenzene formulations, were mainly non-polar and did not dissolve and
hold significant amounts of residual materials of construction, assembly cleaning solvents, and the like in suspension.
The solubility of such compounds is much higher in many of
413
Copyright'
2003 by A S I M International
www.astm.org
414
MANUAL
HANDBOOK
Very recently, the use of immiscible lubricants, such as mineral oils, in systems using hydrofluorocarbon refrigerants, has
been the subject of renewed discussion in the Heating, Ventilation, and Air Conditioning, (HVAC) and refrigeration industry. The initial decision of the HVAC industry to use
polyalkylene glycol (FAG) and polyolester (POE) lubricants in
conjunction with the new hydrofluorocarbon refrigerants was
based on the assumption that high mutual solubility and miscibility between a lubricant and refrigerant were required for
proper lubricant circulation and compressor operation. Thus,
lubricants such as POEs were chosen because their polar
characteristics are similar to hydrofluorocarbons, resulting in
good mutual solubility and an assumed system behavior similar to the older hydrochlorocarbon and mineral oil mixtures.
Recent lubricant circulation studies have shown, however,
that except for low temperature refrigeration applications,
immiscible lubricant (alkyl based)/refrigerant mixtures can
be used in systems where return lines have been properly
sized [12,13]. The potential for significant cost reductions due
to the use of lower cost lubricants, such as mineral oils, rather
than the more expensive synthetic lubricants, has generated
renewed interest from HVAC system manufacturers. However, there are many issues associated with proper lubricant
circulation, mixture chemical stability, and compressor lubrication that must be addressed before there will likely be a
significant industry movement toward the use of immiscible
lubricant/refrigerant mixtures.
In the sections below, the properties of mineral oil based
and synthetic refrigerant lubricants will be described. These
lubricants differ in their chemical stability, solubility characteristics in different hydrohalocarbons, and viscosity and lubricity properties. There is extensive literature on the natural
mineral oil based lubricants [14,15]. This review will focus
more on the properties of the newer synthetic lubricant structures. The critical system issues such as oil holdup and compressor compatibility are also reviewed.
CHEMICAL STRUCTURE OF
REFRIGERANT LUBRICANTS
Mineral oil based lubricants used in refrigeration are generally of three types: paraffinic, which consist of both straight
and branch chain saturated hydrocarbons; napthenic, which
are saturated hydrocarbons that mainly consist of cyclic or
ring structures; and aromatics, which are comprised mainly
of unsaturated cyclic hydrocarbons. Typically, the crude oil
sources from which these lubricants are distilled and refined
contain a mixture of these mineral oil types. For this reason,
it is c o m m o n to identify mineral oils in terms of the number
of carbon atoms associated with each of the structures, paraffinic (Cp), napthenic (CN), and aromatic (NA): the carbon-type
composition is usually expressed in terms of weight percent.
Since this type of identification requires a time consuming
laboratory analysis, more qualitative methods of analysis
based on refractive index and photoabsorption have been introduced and standardized as ASTM D 2140, ASTM D 2549,
and ASTM D 2008. In general, paraffinic oils have a higher
percentage of paraffin wax (saturated straight chain
molecules) than napthenic oils, which results in high pour
points (ASTM D 97), the temperature at which the oil will flow
CHAPTER
15: REFRIGERATION
LUBRICANTSPROPERTIES
AND APPLICATIONS
415
Naphthenic
Parafflnic
0.92
33
12
0.86
34
95
25
300
-43
170
30
378
-18
200
52*
0*
Alkylbenzene
0.87
32
27
25
320
-46
178
-70*
Polyalkylene
Glycol
0.99
30
210
14
750
-46
200
Polyolester
Polyvinylether
0.97
30
90
0.92
30
69
15-18
500-600
-48
234
20
500-600
-45
212
<34
S50
CH3
CH3
I
CH3 CH CH2 - C -
I
CH3
I
/ ^
[CHCH2]CH CH3
'
CH3
n = 2-5 branched alkyl groups
CH3 - CH - CH2
I
[CHd^
I
CH3
CH - CH2 - CH2
I
I
[CHz]^
[CHj],
I
I
CH3
CH3
under gravity at prescribed conditions. Parafflnic oils, however, exhibit a m u c h higher viscosity index (ASTM D 2270) a
measure of the viscosity change with temperature, t h a n
napthenic oils. Owing to concerns about expansion valve and
capillary line plugging, and oil trapping in evaporators, typical mineral oil formulations that have been in use in refrigeration have low wax content. Mineral oils are formulated in a
fixed range of viscosity by adjusting the refining process. Specific system requirements, such as high resistance to oxidation, are mainly addressed by the use of additives.
Synthetic lubricants are produced by chemically combining
base stock hydrocarbon components in fixed proportions to
form a mixture with the desired lubrication characteristics.
Unlike mineral oils, which may consist of hundreds of different hydrocarbon molecules and whose composition varies
with the source of the crude oil, synthetic lubricants are tailored from a small number of different molecular weight starting components that are reacted to yield a final mixture of
compounds with the desired viscosity properties. These manmade lubricants can be classified by the type of base stock used
in their manufacture. The following synthetic types are commonly used in A/C and refrigeration systems: alkylbenzenes,
olefin oligomers (poly-a olefins), dibasic acid esters, polyolesters, and polyalkylene glycols [16,18]. Other synthetic lubricants such as the phosphate esters, silicones, monocarbonates, and fludrocarbon lubricants have not met with wide
usage due either to their poor thermal stability, their viscosity
and/or solubility characteristics with refrigerants, or their high
cost of manufacture. Typical properties for several of the comm o n refrigerant lubricants are given in Table 1.
group can be either a straight chain or branched chain paraffin, usually containing 10-20 carbon atoms. A typical structure of a commonly used branched chain alkylbenzene is
shown in Fig. 1.
Alkylbenzenes have excellent low temperature fluidity and
low pour points. Their viscosity indexes are somewhat lower
than those of typical mineral oils. They are stable against
oxidation, high temperature decomposition, and hydrolysis,
and are completely compatible with mineral oils [19]. Alkylbenzenes have found widespread use with refrigerant systems using R-22 and R-502, but have had limited use to date
with hydrofluorocarbon refrigerants owing to their immiscibility with these more polar molecules. However, since alkylbenzenes are man-made compounds, there have been several
recent studies directed toward changing the typical balance
of low, intermediate, and high molecular weight compounds
that are formed in the synthesis process [12,13]. If the percentage of high molecular weight components could be kept
low, the resulting alkylbenzene blend may have sufficient
fluidity to be carried by the vapor stream back to the compressor with m i n i m u m holdup in the evaporator, for example. These newer alkylbenzene formulations are sometimes
referred to as hard alkylbenzene lubricants (HAB). They are
currently under evaluation for use in hydrofluorocarbon systems using rotary compressors, where vane wear is a serious
issue with several of the synthetic lubricants.
Alkylbenzene (AB)
These synthesized hydrocarbon molecules are formed by the
alkylation of an aromatic compound, usually benzene, in the
presence of a catalyst such as aluminum chloride. The alkyl
416
MANUAL
HANDBOOK
thesized that exhibit similar physical properties [23]. These
polybasic esters have tetrahedral character about a central
carbon atom, similar to several of the polyolesters. They can
be formed by the reaction of acrylate esters with malonate esters to form, for example, estrs of 1,3,3,5-pentanetetracarboxylic acid. Dibasic esters are used in the formulation of
sjTithetic automotive lubricants and in jet engine oils. They
are not highly miscible with the new hydrofluorocarbon refrigerants but their use in some refrigeration systems has
been reported. However, this class of synthetic lubricants has
not yet found widespread usage in new A/C and refrigeration
systems.
Polyolesters (POE)
Polyolesters are the condensation product of an alcohol with
two or more hydroxyl groups (polyhydric alcohol or polyol),
and a monobasic (carboxylic) acid. In these structures, the
carboxylic acid links to all available hydroxyls in the polyol,
splitting off water molecules at each linkage. A typical polyolester is shown in Fig. 4.
Similar to the dibasic esters, the polyolester structure can
be varied by changing the carboxylic acid and by the use of
one or more polyols [22]. Typically, neopentyl glycol, pentaerythritol, and dipentaerythritol are chosen as the polyols.
Dipentaerythritol is used mainly to form polyolesters of
higher viscosity but is typically found as a significant (12%)
by-product in commercial grades of pentaerythritol. Upon esterfication with a carboxylic acid, the result is a compound of
high molecular weight and high viscosity. Such compounds
are desired for high viscosity lubricant formulations but can
lead to plugging and waxing in certain low temperature systems. Generally, pentaerythritol is reacted with two or more
carboxylic acids to form an ester mixture with desired properties. Owing to the tetra-hydroxy structure of pentaerythritol, the use of two carboxylic acids results in the formation of
five different esters. The number of possible esters increases
rapidly if more carboxylic acids (or alcohols) are used resulting in complex chemical mixtures of the possible esters.
O
CH3 [CH2]3 CH CH2
O -
C -
O
[CH2]4 -
C -
0 -
CH2 - C H
[CHzls - C H 3
I
CH2
CH2
CH3
CH3
O
CH3 -
(CH2)4 -
C -
O
O -
CH2 ^
CH2 -
O -
C -
(CH2)4 -
CH3
CH2 -
O -
C -
(CH2)4 -
CH3
c
CH3 -
(CH2)4 -
C -
O -
CH2 /
II
11
CHAPTER
15: REFRIGERATION
LUBRICANTSPROPERTIES
AND APPLICATIONS
417
Ri O [CH2 CH 0 ] n R2
I
CH3
n = # of branched [CH2 CH O] groups
I
CH3
Rl ,R2 = alkyl end groups
FIG. 5Polyalkylene glycol derived from propylene oxide.
0-[R4-0]m-R5
R,
Rx (x = 1-5) = alkyl groups
FIG.
6General
polyvinylethers.
molecular
structure
for
CHAPTER
15: REFRIGERATION
Anti-Wear Additives
Lubricants that are used in A/C and refrigeration systems
suffer from dilution effects of the refrigerant with a corresponding decrease in viscosity. In systems that employ chlorofluorocarbon refrigerants, the refrigerant can react with
the bearing metal under pressure, and the resulting frictional
heat generated by sliding metal surfaces forms a metal chloride coating that protects against direct metal to metal contact. Hydrofluorocarbon refrigerants do not offer this protective feature and anti-wear additives are tj^ically added to the
synthetic lubricants that are used in these newer systems.
These additives can be classified into two categories: those
that are formulated to provide protection under normal operating conditions (anti-wear agents) and those that are formulated for use during system break-in and extreme operating conditions (extreme pressure agents) [36]. Extreme
pressure (EP) agents can be evaluated using the ASTM D
3233 test procedure. Both anti-wear and extreme pressure
agents function by thermally activated chemical reactions,
forming compounds that react with the metal surface to form
a protective layer. Thiophosphates have t3TDically been used
as anti-wear agents. Extreme pressure agents include aryl
disulfides, thiocarbamates, and several classes of organic
phosphorous compounds [37,38]. Extreme pressure agents
react at higher temperatures than anti-wear agents. At higher
temperatures (>200 C) and under heavy loads, these agents
modify the structure of sliding surfaces by lowering the
height of aspertites and forming a protective film. In effect,
they act as polishing agents that reduce the high level of friction that may be encountered during system break-in.
Experience with the use of anti-wear and extreme pressure
agents in hydrofluorocarbon/synthetic lubricant systems has
LUBRICANTSPROPERTIES
AND APPLICATIONS
419
Acid Catchers
The use of compounds to control acid levels is especially important in synthetic lubricant systems. In contrast to mineral
oil lubricants, polyolester and polyalkylene glycols can adsorb (by hydrogen bonding), significant amounts of water. In
some cases, the lubricant or system processing fluids can react with water, forming organic acids that can result in wear
and corrosion. Tjrpical compounds that are used to control
acid level are the alkanolamines, long chain amides and
imines, carbomates, and epoxides. This latter class of compounds has found extensive use in polyolester based systems.
T5rpical concentrations of 0.1-0.5 weight percent are used for
water and acid control in hydrofluorocarbon systems. A potential disadvantage in the use of acid catchers is their reactivity with other additives such as anti-weeir agents. Control
of water and acid by proper system design, cleanliness in system assembly, and proper maintenance are preferred strategies.
Anti-Foaming Agents
Foaming in a refrigeration system is caused by mechanical
mixing of the lubricant and the refrigerant, by the sudden release of refrigerant gas from the lubricant when pressures are
reduced, and by outgassing that can occur at system start-up.
The type of foam that is formed in chlorofluorocarbon/mineral oil systems is persistent and undergoes a slow collapse.
In hydrofluorocarbon/synthetic lubricant systems, foam typically forms and collapses rapidly with the potential of lubricant transport out of the compressor sump zind ineffectiveness in its action to modify compressor noise. Compounds
that have been used to control foaming characteristics include the poly dimethyl siloxanes, polyalkoxyamines, a n d
polyacrylates. These compounds act to modify the surface
tension of the lubricant/refrigerant mixture. They are typically employed at the 100-1000 p p m level. Their disadvan-
HANDBOOK
tage is that other chemical compounds in the system can often react with foaming agents rendering them ineffective.
Their chemical stabihty under severe system operating conditions is also uncertain.
Other additives that have been considered for use in A/C
and refrigeration systems are copper deactivators to protect
connecting lines and components, viscosity improvers, sealswell agents, detergents, and emulsifiers/demulsifiers. Such
additives have the potential of creating more problems than
are solved by their usage. Proper system design and choice of
lubricant are more fundamental to long life system operation
than the use of additives with their potential for adverse
chemical reactions.
(1)
(2)
where 77 is the kinematic viscosity given in cSt, T is the absolute temperature in Kelvin degrees and a and b are constants
derived from experimental data. A more rigorous model for
describing the temperature dependence of viscosity is the extended Andrade equation [39]:
lnfi = A + YB + CT + DT^
(3)
where fji. is the absolute viscosity and A, B, C, and D are constants fitted to experimental data. This form is often more
useful for modeling viscosity at the lower temperatures encountered in refrigeration. Eq 3 has been applied to model
the temperature dependence for both refrigerant and lubricant viscosity.
Pure refrigerant density is often represented by the
equation:
ft.(T) = a -I- bX -I- cX^ -t- dX^ + eX''
(4)
a -F bT -(- cT^
(5)
CHAPTER
15: REFRIGERATION
LUBRICANTSPROPERTIES
fects arising from a dilution of the lubricant with refrigerant. Under normal system operating conditions, the lubricant in the compressor crankcase may be diluted by a few
percent of the refrigerant. Upon start-up, however, if the
ambient temperature at the compressor location is cold, the
lubricant in the compressor sump can be highly diluted
(30%) with refrigerant that has migrated to this cold point
in the system. In most A/C and refrigeration applications,
some lubricant is carried out of the compressor and circulates with the refrigerant. Typically, the percentage of circulating lubricant is small, especially for systems with scroll
design compressors, but can be as high as 3% for systems
with reciprocating compressors that have seen extensive
service. This circulating lubricant-rich mixture can impact
system performance in several ways. Refrigerant/lubricant
miscibility limitations may result in a two-phase liquid region under certain conditions of temperature and pressure.
The most serious effect is the possible development of a
highly viscous phase in the evaporator section that may result in decreased heat transfer rates.
In the case of refrigerant blends, such as R-407C, a new
problem arises since the individual system components may
exhibit different solubilities in the lubricant [9,10]. These different component solubilities can give rise to fractionation
(distillation) effects in the evaporator, condenser, or compressor sump that result in different vapor-liquid equilibrium
conditions and corresponding composition shifts. The effects
of these refrigerant/lubricant interactions may impact both
cycle analysis and system performance. If these chemical interactions are significant (non-ideal solution behavior), they
may result in detrimental performance and lower system operating efficiency. Several models have been developed to analyze the solubility effects of lubricant/refrigerant mixtures.
The thermophysical properties, density, viscosity and vapor
pressure, must be modeled to include the effects of mixture
composition.
Density
The molar volume of a lubricant/refrigerant mixture can be
written as:
V
U L V L + nRVR
(6)
Vmixture ^ L V L + X R V R
(7)
AND APPLICATIONS
421
Vmixture X L V L +
XRVR
(8)
xf
PR
(9)
Viscosity
Viscosity models based on empirical polynomial expansions
in temperature and composition have often been used to describe mixture behavior. Almost all models assume or require
that values for the viscosity of the p u r e components be
known. Thus, the primary feature for judging the validity of
viscosity models for mixtures is their utility in interpolating
data from the extreme composition limits of pure refrigerant
and pure lubricant. It is known that the viscosity of liquid
mixtures is not a simple function of composition. The viscosity of mixtures may exhibit a maximum, a minimum, or both
over a specified composition range. For the pure components, the extended Andrade [39] equation, a polynomial in
temperature, is often used to represent the temperature dependence of viscosity. Studies show that a four or five term
expansion can accurately represent viscosity for pure comp o n e n t s over the n o r m a l operating range of interest,
20C-80C, for both refrigerant and lubricant.
Difficulties can arise in developing reliable models to cover
mixtures ranging from pure lubricant to high refrigerant dilution levels. Owing to the large size differences between refrigerant and lubricant molecules, a reliable model must account
for both the difference in molar volumes of refrigerants and lubricants a n d for differences in molecular interaction
strengths. Most studies of the viscosity of liquid mixtures have
focused mainly on systems of molecules of nearly equal size
and have been restricted mainly to near-ideal mixtures. An
ideal mixture is one that undergoes zero volume change and
zero heat exchange upon mixing. For such mixtures, Arrhenius [44] proposed that mixture viscosity should be an additive
property, linearly connected to the viscosity of the pure components. Mixtures that exhibit this type of behavior are typiCcJly non-polar. Examples are hydrocarbons and halogenated
hydrocarbons, such as CFCs. The introduction of HFCs as refrigerants, which are m u c h more polar, has led to the use of polar polyolester lubricants to improve solution solubility and
miscibility. However, these new refrigerant/lubricant mixtures exhibit significant non-ideal character with very Icirge
molecular size differences between refrigerant and lubricant.
Data
Arrhenius:
Kendall:
Frenkel:
(10)
Grunberg-Nissan:
Yokozeki:
(11)
For binary polar mixtures, Irving [47] finds that the Grunberg-Nissan equation has the smallest average error when
tested with nearly 1000 data points, taking 4>i as the mole
fraction of component i and optimizing the value of the adjustable parameter, G12, using mixture data. A variation of Eq
11, based on a kinetic model involving binary pair activation
energies, is due to Frenkel [48]:
In T7ix,ure = xf In Tji + xl In 172 + 2x1X2 In 1712
(12)
In rjn
0.3
0.4
0.5
0.6
Mass Fraction Refrigerant
0.7
0.8
temperature. Yokozeki finds that k ~ 0.58 for many refrigerant mixtures but finds that k must be treated as an adjustable parameter for refrigerant/lubricant mixtures. For k
= 0, the Yokozeki model reduces to the model proposed by
Kendall. For k = 1, the concentration measure becomes
weight fraction rather t h a n mole fraction. A genereilized
definition of the concentration measure, ^i, can be shown to
be related to the familiar q-ratio (the ratio of the van der
Waals surface area for lubricant and refrigerant) in UNIFAC and other solution theory models [50,51]. In Figs. 7
and 8, the viscosities of R-22/AB150 and R-134a/FOE-68
mixtures are compared against several models that have
been proposed [51]. In general, one- or two-parameter models are required to quantitatively represent experimental
mixture data.
(13)
Solubility
In Eq 13, Xj and m^ refer to the mole fraction and molecular weight of component I, respectively, and k is an empirical parameter, often modeled as a simple polynomial in the
Data
-Airheimis: [44]
-Kendall: [45]
-Frenkel [48]
-Grunberg-Nissan: [46]
-Yoko2Eld: [49]
- McAllister 3-Body Model: [47]
- McAllister 4-Body Model: [47]
-Michels-Sienel: [51]
The solubility of a refrigerant in a lubricant has been modeled using several different approaches. The older literature
solubility data on mineral oil/CFC mixtures have mainly been
analyzed using empirical correlations in temperature and
composition [52]. Models that are thermodynamically more
rigorous have been developed that are applicable to the
more polar hydrofluorocarbon/synthetic lubricant mixtures
[9,43,49,53]. These models have been based either on a n
equation of state approach or on non-ideal solution theory. A
comparison of the features of these different approaches is
given in Table 2.
Empirical correlations are usually polynomial fits of the
mixture vapor pressure as a function of temperature (T) and
composition (x).
P = X aioT' + x X a i i P + x^ a i 2 r + .
(14)
P = bio/P + X X b/T> + X2 X b i 2 / r +.
0.1
0.2
0.3
0.4
0.5
0.6
Mass Fraction Reffigerant
0.7
0.8
0.9
InP = C(x)
D(x)
T + constant
C(x) = Yi CiXi;
(15)
where
yi = vapor phase molar composition of component i,
PT = total system pressure at temperature T,
4>i = vapor phase fugacity coefficient which, for moderate
pressure, can be estimated from second virial coefficient data,
Xi = liquid phase molar composition of component i,
Yi = liquid phase activity coefficient,
P,^ = vapor pressure of pure component / at temperature T,
4)* = fugacity coefficient for pure i at the system T and P,
Fi = pointing factor for compressibility of the liquid
phase.
J , * ^= T7?
(f)*
F | = 1.0, this analysis reduces to an idea
solution description and is representative of Raoult's Law.
Combining the fugacity coefficients and Poynting factor into
a correction term, F the vapor-liquid equilibria for component i in solution can be written as:
F o r 4>}'
iVc!
yiPr = Xi7iPrFS
(16)
T=60C.--
T-OfC
-T=20fC
- T=40 C
- T=60 C
c
o
0.2
0.4
0.6
0.8
T=0Cdata
T= 20 C data
T= 40 C data
T=60Cdata
_ .
- T-OPC
-T=2ff'C
- T=40 C
- T=60 C
0.2
0.4
0.6
T=0Cdata
T= 20 C data
T- 40 C data
T- 60 C data
0.8
LUBRICANT CIRCULATION
The purpose of the lubricant in the HVAC system is to lubricate, cool, seal, and otherwise protect the compressor in the
system from failure. In the course of executing these functions, some lubricant is captured in the compression process
and carried by the refrigerant out of the compressor. Within
the remainder of the system, the lubricant serves little to n o
useful function, and acts as a detriment to system performance u n d e r most conditions. The challenge to the system
designer is to ensure that the lubricant returns to the compressor satisfactorily u n d e r all operating conditions, as a prolonged migration of the lubricant from the compressor into
the system will result in performance degradation and eventually compressor failure due to lack of lubricant. The design
considerations influencing adequate lubricant return consist
of line sizing, lubricant and refrigerant selection, system operational envelope, and transient effects, each of which will
be described in further detail. Measurement of the circulation in these systems is also a challenge, particularly when
transient phenomena occur, and this will be considered in
further detail as well.
HVAC Cycle
Vapor compression systems, in basic form, consist of a compressor, a heat rejecting heat exchanger (typically referred to
as a condenser), an expansion device, and a heat absorbing
heat exchanger (t5^ically referred to as an evaporator). The
cycle begins with the refrigerant as a high pressure vapor at
the exit of the compressor. It next flows through the condenser, rejecting heat, cooling, and condensing to become a
liquid at the discharge of the condenser. Next, the pressure of
the refrigerant is dropped as it flows through the expansion
device, which can be as simple as a kink in the refrigerant line
or as sophisticated as a microprocessor-controlled, electronically-actuated stepper motor connected to a needle valve. At
the exit of the expansion device, the refrigerant has typically
entered into the two phase region again and enters the evaporator. The evaporator absorbs heat from the environment and
uses it to evaporate the refrigerant back to vapor form. Finally,
the vapor refrigerant enters the compressor, where it is compressed and heated to begin the cycle again. This process is
shown schematically in Figs. 1 2 a n d l 3 , which depict the pressure-enthalpy and temperature-entropy diagrams of the cycle.
This cycle is important to understand as it influences all of the
design considerations impacting lubricant transport.
In addition to the basic components, many systems are
equipped with additional components serving a variety of
functions. Charge storage devices, such as accumulators and
receivers, are used in systems that have large operational envelopes and, due to the density differences of the refrigerant at
the different operational temperatures, require significantly
different amounts of refrigerant at different conditions. Receivers are employed where liquid flows through the lines, typically in the high pressure part of the system between the exit
of the condenser and the expansion device. The liquid flowing
into the expansion device is drawn from the receiver and, be-
10
20
Temperature (C)
60
30
10000
Liquid
>
1000
i
I
100
10
50
250
450
Enthalpy (kj/kg)
1.5
1
1.5
Entropy (kJ/kg-K)
426
HANDBOOK
100 -|
Insufficient Velocity
r 3
Sufficient Velocity
90 80 .
- 2.5
70 &
^
a
60 50 -
40-
-2
- 1-5 Q
^y>
30 -
-0.5
10 0
r 1
IS
s
OH
20 0 i
-5%
o.
^ ,
- 0
2
CHAPTER
80
60
40
20
0
E
u -20
w -40
H
-60
-80
15: REFRIGERATION
Immiscible
Lower CST
Miscible
Upper CST
Immiscible
20
40
60
80
gions of immiscibility are usually defined by the critical (consolute) solution temperature, as shown in Fig. 15 for R-410A
and POE-68. In the immiscible region, two liquid phases will
form, one lubricant rich and one refrigerant rich. These two
phases will have different densities, and in an actual system,
stagnant liquid will tend to separate according to these density differences. If the lubricant rich phase is less dense than
the refrigerant rich phase, it will float above the refrigerant
dense phase. This is the preferred arrangement for most of
the system lines, as the lubricant rich phase can still be entrained into the vapor flow. If the situation were reversed, the
lubricant rich phase could become trapped below the refrigerant rich phase, leading to poor lubricant return to the compressor. On the other hand, for receivers the situation can be
reversed, as liquid flow to the expansion valve is generally
drawn from the bottom of the device. If the lubricant rich
phase floats above the refrigerant rich phase in this case, it
will not be drawn into the remainder of the cycle and will essentially become trapped. For accumulators, where vapor
flows from the exit and only a small a m o u n t of liquid becomes entrained into this vapor flow through an oil return
mechanism, an immiscible system in combination with system geometry can also produce a situation where lubricant
does not flow back to the compressor. Experiences with this
situation have led to accumulator designs where the contents
are continuously agitated so as to reduce or eliminate stratification. Flooded heat exchangers are also a concern for lubricant holdup. These typically shell and tube heat exchanges
are used in chiller or other liquid heat transfer systems
where, if the lubricant rich phase is less dense than the refrigerant rich phase, oil holdup can occur in portions of the
heat exchanger.
LUBRICANTSPROPERTIES
AND APPLICATIONS
427
be extremely high. Newer refrigerant-lubricant combinations, such as HFC-POEs, have tended to exhibit higher viscosities than the older combinations, such as CFC-MOs that
have been used for these applications. When the lubricant
viscosity becomes sufficiently high, it becomes similar to
wax, and transport becomes difficult, if not impossible. As lubricant continues to build u p in the low temperature portion
of the system (evaporator), this will have a noticeable effect
on heat transfer and pressure drop in the heat exchanger and
thus on performance. The saving grace for these conditions is
often system transients, such as defrost cycles or slugs of relatively w a r m refrigerant, which sufficiently decrease the viscosity of the lubricant to allow transport back to the system.
At the same time, due to the high pressure differences in the
system, compressor discharge temperatures are higher than
at low lift conditions. Both of these conditions lead to contradictory requirements: the desire for a low viscosity lubricant at low temperature, refrigerant dilute conditions; and a
relatively high viscosity lubricant at high temperature, refrigerant rich conditions. This is, of course, the same lubricant,
and must be chosen carefully.
428
MANUAL
HANDBOOK
ASTM STANDARDS
No.
D 97
D 445
D 664
D 891
D 892
D 943
D 1169
D 2008
PERFORMANCE EFFECTS
D 2140
The lubricant in the HVAC system has distinct performance
impacts on the compressor, the heat exchangers, and working fluid, all of which combine to affect system performance.
The compressor requires a certain lubricant viscosity for adequate protection. If the fluid viscosity drops below this limit,
damage to the compressor may occur due to bearing failure.
On the other hand, if the lubricant is too viscous, the drag on
the bearings as weU as any sealing surfaces will increase, resulting in an increase in consumed power and a reduction in
performance.
For the heat exchangers, many of the lubricant impacts
have already been discussed. Some studies have suggested
that trace amounts of lubricant actually aid in heat transfer
properties and thus system performance [75]. However, anything above trace amounts (typically 0.1% OCR) has generally
been reported to have a negative performance impact. Lubricant in the vapor phase of the heat exchanger introduces a
contact resistance, which detracts from the overall heat transfer coefficient. The degree to which this impacts performance
is a function of the amount of OCR and lubricant hold up.
Studies have suggested that the degree of performance degradation caused by the lubricant can be related to the lubricant
viscosity at the exit of the evaporator [76]. Under refrigeration
conditions, the holdup can have a severe performance impact
as the holdup also influences pressure drop.
Finally, the fluid performance is also impacted due to the
displacement of refrigerant from the flow. The lubricant does
not aid substantially in the transfer of heat from the heat absorbing heat exchanger to the heat rejecting heat exchanger.
Thus, for every percent lubricant flowing in the bulk flow, a
corresponding percent drop in performance can be expected.
For multi-component refrigersint mixtures (ctny of the R-400
series of refrigerants), differential solubility effects can cause
the circulating composition to fractionate, changing the per-
D 2270
D2549
D 2670
D 3233
D 5846
D 6304
E 203
F2161
G 125
Title
S t a n d a r d Test Method for Pour Point of
Petroleum Products
Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids
S t a n d a r d Test Method for Acid N u m b e r of
Petroleum Products by Potentiometric Titration
Standard Test Method for Specific Gravity, Apparent, of Liquid Industrial Chemicals
Standard Test Method for Foaming Characteristics of Lubricating Oils
Standard Test Method for Oxidation Characteristics of Inhibited Mineral Oils
S t a n d a r d Test Method for Specific Resistance
(Resistivity) of Electric Insulating Fluids
Standcird Test Method for Ultraviolet Absorbance
and Absorptivity of Petroleum Products
Standard Test Method for Carbon-Type Composition of Insulating Oils of Petroleum Origin
Standard Practice for Calculating Viscosity Index
from Kinematic Viscosity
S t a n d a r d Test Method for Separation of
Representative Aromatic and Nonaromatic Fractions of High-Boiling Oils by Elution Chromatography
Standard Test Method for Measuring WeEir Properties of Fluid Lubricants (Falex Pin a n d Vee
Block Methods)
Standzird Test Method for Measurement of Extreme Pressure Properties of Fluid Lubricants
(FeJex Pin and Vee Block Methods)
Standard Test Method for Universal Oxidation
Test for Hydraulic a n d Turbine Oils Using the
Universal Oxidation Test Apparatus
S t a n d a r d Test Method for Determination of
Water in Petroleum Products, Lubricating Oils,
and Additives by Coulometric Karl Fischer Titration
Standard Test Method for Water Using Volumetric Karl Fischer Titration
S t a n d a r d Guide for I n s t r u m e n t and Precision
Bearing LubricantsPart 1 Oils
S t a n d a r d Test Method for Measuring Liquid
and Solid Material Fire Limits in Gaseous Oxidants
ANSI/ASHRAE STANDARDS
34-1992
Determination of Refrigerant Lower Flammability Limit in Compliance with Proposed Addend u m p to Standard 34.
34-2001
REFERENCES
[1] 'Wills, J.G.,LubricationFundamentals,MarcelDekker,NY,
1980.
[2] Cameron, A., Basic Lubrication Theory, 3'''^ ed., Ellis Honvood,
Ltd., NY, 1981.
[3] Evans, C. R. and Johnson, K. L., "The Rheological Properties of
Elastohydrodynamic Lubricants," Proceedings of the Institute of
Mechanical Engineers, Vol. 200C, 1986, p. 303.
[4] Gunsel, S., Korcek, S., Smeeth, M., and Spikes, H. A., "The Elastohydrodynamic Friction and Film Forming Properties of Lubricant Base Oils," Tribology Transactions, Vol. 42, 1999, p. 559.
[5] Akei, M. and Mizuhara, K., "The Elastohydrodynamic Properties of Lubricants in Refrigerant Environments," Tribology
Transactions, Vol. 40, 1997, p. 1.
[6] Henderson, D. R., Rajewski, T. E., Speich, C. F., and Greig, B.,
"Lubricants in Refrigerant Systems," Chapter 7, ASHRAE Handbook-Fundamentals,
ASHRAE Publications, Atlanta, 1997.
[7] Rizvi, S. Q. A., "Lubricant Additives and Their Functions," ASM
Handbook, ASM International, Materials Park, OH, Vol. 18,
1992, pp. 98-112.
[8] DeVos, R., "R-134a Qualification-Industry Refrigerator Capillary Data," ASHRAE Transactions, BN-97-7-4, 1997, p. 1.
[9] Michels, H. H. and Sienel, T. H., "Solubility Modeling of Refrigerant/Lubricant Mixtures," Proceedings of the 1995 International
CHC and Halons Alternatives Conference, Alliance for Responsible CFC Policy, Frederick, MD, 1995.
[10] Biancardi. F. R., Sienel, T. H., Pandy, D. R., and Michels, H. H.,
"Modeling and Testing of Fractionation Effects with Refrigeration Blends in an Actual Residential Heat P u m p System,"
ASHRAE Transactions, Vol. 103, Pt. 1, 1997, pp. 1-14.
[11] Biancardi, F. R., Michels, H. H., Sienel, T. H., and Pandy, D. R.,
"Study of Lubricant Circulation in HVAC Systems," ASHRAE
Proceedings, GRA19715, 1997, p. 940.
[12] Sunami, M., Takigawa, K., Suda, S., and Sasoki, U., "New Immiscible Refrigeration Lubricant for HFCs," ASHRAE Transactions, SD-95-8-3, 1995, p. 940.
[13] Sunami, M., Taldgawa, K., and Suda, S., "New Immersible Refrigerant Lubricant for HFCs," Proceedings of the ASHRAEPurdue CFC Conference, Purdue University, West Lafayette, IN,
1994, p . 129.
[14] Godfrey, D. and Herguth, W. R., "Physical and Chemical Properties of Industrial Mineral Oils Affecting Lubrication," Lubrication Engineering, Vol. 51, No. 5, 1995, p . 397.
[15] Van Nes, K. and Weston, H. A., Aspects of the Constitution of
Mineral Oils, Elsevier, NY, 1951.
[16] Gunderson, R. C. and Hart, A W., Synthetic Lubricants, Reinhold, NY, 1962.
[17] Sanvordenker, K. S. and Larime, M. W., "A Review of Synthetic
Oils for Refrigeration Use," ASHRAE Lubricants Symposium,
ASHRAE Jandbook-Fundamentals, Atlanta, GA, 1972.
[18] Komatsuzaki, S. and Honama, Y., "Lubricants of HFC Refrigerant Compressors," Sekiyu Gakkaishi, Vol. 37, No. 3,1994, p. 226.
[19] Glova, D. J., "High Temperature Stability of Refrigerants in Lubricating Oils," ASHRAE Transactions, Vol. 90, No. 4, 1984, p.
806.
[20] Daniel, G., Anderson, M. J., Schmid, W., and Tokumitsu, M.,
Performance of Selected Synthetic Lubricants in Heat Pumps,
Heat Recovery Systems, Vol. 2, Pergamon Press, Oxford, 1982, p.
359.
MNL37-EB/Jun. 2003
Gear Lubricants
Vasudevan Bala^
have evolved continuously over the last 200 years [1]. These
improvements were largely attributed to advances in gear design, metallurgy, lubricant additives and base oil refining
[1,2]. Global trends in improved end user satisfaction, fuel
economy, lower down time, cheaper maintenance, and improved equipment durability have provided the necessary
motivation for increased competition among Original Equipm e n t Manufacturers (OEMs) [1-3]. As a result of these
trends, gear lubricants currently are formulated to meet exacting standcirds required to lubricate gear boxes and automotive drivelines. The following sections cover the basics in
gear lubrication and provide information in the selection of
proper gear lubricants depending on their end application.
431
Copyright'
www.astm.org
432
MANUAL
HANDBOOK
Name
Aristotle
Item
Explained gear wheel drives in windlasses; pointed out that the direction of rotation
is reversed when one gear wheel drives another gear wheel.
Made water clocks and water organs using gears.
Made rack and pinion devise to raise water.
Made devices to multiply force or torque many times; studied spiral.
Described the first real use of power gearing in mill drives.
Described gears (cogwheels) for many uses; ceJculated actual gear ratios; devised
distance (cyclometer) eind angle (dioptra) measurements using gears.
330 B.C.
250
230
220
27
60
Otesibius (Greek)
Philo of Byzanitum
Archimedes
Vitruvlus
Hero
B.C.
B.C.
B.C.
B.C.
A.D.
Gear Theorists
Name
Approximate
Date
Nicholas of Cusa
Albert Durer
Girolamo Cardano
Philip de la Hire
1451
1525
1557
1694
French
German
Swiss
French
Charles Camus
1733
French
Leonard Euler
1754
Swiss
Abraham Kaestner
1781
German
Robert Willis
Edward Sang
1832
1852
English
Scotch
Nationality
Contribution
Studied cycloidal curve.
Discovered epicycloids.
Developed first mathematics of gears in print.
Developed full mathematical analysis of epicycloids; recommended involute
curve for gearing (involute not used in practice until about 150 years later.
Expanded on work of la Hire; developed theories of mechanisms; studied
lantern pinion and gear, crown gears, and beveled gears.
Worked out design principles and rules for conjugate action some consider
him the "father of involute gearing."
Wrote practical methods for computing tooth shapes of epicycloid and
involute gear teeth; considered 15 degrees to be a minimum pressure angle.
Wrote and taught extensively in gear fielda pioneer in gear engineering.
Developed generaJ theory of gear teeth; provided theoretical basis on which
all gear tooth generating machines are based.
S:3
S:4
Date
S:l
1935
1948
1957
Cliemistry Type
S, CI
S, CI, P
Pb, CI, S*
Zn, S, CI, P*
Chlorine, %
Sulfur, %
Phosphorus, %
Lead, %
Zinc, %
Performance Level
Dosage, Wt %
Application
34
10
26
8
0.5
4.6
4.9
15
13
4
7.55
5-10
Automotive
GL-4'"
5-10
Automotive
GL-4*
28
Automotive
3.5
GL-4, GL-5*
5-10
Automotive
GEAR TYPES
Gears can be classified according to their tooth profile,
shape, loading, and direction of torque transfer [8a]. The
choice of these different gear types depends on these factors
and is seen in automotive and industrial applications. The
basic function of gears is to transmit power along with increasing or decreasing shaft speed. Gears can also be used to
deliver the required torque and, depending on the gear design
used, can be used to change the direction or axis of rotation.
In specific automotive applications, gears are used to synchronize shaft speeds in transmissions and change torque
transfer in front and rear axles.
There are different gear types used in automotive and industrial applications. The c o m m o n gear types are spur, helical, herringbone, w o r m , straight, and spiral-bevel a n d
hypoid. Spur gears come in straight, helical, and herringbone
designs. The most c o m m o n type is the straight spur gear type
that sees no axial forces a n d uses simple bearing design.
433
HELICAL GEARS
WORM GEARS
SPUR GEARS
Teeth In Parallel Plane To The
Axis
Oast Iron Or Steel
Noisy
Rough Operation
simple And Economical To
ManufQeture
single Tooth Contaot
Rolling And Sliding Motion
HERRINGBONE GEARS
Expensive To Manufacture
Quiet
Smoom Operation
Used For High Speed
Gearing
HYPOID GEARS
BEVEL GEARS
Noisy
Rough Operation
Limited To Low Siseeds
Greater Load Capabiltly
With Spiral Bevel
Intersecting
Gear Type
Spur
Straight
Helical
Bevel
Straight
Skew
Maximum
Transmission
Ratio
Maximum
Peripheral
Speed
Maximum
Output
(kN)
Maximum
Torque
(kNm)
10
10
10
10
5
25
200
2250
7500
22500
22500
22500
9000
2300
600
375
3750
3750
90
90
45
750
75
750
300
170
7
7
7
2.5
2.5
60
Crossing at 90
Worm
Crossed Helical
H5^oid
50
50
50
60
Crossing at 80-100
(not 90)
Worm
Crossed Helical
50
50
50
115
170
Brittle fracture
Ductile fracture
Plastic deformation
Cold flow
Hot flow
Indention
Rolling
Bruising
Peening
Brinelling
Rippling (fish scaling)
Ridging
Bending (3aelding)
Tip-to-root interference
Low-cycle fatigue
(scycles to failure)
High-cycle fatigue
( a 1000 cycles to failure)
Lubrication-related Failures
Hertizan Fatigue
Wear
ScuiBng
Pitting
Initial
Superficial
Destructive
Spalling
Micropitting
Frosting
Gray staining
Peeling
Subcase fatigue
(case crushing)
Adhesion
Running-in
Mild
Moderate
Severe
Excessive
Abrasion
Scoring
Scratching
Plowing
Cutting
Gouging
Corrosion
Fretting corrosion
Cavitation
Electrical dischsirge damage
Polishing (burnishing)
Scoring
Galling
Seizing
Welding
Smearing
Initial
Moderate
Destructive
CHAPTER
and frosting [8a] (Fig. 3). The specific film thickness has been
identified as a key parameter that influences micropitting [8].
The recommended guidehnes to prevent the onset of micropitting in gear sets are [11a]:
use smooth tooth surfaces produced by grinding or honing
use adequate amount of gear lubricant of the highest viscosity possible
use of high speed
use of carburized steel
Adhesive wear can be classified as mild or severe depending
on the cimount of wear seen on the gear tooth [10,11 a, 12]. Mild
adhesive wear generally occurs during break-in when the tooth
surface asperities are removed to improve the specific film
thickness. Severe wear has occurred when there is a significant
change in the tooth profile. The recommended guidelines for
preventing the onset of adhesive wear in gear sets are [11a]:
use smooth tooth surfaces
run-in new gear sets at 1/2 the load before use
Use higher speeds when possible. Under slow-speed high
loads, use nitrided gears combined with highest viscosity
lubricants
Abrasive wear is usually caused by foreign contamination
or wear debris from run-in of the gear sets [8a, 10,11a, 12]
(Fig. 4). Contamination can originate from inherently unclean gear boxes during build-up, ingressed through breather
valves a n d seals. Proper m a i n t e n a n c e of the gear box by
regular visual inspections and analyses of the lubricants can
reduce abrasive wear. The recommended guidelines for preventing abrasive wear in gear sets are [11a]:
1. Remove contamination during build-up with proper flushing and draining of the lubricant.
2. Refill with fresh lubricant and filter where applicable.
3. Use smooth surface hardened gears in combination with
high viscosity lubricants
4. Adopt regular maintenance schedules
5. Use filtrating systems with circulating oils
6. Follow OEM recommended drain intervals
7. Conduct used oil analyses to m o n i t o r condition of the
lubricant
Polishing wear is believed to be caused by continuous removal of the reactive boundary layer by fine abrasive material
435
436
HANDBOOK
GEAR LUBRICATION
The conforming surfaces of gear teeth in mesh can operate
under three different modes of lubrication: boundary, mixed,
and elastohydrodynamic. Boundary lubrication occurs
during start-up or stopping conditions. In certain conditions of heavy loads and slow speeds e.g., towing, boundary
condition persists between the pinion and ring gears in automotive hypoid axles. Under boundary conditions, the additive system present in the gear lubricant prevents scuffing,
metal adhesion, and wear.
Under higher speeds and/or lighter loads, the gears operate
under mixed lubrication. Under mixed lubrication, gear surface asperities still come in contact and wear occurs at a
slower rate than under boundary lubrication. Both the viscosity of the gear lubricant and the additive system can influence
optimum gear performance under mix lubrication. ElastohydrodjTiamic (EHD) lubrication provides the optimum condition under which separation of gear teeth occurs, minimizing
wear. The lubricant's viscosity is important under EHD lubrication and is affected by proper selection of the lubricant viscosity grade. Table 5 provides the necessary equations that describe the calculation of film thicknesses under EHD for spur
and bevel gears with straight and helical teeth [9].
Figure 7 shows the typical contact between gear teeth for
spur, helical, and bevel gears [14]. The contact starts with
high sliding and some rolling. The sliding reduces to pure
rolling at the center of the gear tooth or pitch line after which
rolling decreases with increasing sliding. Generally, under
these conditions, the gear teeth undergo boundary to EHD
and back to boundary lubrication. Mixed and boundary lubrications generally persist for hypoid gear sets. EHD theory
has shown that film thicknesses of ~1 micron can prevent
surface asperities from coming in contact [15]. Under the
conditions of high pressure, the lubricant can exhibit viscosity increases that maintain film thickness. Increases in the
relative velocities of the gear tooth surfaces, gear lubricant
viscosity, and in the radius of curvature at the point of contact, can lead to gear oil film thicknesses more dramatically
than proportionate reductions in unit tooth load, or elastic
modulus of the gear metal [9].
^ = "4
G'=^aE
^mia
^O
a
= ! ( , + uj)
p^
PI
Pi +
E
PI
PJ
X ,
^^>
2(1 - <^i) + (! - 'I)
T ffj
w'^FIb
Velocity parameter
Material parameter
Minimum film thickness between surfaces
Operating viscosity at atmospheric
pressure
Pressure coefficient of viscosity
Effective peripheral
velocity of two surfaces
Effective radius of curvature of the
two surfaces
Effective modulus of elasticity
of the two materials
Poisson's ratio for the two materials
Normal tooth force per unit tooth
width
437
FIG. 7Relative motion of meshing gear tooth surfaces. Reprinted with permission of CRC Press, Boca
Raton, FL. [14].
Table 6Calculation of the effective radius of curvature [9].
I l l
2
i
- = + = -r-r-x
p />! P2 sin/J ' V"0.
Spur gear
Straight teeth
p =
Helical teeth
Pn =
1 = pinion;
"0. 2 /
ai sin p
p = /! sin P,
( 1)'
ai sin ^
CDS'* Y{i 1)^
2 = gear;
'yAi' + iJ
4- = external teeth;
p radius of curvature
d^ = pitch diameter
a centre distance
A - cone distance
= internal teeth
t = transmission ratio
P = mesh angle
Y = helix angle
A
~ cos*
"
a=1.030+3.509(logvo)^
+ 2.412*10-'*mgi'^(logvo)1.5976
-3.387 (logVo)^'V"".
where:
a =
mo =
vo
p =
These values are used to calculate the minimum film thickness. Table 9 provides the variation for the different paired
gears of spur and bevel types.
where:
log
V
T
AandB
logarithm to base 10
kinematic viscosity, [cSt] or [mm^/s]
Temperature, [K] or [R]
dimensionless constants
438
HANDBOOK
( j sm ^.
= - ^
u= ^
(^-A.) 3i ^
>t sin ^
= __^^^sin^
F
w= F
F = ^;
cos fit,
P=
^
w
F
b
Fu
straight teeth
F
T-^
77:; hehcal teeth
(cos ^ i , cos y,)
2M
M = torque
dy, = pitch circle diameter
^ = mesh angle
7 = helix angle
2.65 X,
'miB
0.54 /
_ \0.7
rO.*S
0.03
Helical teeth
2.65 X a-^* /
nnj^y
(a sin ^ J " ^
i*'
'mi- 0.03^0.13 ^^'^o 3 Q J X c o s " y ( i l ) '
Bcpc/ gear
Straight teeth
2.65 X ' * /
nn,Y\
i^m Sm P)
'13
0.27
'
(,2 + j)0.43
Helical teeth
2.65 X a '* /
'''"
"H''''M''*'
nnX''
30;
i^m sn ^ , 1.13
) " ' , 0 . 2 7
cos''*y
(F + l ) * '
CHAPTER
scribe the Vcirious types of gear lubricants and their general
applications [14,15]. Gear lubricants can fall under any one
of these categories and their fined application, whether industrial or automotive, is predicated on the meeting of specific performance requirements that will be discussed later in
the chapter.
R u s t a n d O x i d a t i o n I n h i b i t e d ( R & O) O i l s
R & O oils are mineral oils containing rust and oxidation inhibitors, antifoamants, and/or antiwear additives. The rust inhibitors prevent corrosion of the metal surfaces by slowing the
formation of acids and free radicals that are the by-products
formed at the onset of oxidation. Without oxidation inhibitors,
these acids and free radicals can form high moleculeir weight
sludge and deposits manifesting as viscosity increase [26]. Inhibited oils are used in gear application under light to moderate loads. This type of gear lubricant can be used to lubricate
bearings and gears operating between - 2 0 to 120C. Inhibited
oils can be reconditioned with filters to ensure cleanliness even
with wear debris and contaminants are present.
439
cation in w o r m gear drives where high sliding speeds between the gear teeth requires lubricity additives to reduce
friction and improve torque efficiency. Compounded oils are
required to operate in the temperature range of 5-120C.
Constant relubrication of the gear teeth is recommended due
to the unique gear mesh that wipes off the oil from the teeth
after contact. Reconditioning of the oil similar to inhibited
oils is quite common.
Open Gear Compounds
These oils are used in large gear sets t h a t move at slow
speeds. These lubricants contain tackifiers that adhere to the
gear teeth that resist being thrown-off or squeezed out of the
mesh. Solvents are sometimes used to help in the application;
they then evaporate leaving behind a thick lubricant film.
The normEd operating temperature range for these lubricants
is 5-120C. This type of lubricant does not offer any advantage that circulating lubricants do for cooling and heat
removal.
Greases
E x t r e m e P r e s s u r e Oils
Extreme pressure oils contain additives predominantly of the
sulfur & phosphorus type to reduce destructive wear and
scoring. These additives combine with the metal surface under frictional heating and provide a sacrificial boundary film
that is easily sheared. EP oils can also contain other surface
active non-sulfur/phosphorus based additives. Examples include graphite, molybdenum disulfide, potassium triborate,
and additives containing bismuth. EP oils are used to lubricate spur, helical, and spiral-bevel gears u n d e r loads too
heavy for inhibited oils. EP oils with the addition of dispersants and detergents can b e used in hjrpoid axles that are exposed to heavy loads or shock loading. Shock loading occurs
under sudden heavy accelerations and decelerations that can
promote scoring at the gear surfaces. These automotive applications will be elaborated later in the chapter. The useful
temperature range for EP oils is generally - 2 0 to 120C. It is
not u n c o m m o n to see automotive gear lubricants subjected
to temperatures from 54 to 170C.
C o m p o u n d e d Oils
These oils contain fat or tallow as lubricity agents in heavy
cylinder basestocks to reduce friction. These oils find appli-
Spur
Normal loads
Helical
Normal loads
EPoil
Heavy or shock
loading
Not normally
used
Slow-speed
Open gearing
Slow-speed
Open gesiring
Compounded oil
(ca. 5% tallow)
Heavy-bodied
open gear oils
Grease
Bevel
Normal loads
Hypoid
Not recommended
Heavy or shock
loading
Not normally
used
Slow-speed
Open gearing
Worm
Light loads
Slow speeds only
Satisfactory for most
applications
Preferred by most
gear manufacturers
Slow-speeds only
EP additive desirable
Heavy or shock
loading
Not normally
used
Slow-speeds
Open gearing
Slow-speed
Open gearing
Slow-speeds only
EP additive desirable
Slow-speeds
Open gearing
440
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
Detergents
Detergents keep metal surfaces clean of deposits. Tjrpical
types of detergents are alkali earth metal (sodium, calcium,
magnesium) sulfonates, phenates, salicylates, and carboxylates. These additives neutredize organic acids from lubricant
oxidation and also associate with precursors that form sludge
and varnish. This has the overall effect of keeping metal surfaces clean of deposits. Consequently, the m a n n e r in which
detergents react with oxidation byproducts can result in prolonging the use of gear lubricants and maintaining clean
working gear boxes. Neutral and basic metal sulfonates are
formed by reacting alkylbenzenesulfonic acids with metal hydroxides or oxides (calcium, magnesium, sodium types) to
form salts. Neutral salts are formed with correct stoichiometry and overbased salts are formed in the presence of carbon
dioxide. Neutral and overbased metal phenates and carboxylates are prepared similarly to sulfonates except cJkylphenols
and alkylsalicylic acids, respectively, are used instead of
alkylbenzenesulfonic acids.
Dispersants
Dispersants keep insoluble contaminants dispersed in the
bulk lubricant. Typical examples of dispersants used in gear
lubricants are of the alkenylsuccinimide, succinate ester,
Mannich derived, and alkenylphosphonic acid derivatives.
The latter is seldom used as the other three types see dominant use in crankcase engine lubricants. In manufacturing
alkenylsuccinimides, succinic anhydride is prepared first by
reacting polyalkenes with mzJeic anhydride. The most comm o n polyalkene used is polyisobutene. The resulting polyisobutene succinic a n h y d r i d e is then neutralized with
aJkylenepolyamines to form polyisobutene succinimides.
In some instances, further reaction of polyisobutene
succinimides with m e t a b o r i c acid is commonly used to
impEirt seal compatibility and enhance deposit and Vcimish
control. Alkenylsuccininate esters are formed by reacting
polyisobutene succinic anhydride with polyhydric alcohols. Mannich derived dispersants are formed by reacting
CHAPTER
formaldehyde, pol}dsobutenyl, and alkylenepolyamines. Disp e r s a n t s associate with p r e c u r s o r s of insolubles, t h u s
controUing deposit formation. The presence of a long hydrocarbon chain in polyisobutene helps in suspending the precursors of insolubles in the bulk lubricant.
441
are edkylated naphthalene and phenolic polymers and polymethacrylates. Alkylated naphthalene is formed by the reaction of napthalene with chlorowax or olefins in the presence
of aluminum chloride. Alkylphenolic polymers are also prepcired in similar fashion. These pour point depressants all act
in similar fashion by hindering the formation of wax from the
base lubricant by adsorption on wax crystals.
POLYMERIC THICKENERS
Polymeric thickeners are also c o m m o n l y referred to as
viscosity modifiers a n d viscosity index improvers. They
function to reduce the lubricant viscosity's dependence on
t e m p e r a t u r e . Typical examples of these include polyisobutene, polymethacrylates, and copolymers of st5Tene and
butadiene. Isobutylene is polymerized to desired molecular
weights in the presence of a Lewis acid. Polymethylacrylates
are prepeired by free radical polymerization of alkyl acrylates
and methacrylates. Styrene butadiene polymers are formed
by free radical polymerization of styrene-butadiene mixtures
in the presence of vanadium based catalysts. Similjir process
is used in the polymerization of olefin block copolymers. This
latter type of poljTner is not commonly used due to its high
manufacturing cost. The molecular weight of these polymers
vary greatly. Due to shear stability constraints imposed by viscosity classification for gear lubricants, the molecular weights
(MW) generally range from 5000-50 000, depending on polym e r type. The most c o m m o n tj^e of viscosity modifier used
for gear lubricants is polyisobutene, whose MW is around
5000. All viscosity modifiers act in similar fashion. At low temperatures, the polymers are tightly coiled cind their effects on
the viscosity are low. As temperature increases, the polymer
uncoils and occupies more space. This has the overall effect of
not reducing the lubricant's viscosity at high temperatures.
F o a m Inhibitors
Foam inhibitors act to deter the formation of foam in applications where there is substantial a m o u n t of churning and
p u m p i n g , e.g., automotive axles. Typical c o m p o u n d s are
polydimethylsiloxanes a n d polyalkylmethacrylates. These
compounds effectively reduce the surface tension of the airlubricant interface, thereby facilitating their collapse.
Polydimethylsiloxanes a n d alkyl methylacrylates are prep a r e d by polymerization of dimethylsiloxane a n d alkyl
methylacrylates.
Friction Modifiers
Friction modifiers are c o m p o u n d s that act to reduce the
coefficient of friction. Certain antiwear and EP agents such
as long chain edkyl phosphates and molybdenum compounds
can be used as friction modifiers. Other examples of friction
modifiers are graphite, fatty alcohols, acids, and amides.
Friction modifiers adsorb on the metal surfaces with their
polar ends, thus forming a b o u n d a r y film with desired
properties.
Pour Point Depressants
These compounds enable the gear lubricant to flow at low
temperatures. Tjqjical examples of p o u r point depressants
Oxidation Inhibitors
Oxidation inhibitors function to inhibit the oxidation and
decomposition of the gesir additives and lubricant. Examples
of oxidation inhibitors are ZDDPs, polysulfides, hindered
and sulfurized phenols, and aromatic amines. The preparation of ZDDPs and polysulfides has been described. Hindered
phenols are made by Lewis acid catalyzed alkylation of phenol or aJkylphenol with poljdsobutylene. Sulfurized phenols
are formed by reacting alkylphenol with sulfur monochloride. Arylamines are prepared by alkylating diphenylamine
with a n olefin in the presence of aluminum chloride. Oxidation inhibitors function to decompose hydroperoxides and
radicals formed during oxidation. The reduction in hydroperoxides and radicals slows down the rate of oxidation of
the gear lubricant.
Corrosion Inhibitors
Corrosion inhibitors function to prevent corrosion and rusting of metal peirts in contact with the gear lubricant. Comm o n examples of these are ethoxylated phenols, sulfonate
based detergents, triazoles, and thiadiazoles. Polyethoxylated phenols and amines are formed by reacting ethylene
oxide, alkylphenols, a n d amines. Benzotriazole is m a d e
from diazotization reaction with nitrous acid. Dimercaptothiadiazole (DMTD) derivatives are made of sodium salt
of DMTD with Ein alkyl halide. Corrosion inhibitors adsorb
on the metal surface via their polcir ends. Some of these,
such as DMTD derivatives, can be used to prevent corrosion
against yellow metals s u c h as synchronizers and brass
washers.
Purpose
Reduce Mction and Wear,
and prevent scoring and
seizure
Typical Compounds
Zinc dialkyl dithiophosphates, di or
tri-alkyl and atyl phosphites, alkyl
phosphoric acid esters and salts,
organic sulfides and polysulfides,
sulfurized fats, dithiocarbamic acid
derivatives, and chlorowaxes."
Mechanism of Performance
These additives react with the metal
surface to form a sacrificisil
chemical film with lower shear
strength than the metal itself.
This not only inhibits welding of
two surfaces in contact but also
minimized metal removal due to
friction.
Detergents
Dispersants
"Tlieir use is being discontinued due to perceived negative impact of chlorine on the environment.
^Heterocyclic compounds are useful in controlling yellow metal corrosion.
A11 additives except some viscosity modifiers and pour point depressants have a polar end and a non-polar hydrocarbon chain.
Polarity is due to the presence of a nitrogen, oxygen, sulfur, or phosphourus-containing functional group.
443
Purpose
Typical Compounds
Functions
These materials have the ability to
complex with metal ions to make
them inactive. This inhibits the
oxidation-promotion action of
metal salts.
Metal deactivators
Oxidation inhibitors
Inhibit oxidative
decomposition of
lubricant and
additives
Emulsifiers
Promote mixing of
water and oil to
form an emulsion"
Demulsifiers
Enhance water
separation from
oil contaminated
with water
Foam inhibitors
Prevent lubricant
from forming a
persistent foam
Friction modifiers
Alter coefficient of
friction
Pour point
depressants
Enable lubricant to
flow at low
temperatures
Viscosity modifiers
"Desired for some hydraulic and metalworking lubricants tiiat use such emulsions.
''The term solubility is often used to describe this phenomenon. However, the term association may be more appropriate.
444
Compound
Zinc dialkyl
dithiophosphates
Phosphites and
phosphates
HANDBOOK
(RO),E^
O
(RO)2P^
H
Dialkyl Hydrogen
Phosphite
o
Triaryl Phosphite
o
R O P a RNHj
ROpff
OR
RNHj
OH
Phosphoric Acids
CHj
HjC-
I
-css- - C C H ,
CH,
CHj
:cssscCH,
GH,
CHJ
Dialkyl Disulfide
CHJ
Dialkyl Trisulfide
RCH=CH-CH;
Sulfiirized olefins
Sa
s/
s.
R-CH2-CHCH2
RCH2'
R-CH2-CHCHJ
R2Nc:^
Dithiocarbamates
Zinc Dithiocarbamates
Compound
Neutral and basic
metal sulfonates
Table 14Detergents.
Structure
Methods of Synthesis
Alkybenzenesulfonic acids are reacted with stoichiometric
S0j)M^003
S05)2M
amount of lime (calcium hydroxide) or magnesium oxide to
form neutral salts. One can use excess of these reagents if
Neutral Metal
Basic Metal
carbon dioxide is used as a co-reactant. The materials thus
Sulfonate
Sulfonate
M = Ca or Mg
obtained, called basic or overbased salts, contain excess
base as metal carbonate.
<r
'<r
oyn^ooj
.0J2M
Basic Metal
Phenate
Neutral Metal
Phenate
M = Ca or Mg
-CCs - -ex,..
o
o
Neutralc Metal Salicylate
,QH
M=Ca or Mg
CHAPTER
Table 15Dispersants.
Compound
Methods of Synthesis
These materials are made by reacting alkylenepolyamines
with polyisobutenylsuccinic anhydride. Succinic
anhydride is an ene reaction product of polyisobutylene
and maleic anhydride.
Structure
Alkenylsuccinimides
./
\
NCHjCHjNHCHjCHiN
Polyisobutenvlsyccinimtde
Alkenylsuccinate esters
L
Polvisobutenytsuccinate Ester
Mannic products
1^
"^1^5^
Alkenylphosphonic acid
derivatives
CHjNHCHjCHNHCHjCHzN
Polyamtnomethylalkylphenol
PIBPOCHjCH-CW
OCHiCH-OH
CH,
Bis-hydroxypropyl
Alkenvlohosohonate
Methods of Synthesis
These materials are made by reacting alcohols with
phosphorus pentasulfide to form dialkyl dithibphosphoric
acids. These acids are reacted with zinc oxide to form
zinc salts.
Structure
Zinc dialkyl
dithiophosphates
CH,
H,CCSSCHj
HjCCSSS-
CHj
CH,
CH,
Dialkyl Trisulfide
Dialkyl Sulfide
Sulfur-coupled phenols
(phenol sulfides) and
hindered phenols
Aromatic amines
Arylamine
445
446
MANUAL
HANDBOOK
Methods of Synthesis
Structure
CH,
Polyolefins
CHj-C
CH,
^3 J n
Polyisobutylene
Olefin copolymers
CH,
-fCH2-CH2^
-CHCHj-
Ethyiene-propylene Copolymer
Styrene diene
copolymers
CH3
CH-CH2-
-CH2CH=C-CH2-
Styrene-diene Polymer
Alkyl methacrylate
polymers
CH,
CH2-C-
COORJj,
Alkyl Methacrylate Polymer
Styrene ester
polymers
RO^
-C^o
-CH-CHj-CH-CH
0=0
RO
These polymers are prepared from mixtures by vanadiumbased Ziegler-Natta catalysis. In these polymers, the ratio
of different olefins in the monomer mixture determines
the polymer's low and high temperature properties. Two
common polymers of this type are EPRs and EPDMs.
EPRs are made fi^om ethylene-propylene mixtures.
EPDMs, on the other hand, contain butadiene or isoprene
as the third monomer. These materials result from free
radical polymerization of styrene-butadiene mixtures.
Because of the presence of unsaturation (double bond),
these polymers are more susceptible to oxidation. Their
oxidation resistance can be improved by removing the
double bonds through hydrogenation.
Free radical polymerization of alkyl acrylates and
methacrylates results in these polymers. In addition to
being good viscosity modifiers, these polymers have the
ability to lower pour point. Hence, they are also used as
pour point depressants.
These esters are prepared by reacting styrene-maleic
anhydride polymer with alcohols. Styrene reacts with
maleic acid in the presence of fi-ee radical initiators to
yield this polymer.
447
Compound
Methods of synthesis
CH2CH2OH
RN^
Ca
CH2CH2OH
Diethanolamine
O
SO3
RCHCOH
^f
CaxCaCOs
CHCOH
II
O
Basic Calcium Sulfonate
Alkenylsuccinic Acid
0(CH2CH2)xCH2CH20H
^ ^ ^
Polyethoxvlated Phenol
SR
RS.
NN
Oimercaptothiadiazole
Alkylbenzotriazole
Derivative
CH2OOOH
N=CHCH2CX30H
Metal deactivators
-CH2COOH
W
HO
CH2COOH
Emulsifiers and
demuisiflers
N, N-Disalicylidene-1,2Propanediamine
Ettivlenediaminetetraacetic
Acid
R0(CH2CH20)xCH2CH20H
NH(CH2CH2);P
Polymhoxylated Alcohol
IHydraxyalkyI Etherl
N-Hydroxyalkvlamide
CH2CH2OH
RN'^
CH2CH2OH
Diethanolamine
R'
R'
I
RNH X
OSi-
I
CH;
CH,
R"
R"
Trialkylammonium
Salt
CH3
Sodium
Cartoxylate
RN^-CHjCHjC
Foam inhibitors
ONa'*'
Tetraalkylammonium
Carboxylate
1 CH,
CH3
OSiO-j-SiCH,
CHj-C
COORj n
CH,
Alkyl Methacrylate
Polymer
Dimethylsiloxane
Polymer
OH
Pour point
depressants
R'
Alkylnaphthalene
CH,
Alkylphenol
-CH2-C
COORj
AlkylMethacrylate
Polymer
R, R' Waxy Alkyl Groups
HANDBOOK
TABLE 19Physical properties: mineral oils versus synthetic base stocks [8b].
Type
90
100
200
350
650
150
Neutral
Neutral
Neutral
Neutral
Neutral
Bright Stock
Kinematic
40C
17,40
20,39
40,74
65,59
117,90
438,00
Alkylated aromatic
Olefin oligomer
Dibasic acid ester
(Dioctyl sebacate)
Trimethylolpropane
Ester (C7 Acid)
Polyglycol
Viscosity, cSt
100C
3,68
4,11
6,23
8,39
12,43
29,46
Solid
Solid
Solid
Solid
Solid
Sohd
(B) Synthetic Base Stocks
26,84
16,77
18,2
4,99
3,87
9047
2371
3450
13,94
45,69
3,4
2360
Viscosity
Index
Pour Point
(X)
92
101
99
97
96
95
-15
-13
-20
-18
-18
-18
190
192
226
252
272
302
119
126
176
-18,3
-43,0
-15,6
224
221
232
-18.3
232
177
150
Performance Demands
1925
1940s
1950s
Service Classification
MIL-L-2105A updated
1962
MIL-L-2105B revised
1975
Mack GO-G
1976
MIL-L-2105C
1987
1994
MIL-L-2105D
MT-l/PG-1
1995
MIL-PRF-2105E
1996
Extended Service
1998
2001
SAE J306
MIL-PRF-2105E
Modified
GL-2
GL-3
GL-4
GL-5
GL-6
MT-I
COC Flash
Point (C)
Equivalent to obsolete
MIL-L-2105; usually
satisfied with 50%
GL-5 additive level.
Virtually equivalent to
present MIL-L-2105D;
primary field service
recommendation of
most passenger car
a n d truck builders
worldwide.
Obsolete.
Contains t h e m a l
stability and EP
additives
Truck manual
transmissions.
Worm gear drives.
industrial gear oils.
Manual transmissions
and spiral bevel
final drives.
Manual transmissions
and spiral bevel a n d
hypoid gears in
moderate service.
Moderate and severe
service in hypoid
and other types of
gears. May cdso be
used in manual
transmissions.
Severe service
involving high
offset hypoid gears
Nonsynchronized
manual
transmissions in
heavy-duty service.
CHAPTER
449
Characteristic
Conditions/Modifications
CEC L-66-X-96
ASTMD5182
GFC Procedure A
Under development
90C, 3600 rpm
160C, 192 hours
CEC-L-45-T-93
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
Rust Prevention
Copper Corrosion
Seal Compatibility
D
D
D
D
D
D
D
D
97
2983
5293
892
6082
665 (Method A)
130
5662
Type
L-33
L-37
L-42
L-60
ASTM D 892
ASTMD 130
Bench test.
Characteristics
Measured
Resistance to
corrosion in the
presence of
moisture.
Resistance to
gear distress
under the
conditions of
low speed high
torque.
Resistance to
gear distress
(scoring) under
conditions of
high speed and
shock loads.
Thermal oxidation
stability.
Foaming
tendencies.
Stability in the
presence of
copper alloys.
-40^
-30C
Seq I, II, III
SeqIV
3 hrs, 1 2 r C l
Limits
No clash at 100 000 cycles
10 load stage pass
50% vis inc. max
2.5 m g KOH/g
25% max
5.8 cSt m i n at lOOX
Less t h a n - 3 9 C
50 000 cP max
5000 cP max
20,50,20/0 ml
100/0 ml
Pass
lb max
Pass
450
HANDBOOK
Scoring resistance u n d e r
high speed shock load
conditions
Resistance to gear
distress under high
torque, low speed
conditions.
Corrosion resistance in
the presence of water.
No requirement.
Antiwear
No requirement.
No requirement.
High temperature
lubricant stability.
No requirement.
No requirement.
Antifoaming
characteristics
Cooper corrosion
Channeling
characteristics
API MT-1
No requirement.
No requirement.
No requirement.
at 12rc.
SS&CFED-STD-791
Compatibility with
existing gear
lubricants
Solubilitymeasure
separated material
after centrifuging oil
stored for 30 days at
room temperature
(29.4 9.5C).
Compatibilitysame
solubility except
mixed 50/50 with each
of six reference oils.
SS&CFED-STD-791
70W
75W
SOW
85W
80
85
90
140
250
4.1
None
4.1
None
7.0
None
11.0
None
7.0
<11.0
11.0
<13.5
13.5
<24.0
24.0
<41.0
41.0
None
-55
-40
None
None
None
None
Properties
Viscosity at 100C
Min (cSt)
Max (Cst)
Vis of 150,000 cP
Max Temp, C
Channel Point, min. "C
Flash Point, min C
-26
-12
None
iUilitary Specification
75W
80W90
4.1
85W140
-40
13.5
<24.0
-26
24.0
<41.0
-12
-45
150
-35
165
-20
180
CHAPTER
451
SAE 75W
SAE 80W-90
SAE 85W-140
ASTM Method
Viscosity
Channel Point, C, max
Flash Point, "C, min
API Gravity
Viscosity Index
Pour Point, "C
Pentane Insolubles, wt%
Sulfur, wt%
Sulfur from Additive, wt%
Phosphorus, p p m
Chlorine, p p m
Nitrogen, p p m
Zinc, p p m
Boron, p p m
Potassium, p p m
Organo-metals, ppm
D445
FTM 3456
D92
D287
D2270
D97
D893
D1552
D 1552
D 1091
D808
D3228
D4951
D4951
D4951
D4951
OEM Specifications
Many OEMs have developed their own performance classifications for standard and extended drain services. These factory and service fill requirements generally meet API GL-5
performance requirements [1,24]. In addition, performance
considerations for these lubricants meet specific performance targets in the areas of improved fuel economy, temperature reduction, improved fatigue performance, enhanced
Test Method
Copper Corrosion,
ASTM D 130,
12rC, 3 h
Foam Tendency,
ASTM D 892
Seq
I
II
III
20 ml
50 ml
20 ml
Oxidative and
Thermal Stability,
ASTM D 5704,
50 hrs, 163C
(L-60-1)
Cyclic Durability
Test, ASTM 5579
Seal Compatibility,
ASTM D 5662
<100%
< 3 wt%
< 2 wt%
>7.5
>9.4
Min
No limit
-35
-5
Max
-60
+5
+ 30
Parameters
Min
Max
Elongation change, %
Hardness change, points
Volume change, %
No limit
-5
-5
-75
+ 10
+ 15
Test Mileage
Sampling Interval
ASTM Method
D445
D 1091
D1552
D808
D3228
D4951
D4951
D4951
D4951
D664
D4739
D983
SAE Viscosity
Grades
Specification
No.
GO-J
80W-90, 85W-140
GO-J Plus
Performance Requirements
Mil-PRF-2105E
Seal immersion test
Mack spalling test(*)
500 000 mile field test
100 h o u r L-60-1
Extended Mack cycling testC)
250 000
500 000
500 000
Eaton/Dana
PS-163/
SHAES-256
Mil-PRF-2105E
Copper & bronze corrosion tests
Dynamic seal tests
Spalling test
500 000 mile field test
Wet L-37 Test
ArvinMeritor
076-D & A
80W-90, 85W-140
MiL-PRF-2105E
Mercedes Benz
235
API GL-5
In-house axle tests
Mercedes Benz
235.6
80W90
85W90,90
API GL-5
In-house axle tests
Volvo
MAN
97 310
97 312
342N
342ML
90
80W90
342SL
75W90
80W90
Iveco
ZF
TEML05
API GL-5
API GL-5
FZG PITS field test
API GL-5
FZG PITS field test
(FSS)
220 000 for FSS
75 000 (long haul)
110 000 current (long haul)
250 000 target
50 000
100 000 (long haul)
200-250 000
90
85W140
API GL-5
75 000
90
API GL-5
In-house axle and FZG tests
50 000
453
Limits
25 min
95 min
Trace
- 9 C max (based
on viscosity)
232.2C min
203.4C min
l b max
Pass
6% max
0.1% max
80 ml min
1.0 ml max
2.0% max
45 kg min
250 kg m i n
Scar Diameter of
0.35 m m max
O.K. 60 lbs min
1 1 * Stage min
AGMA 9005-D94 E P
60 lbs min
12
11
AISE 224
60 lbs min
11
250 kg min
45 min
Scar Diameter0.35
max
lb max
PassB
Pass A
lb max
Pass A & B
6 max
6 max
0.1 max
75/10
75/10
75/10
Table 33Minimum physical and performance specification for inhibited and compounded gear lubricants.
Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Property
Viscosity
Viscosity
Index
Oxidation
Stability
Rust
Protection
Corrosion
Protection
Foam
Suppression
Demulsibility
Cleanliness
Test Procedure
ISO 3104
ASTM D 445
ISO 2909
ASTM D 2270
ISO 4263
ASTM D 943
ISO 7120
ASTM D 655B
ISO 2160
ASTM D 130
ASTM D 892
ASTM D 2711
None
10 min. rest
10
10
30.0 ml
0.5%
2.0 ml
30.0 ml
"The criteria for acceptance indicated for oxidation stability and demulsibility is not applicable to compounded gear oils.
455
Property
Viscosity
Viscosity
Index
Oxidation
Stability
Rust
Protection
Corrosion
Protection
Foam
Suppression
Demulsibility
ISO 3104
ASTM D 445
ISO 2909
ASTM D 2270
ASTM D 2893
ISO 7120
ASTM D 655B
ISO 2160
ASTMD 130
ASTM D 892
ASTMD 271IMOD
5 min. blow
75
75
75
10 min. rest
10
10
10
AGMA Grades
2EPto7EP
8 EP to 13 EP
2.0%
2.0%
Cleanliness
Load carrying property
None
ASTM D 2782 (Timken Test)
and DIN 51 354 (FZG Test)
Filterability
None
Table 35Minimum physical and performEince specification for synthetic gear lubricants.
Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Property
Viscosity
Viscosity Index
Oxidation Stability
Rust Protection
Corrosion Protection
Foam Suppression
Demulsibility
Cleanliness
Mciximum Pour Point
Test Procedure
ISO 3104
ASTM D 445
ISO 2909
ASTM D 2270
ASTM D 2893
ISO 7120
ASTM D 665B
ISO 2160
ASTMD 130
ASTM D 892
None
ISO 7120
ASTM D 665
DIN 51 354
Filterability
None
10 min. test
10
10
10
1.0%
2.0 ml
60.0 ml
An oil must meet 11 stage fail (10 stage pass) on FZG machine with A/8.3/90C
parameters for acceptance.
Must be filterable to 25/i (microns) wet or dry without loss of additives
(/325 = 200 filter rating).
" Esters having a lower viscosity index and meeting all other requirements of this specification may be used in specific applications where proper viscosity at
operating temperature has been verified.
* Polyglycols which will not pass the demulsibility test, but meet all other requirements of this specification, may be used in specific applications where there
is no danger of water contamination.
456
MANUAL
HANDBOOK
Table 36Viscosity ranges for AGMA gear lubricants. Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Rust and Oxidation
Inhibited Gear Oils,
AGMA Lubricant No.
0
1
2
3
4
5
6
7, 7 Comp''
8, 8 Comp''
8A Comp''
9
10
11
12
13
Residual compounds'^
AGMA Lubricant No
14R
15R
Viscosity
Range " mm'^/s
(cSt) at 4000
Equivalent
ISO Grade"
28.8-35.2
41.4-50.6
61.2-74.8
90-110
135-165
198-242
288-352
414-506
612-748
900-1100
1350-1650
2880-3520
4140-5060
6120-7480
190-220 cSt at
100C (212F)
Viscosity ranges"
cStatl00C(212F)
428.5-857.0
857.0-1714.0
32
46
68
100
150
220
320
460
680
1000
1500
Extreme Pressure
Gear Lubricants *
AGMA LubricEint No.
2EP
3EP
4EP
5EP
6EP
7EP
8EP
8AEP
9EP
10 EP
11 EP
12 EP
13 EP
OS
IS
2S
35
4S
5S
6S
7S
85
95
10 S
US
12 5
13 S
"per ISO 3448, Industrial Liquid Lubricants - ISO Viscosity Classification, Also ASTM D 2422 and British Standards Institution B.S. 4231.
''Extreme pressure lubricants should b e used only w h e n recommended b y the gear manufacturer.
"Synthetic gear oils 9S -13S are available but not yet in wide use.
''Oils marked Comp are compounded with 3 % to 10-% fatty or synthetic fatty oils.
"Viscosities of AGMA Lubricant N u m b e r 13 and above are specified at 100C (212F) as measurement of viscosities of these heavy lubricants at 40C (lOOT)
would not be practical.
l i e s i d u a l compounds - diluent type, commonly knows as solvent cutbacks, are heavy oils containing a volatile, no-flammable diluent for ease of applications.
The diluent evaporates leaving a thick film of lubricant on the gear teeth. Viscosities listed are for the base compound with diluent.
CAUTION: These lubricants may require special handling and storage procedures. Diluent can be toxic or irritating to the skin. Do not use these lubricants
without proper ventilation. Consult lubricant supplier's instructions.
Acid N u m b e r ASTM D 6 6 4
This method determines the acidic constituents in gear lubriceints that are present as additives or as degradation products during service. It is applicable for the determination of
acids whose dissociation constants in water are Isirger than
10~^; extremely weaJs acids whose dissociation constants are
smaller t h a n 10~^ do not interfere. Salts react if their hydrolysis constants are larger than 10"*. The sample is dissolved in
a mixture of toluene a n d propan-2-ol containing a small
amount of water and titrated potentiometrically with alcoholic potassium hydroxide (KOH). The acid n u m b e r is reported as mg KOH/g of sample. Since a variety of oxidation
products contribute to the acid n u m b e r and the organic acids
vary widely in corrosion properties, this test method cannot
be used to predict corrosiveness of the geeir oil u n d e r service.
Rust Inhibition ASTM D 6 6 5
This method evaluates the ability of oils to prevent rusting of
ferrous parts if water mixed with the oil. A mixture of 300 mL
of the oil under test is stirred with 30 mL of distilled water
(Method A) or synthetic seawater (Method B) at 60C in the
presence of a completely immersed cylindrical steel rod. The
duration of the test is 24 h. At the end of 24 h, the test rod is
inspected for signs of rust.
F o a m Characteristics ASTM D 892
This method covers the determination of foaming characteristics of oils at 24C and 93.5C. The tendency of oils to
CHAPTER
foam can be serious in systems such as high-speed gearing,
high volume pumping, and splash lubrication. Inadequate
lubrication, cavitation, and overflow loss of oil can lead to
m e c h a n i c a l failure. The s a m p l e is m a i n t a i n e d at 24C
while air is blown into it at a constant rate for 5 m i n a n d
allowed to settle for 10 min. The volume of foam is measured at the end of both periods. The test is repeated on a
second sample at 93.5C a n d t h e n after collapsing the
foam, at 24C.
Insolubles in U s e d Oils ASTM D 8 9 3
This m e t h o d covers the d e t e r m i n a t i o n of p e n t a n e a n d
toluene insolubles in used oils. Procedure A covers the
determination of insolubles without the use of coagulant in
pentane. Procedure B determines insolubles of oils containing detergents and employs a coagulant for both the pentane
and toluene. In both procedures, a representative amount of
sample is mixed with pentane and centrifuged. The solution
is decanted and washed with either pentane and/or toluene.
The "wet" insolubles are dried and weighed.
457
This method specifies the procedures for calculating the Viscosity Indices (VI) of oils from 40C and 100C. Described
Procedures A and B determine the VI of oils u p to 100 and
greater than 100, respectively. The VI is a widely accepted
measure of the variation in kinematic viscosity due to the
changes in temperature. The higher the VI of the oil is, the
less the dependence of viscosity on temperature. JCnowledge
of a gear lubricant's VI can be used to predict performance
and quality.
T i m k e n M e t h o d for E P ASTM D 2 7 8 2
This method covers the determination of the load-carrying
capacity of oils by means of the Timken EP Tester. The tester
is operated with a steel test cup rotating against a steel test
block. The rotating speed is 123.71 0.77 m/min or 800
rpm. Oil samples Eire preheated to 37.8C before starting the
test. Two determinations are made: the minimum load (score
value) that will compromise the lubricant film between the
rotating cup and stationary block and cause seizure or scoring; and the maximum load (OK value) at which the rotating
cup will not compromise the lubricant film.
Four Ball E P ASTM D 2 7 8 3
This method also determines the load carrying properties of
lubricating oils. This method differentiates between lubricating oils having low, medium, emd high level of EP properties.
The tester is operated with one steel ball under load rotating
against stationary three balls. The rotating speed is 1760 40
r p m . The test lubricant is b r o u g h t between 18.33-35C
(65-95F) and a series of 10 s durations are made at increasing loads until welding occurs.
DemulsibUity ASTM D 2711
This method determines the ability of oil and water to separate from each other. It is intended for oils with medium and
high viscosity. The test provides a guide for determining the
458
HANDBOOK
demulsibility of gear lubricants that are prone to water contamination and may encounter the turbulence of pumping
and circulation capable of producing water-in-oil emulsions.
The ability to separate water is desired in applications where
it is relatively easy to perform maintenance without draining
the oil sump completely.
Oxidation of EP Oils ASTM D 2893 (S-200)
This widely used method determines the oxidation characteristics of EP gear oils. The oil sample is subjected to a
temperature of 95C in the presence of dry air for 312 h. The
oil is then tested for precipitation number and viscosity
increase.
Low Temperature Brookfield Viscosity ASTM D
2983
This test method describes the use of the Brookfield viscometer for the determination of the low-shear rate viscosity
of gear lubricants in the temperature range from - 5 to
-40C. The viscosity range is 1000-1 000 000 cP. A lubricant
sample is cooled in an air bath at test temperature for 16 h. It
is carried in an insulated container to a nearby Brookfield
viscometer where its viscosity is measured at the temperature
of the bath. The low temperature properties of gear lubricants are critical for equipment starts that may be subjected
to low temperatures. The lack of lubrication can cause severe
catastrophic distress to the gears and bearings.
459
GFC Oxidation
This test method measures the oxidative stability of gear lubricants under high temperatures. A quantity of sample
placed in a flask is heated at a specific temperature with air
bubbled throughout the duration of the test. At the end of the
test, the viscosity increase, wt% insolubles, and acid number
are reported.
Synchronizer SSP 180 Test
This test measures the ability of a transmission lubricant to
provide proper synchronized shifts at a specified temperature and synchronizer friction material. The test rig uses
cone t)rpe synchronizers of several friction types. The industry is currently conducting round robin testing to formulize a
test procedure for PM-1.
Shear Stability CEC-L45-T-93
The test procedure eveJuates the shear stability of lubricants
containing polymeric additives. Polymeric additives are usually used for thickening and improving low temperature flow
properties. A specified quantity of oil is placed in a tapered
roller bearing fixture that is motored by the Four Ball Machine. The temperature is controlled at 60C for 20 h with a
load of 5000N. At the end of this duration, the percent change
in viscosity at 100C is determined. SAE J306 has shear stability requirements for gear lubricants to not shear out of
grade. Loss in viscosity can caused compromise to lubricant
films for proper bearing and gear performance.
FZG (Forschungsstelle fur Zahnrader und
Getriebebau) Pits C 180 TS
This test procedure evaluates the influence of oil aging on the
pitting life of gears under conditions of variable load, speed,
and high temperature. The results are compared to a reference oil in the same test. The failure criterion is to report less
than 4% of the active flank area of one single tooth at the
end of the test. The pitting performance of gear lubricants is
critical
Channel Point FTM 3456
This test method is used to determine the channeling characteristics of oils at low temperature. The test consists of storing the oil sample for 18 h at the temperature required by the
specification, cutting a channel in the oil with a metaJ strip,
and determining whether the lubricant flows together to
cover the bottom of the container within IDs. The ability of
a lubricant to resist channeling at low temperatures provides
adequate lubrication at startup conditions.
Gear Scoring Test L-42
This test method evaluates the anti-scoring characteristics of
a gear lubricant under high-speed and shock loading conditions using a hypoid axle. The axle is driven by a 5.7 liter V8 engine that drives the test axle, a 4-speed truck transmission, and
two inertia dynamometers at a rate to simulate hard acceleration to approximately 100 mph. After break-in, the axle is ac-
460
MANUAL
HANDBOOK
celerated through the gears to a speed of lOSOrpm, then decelerated to 530 rpm. This cycle is repeated five times. The highspeed sequence is followed by ten shock loadings. The gear lubricant is required to equal or better the scoring on the coast
side of the pinion Eind ring gears of a passing reference oil.
Gear Corrosion Test L-33
This test evaluates the rust and corrosion inhibiting properties of a gear lubricant when subjected to water contamination and elevated temperatures. The test utilizes an unloaded
hypoid axle unit mounted on a test stand, which enables the
unit to be motored over with heat lamps. The axle is filled
with 1200 mL of oil and 30 mL of water and motored for 4 h
at 82.2C. On completion of this motoring phase, the axle is
stored for 162 h for 51.7C in an environmental oven. At the
end of storage, the axle is disassembled and rated for corrosion, sludge, and other deposits.
Dynamic Seals Test
This test method evaluates the seal compatibility during operation at a specified temperature and high shaft speed of
2500 r p m for 1000 h. The lip shaft seals are inspected for wear
and deviations from original dimensions at the end of test.
Modifications to this test specific to OEM seal materials and
shaft diameters can be made. This test attempts to simulate
seal performance and the gear lubricant's effect in the field.
Compatibility of Gear Lubricants FTM 3430
This test procedure is used to determine the compatibility of
gear lubricant when blended with a reference gear lubricant
by observing for precipitation of additive matericd after storage. The test consists of storing the blended oils for 30 days
' Consequences
Extended Drain
Improved Component
Durability
Lubricant Effect
Improved
Pitting
Performance
Improved
Synchronizer
Performance
Improved Seal
Compatibilty
Better
Thermal/Oxidative
Stability
461
Trend
Extended Drain
Lubricant Effect
Consequences
Improved Component
Durability
Use of Filters?
improved Pitting
Performance
Improved Seal
Compatibilty
I Higher Speeds
< Reduced Airflow
I increased Unit Loading
I iVIore Environmentally
Friendly
Easier Disposal
Improved
Thermal/Oxidation
Stability
Reduced Chlorine
(Target 50 ppm Max)
I Simplified
Technology
IMore Robust
Performance
Improved EP
Performance
ASTM STANDARDS
Unless otherwise indicated all of the following standards are
current.
No.
D 91
D 92
CONCLUSIONS
D 97
This chapter described gear lubricants and summarized their
requirements for automotive a n d industrial gear applications. Lubricating gears in axles or gearboxes is challenging,
as gear lubricants are required to provide efficient operation
with minimized maintenance. Gear lubricants collectively
provide various attributes such as: scuffing resistance, extreme pressure (EP), antiwear, corrosion resistance against
ferrous and yellow metals, compatibility with various elastomeric seals, oxidative and thermal stability, possession of
varying degrees of demulsibility depending on application,
low and high temperature film strength, good low temperature fluidity, cost effectiveness, and environmental safety.
Commonly used gear sets were described in this chapter
along with some tj^ical gear failure modes. A list of typical
additives used to formulate gear lubricants were also given.
Current classifications for automotive and industrial gear lubricants were compared along with their testing and perfor-
D 130
D 287
D 445
D 664
D 665
D 808
D 892
Title
Test Method for Precipitation Number for Lubricating Oils
Test Method for Flash and Fire Points by Cleveland
Open Cup
Test Method for Flash Point by Pensky-Martens
Closed Cup Tester
Test Method for Detection of Copper Corrosion
from Petroleum Products by the Copper Strip Tarnish Test
Test Method for API Gravity of Crude Petroleum
and Petroleum Products (Hydrometer Method)
Test Method for JCinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Test Method for Acid N u m b e r of Petroleum Products by Potentiometric Titration
Test Method for Rust-Preventing Characteristics of
Inhibited Mineral Oil in the Presence of Water
Test Method for Chlorine in New a n d Used
Petroleum Products (Bomb Method)
Test Method for Foaming Characteristics of Lubricating Oils
OTHER STANDARDS
AGMA 9005-D94Industrial Gear Lubrication
Federal Test Method 3456Channel Point of Federal Test
Method Std. No. 791
FZG-PITS Test C 180 TSTest Method for Evaluating the
Influence of Oil Ageing on the Pitting Load Capacity of
Lubricants
GFC (Groupement Francais De Coordination) or CEC L-48-A00Oxidative Stability of Lubricating Oils Used in Automotive Transmissions by Artificial Ageing (Laboratory Test)
MIL-PRF-2105E or SAE J2360Lubricating Oil, Gear Multipurpose (Metric) Military Use
SAE J308Axle and Manual Transmission Lubricants
REFERENCES
[1] Bala, v., MacPherson, I., and Walters, D. K., "Gear Additive
Technology for Extended Drain Commercial Driveline Requirements," NLGI Paper No: 9719, Presented at The 64th Annual
Meeting of National Lubricating Grease Institute, Carlsbad, Oct.
1997.
[2] MacPherson, I., Kuhlman, R. E., Carlson, J. W., and Taylor, J. M.,
"Gear Additive Considerations for the Next Decade," NLGI Paper
No: 9719, Presented at The 62"^ Annual Meeting of National Lubricating Grease Institute, Ponte Vedra Beach, Oct. 1995.
[3] Norman, S., Kovitch, G. H., and Klein, R. M., "Industry Requirements for a New Generation of Automotive Gear Oils,"
NLGI Spokesman, Vol. 53, 1989, pp. 183-196.
[4] Drago, R. J., Fundamentals of Gear Design, Butterworth Publishers, Boston, 1988.
[5] NLGI Gear Education Course Material, Presented at The 65"'
Annual Meeting of National Lubricating Grease Institute, Naples,
1998.
[6] Hendrick, E. E., "Improved Compound for the Manufacture of
Lubricating Oils," U.S. Patent No. 90,100, Washington D.C.,
May 1869.
[7] Papay, A. G. and Dinsmore, D. W., "Advances in Gear Additive
Technology," Presented at The 30th ASLE Annual Meeting, Atlanta, GA, May 1975.
[8] a. Ethyl Petroleum Additives Specialties Gear Training Manual,
Ethyl Petroleum Additives, Inc., Richmond, VA, 1996. b. Lubrizol Corporation's Additive Ready Reference for Lubricant and Fuel
Performance. Lubrizol, Wickliff, OH, 1998.
[9] Bartz, W. J., Lubrication of Gearing, Mechanical Engineering
Publications, Ltd., London, 1993.
[10] Benedict, G. H., "Gears," Ch. 20, Standard Handbook of Lubrication Engineering, McGraw-Hill, NY, 1968.
[11] American Society of Metals Handbook on Friction, Lubrication
and Wear Technology, Vol. 18, Oct. 1992. a) Errichello, R., "Friction, Lubrication, and Wear of Gears," pp. 535-545; b) Rizvi, S.
Q. A., "Lubricant Additives and Their Functions," pp. 98-112.
[12] ANSI/AGMA 1010-E95: Appearance of Gear TeethTerminology of Wear and Failure, AGMA, Alexandria, VA.
[13] Ludema, K. C, Friction, Wear, LubricationA Textbook in Tribology, CRC Press Ltd., Boca Raton, FL, 1996.
[14] Stucker, J. B., "Rear Axle and Gear Box Lubricants," CRC Handbook of Lubrication, Vol. I, CRC Press, Boca Raton, FL, 1992.
[15] Radovich, J. L., "Gears," CRC Handbook of Lubrication, Vol. II,
CRC Press, Boca Raton, FL, 1992.
[16] AGMA 9005-D94: Industrial Gear Lubrication, AGMA, Alexandria, VA, August 1994.
[17] SAE J308: Axle and Manual Transmission Lubricants, Society
of Automotive Engineers, Warrendale, PA, 1989.
[18] SAE J306: Automotive Gear Lubricant Viscosity Classification,
Society of Automotive Engineers, Warrendale, PA, 1998.
[19] MIL-PRF-2105E: Lubricating Oil, Gear Multipurpose (Metric)
Military Use, U.S. Military, Aug. 1995.
[20] SAE J2360: Lubrication Oil, Gear Multipurpose Military Use,
Society of Automotive Engineers, Warrendale, PA, 1998.
[21] Laboratory Performance Tests for Automotive Gear Lubricants intended for API GL-5 Service, ASTM STP 512A, ASTM International, West Conshohocken, PA, 1991.
[22] Proposed Specification for Passenger Manual Transmission,
Minutes of ASTM Committee D02.B0.003 Meeting, Nashville,
TN, Nov. 2000, ASTM International, West Conshohocken, PA.
463
MNL37-EB/Jun. 2003
Automotive Lubricants
Shirley E. Schwartz, ^ Simon C. Tung,^ and Michael L. McMillan'
LUBRICANT TYPES
MANY TYPES OF LUBRICANTS ARE USED IN A VEHICLE. Engine oil
465
Copyright'
2003 by A S I M International
www.astm.org
466
MANUAL
HANDBOOK
COMPOSITION OF AUTOMOTIVE
LUBRICANTS
In general, automotive lubricants consist of a base stock and
various additives. The choice of base stock depends on the
function of the lubricant. In the case of engine oil, various
types of organic oils may be used: paraffinic, naphthenic, and
synthetic. Paraffinic hydrocarbons consist of hydrogen and
carbon atoms that are chemically bonded together in the
form of branched chains. Naphthenic hydrocarbons contain
carbon atoms that are bonded together in the form of rings.
Paraffinic and naphthenic hydrocarbons are typically derived by refining oil from oil wells. Synthetic hydrocarbons
CHAPTER
placed by a bench test, ASTM D 6557, Standard Test Method
for Evaluation of Rust Preventive Characteristics of Automotive Engine Oils, also known as the "BEJI Rust Test." During
the creation of the Ball Rust Test, extensive testing was conducted to identify appropriate chemiccJ reagents and test conditions to ensure that the bench test would provide the same
useful information as was gleaned from the engine test.
AUTOMOTIVE E N G I N E OILS
Introduction
Identifying appropriate test methods for engine oils represents one of the most difficult challenges facing automobile
and lubricant manufacturers. The reason for the difficulty is
not because of any inherent characteristic of engine oil. The
challenges in the development of test methods for engine oil
arise because the environment in which engine oils must operate can be exceedingly harsh and difficult to control. Combustion gases, fuel and water in the oil, and outside contaminants (dirt, sand, other airborne materials) accelerate oil
degradation, cause unique filtration problems, and result in
m u c h shorter change intervals compared to other typical automotive lubricants. Engine oil properties and composition
also affect vehicle fuel economy (as is the case for transmission fluids and rear axle lubricants). Engine oil influences
vehicle emissions as a consequence of emission system contamination and catalyst poisoning. Engine oil can escape
from the engine via mist exiting the exhaust system. In addition, small amounts of engine oil or oil mist can b u m when
exposed to a flame front, which can create particulate emissions containing charred hydrocarbons and degraded oil additives.
It is for these reasons that engine oil is the focus of much
attention in the technical literature as well as in the standard
test-development arena. The following sections describe
standard test methods for evaluating engine oil performance
(including both engine and bench tests) and the terminology
used to describe engine oil performance, from both historical
and current perspectives. The discussions are limited primarily to performance designations a n d associated test
methods commonly used in North America. Oils described by
other means and defined by different test methods are used
in various other areas of the world, for example Europe and
Japan. However, these international test methods are not addressed in detail in this chapter.
E n g i n e Oil P e r f o r m a n c e S t a n d a r d s - - P a s t
and Present
Over the years, many organizations have contributed to the
development of engine oil performance standards. Among
these organizations are ASTM International (ASTM), the
American Petroleum Institute (API), the Engine Manufacturers Association (EMA), the Coordinating European Council
(CEC), the Japan Automobile Manufacturers Association
(JAMA), and the International Lubricant Standardization and
Approval Committee (ILSAC). ILSAC includes automotive
and engine builders JAMA, EMA, and the former American
Automobile Manufacturers Association (AAMA, whose members were General Motors, Ford, and Chrysler). When AAMA
17: AUTOMOTIVE
LUBRICANTS
467
468
MANUAL
HANDBOOK
CHAPTER
plete description of each of these performance categories
(both the current categories and those declared technically
obsolete) is provided in SAE Standard J183, Engine Oil Performance and Engine Service Classification. Only the tests
used to define the current performance categories (API SJ
and ILSAC GF-2) and the tests used in the categories effective
in 2001 (API SL and ILSAC GF-3) are discussed in this section. Some of these tests have been developed into ASTM
Standard test methods, and others are in the process of being
developed into ASTM Standards. It is not a requirement that
all tests used to define a n engine performance category be
ASTM Standards. However, those tests that are not ASTM
Standards are usually advanced to ASTM Standards during
the lifetime of a given category. ASTM Subcommittee D02.B0
on Automotive Lubricants maintains a section devoted exclusively to converting test methods developed for new lubricant performance categories into ASTM Standards.
17: AUTOMOTIVE
LUBRICANTS
469
The temperatures and loads of the test should be appropriate for the tjrpe of service being emulated.
For a given test method, a desired chemical environment is
created by utilizing an appropriate fuel (including its degradation products) and generating oil degradation products
that are similar to those generated in the driving style of interest. A desired materials environment is created by using
engine and hardware materials that are representative of the
engines that the test method is designed to protect. In addition, hardware should be chosen for the test such that interactions between hardware surfaces and chemicals used or
generated in the tests (such as fuels, lubricants, and their
degradation products) are similar to those in the real world.
A desired t h e r m a l environment m e a n s that test temperatures, even if they are severe, are not so severe that fundamental mechanisms of damage have changed.
Creating an appropriate test environment, but also finding
test conditions such that the test does not require an inordinate a m o u n t of test time, is often difficult to achieve. An example of this difficulty is as follows. If a lubricant test
method is designed to determine the corrosive effects of fuel
degradation products on engine materials, the test must be
conducted at a temperature such that those corrosive fuel oxidation products will not boil off, but will remain in the engine oil to create corrosive conditions. If a test temperature
differs significantly from operating temperatures, an investigator must determine whether or not any apparent correlation is accidental. In addition, leaded fuel tjrpically contains
chlorine and bromine compounds that can contribute to engine corrosion. If leaded fuel is used in an engine test that
simulates a given type of vehicle operation, but current vehicle operation uses unleaded fuel, one m u s t determine
whether any correlations observed between the leaded-fuel
test and actual vehicle operation are real or accidental. That
is, the investigator must determine whether the chemical environment in the engine test simulates an accelerated version
of reality. Such correlation is often difficult to prove.
Thus, chemical, thermal, and materials properties all influence the outcome of a test, and it is important to ensure
that these properties, as utilized in a given test, are providing
a realistic representation of actual operating conditions. In
addition, when bench tests are used in place of engine tests to
measure a given performance parameter, great care must be
taken to ensure correlation between the bench test and engine effects.
Gasoline Engine-Oil Performance Categories and
Associated ASTM Standard Test M e t h o d s
As of the year 2001, only four designations were widely used
to describe gasoline engine oil performance: API SJ and SL,
and ILSAC GF-2 and GF-3. As stated previously, the engine
test and bench test performance requirements for API SJ and
ILSAC GF-2 are similar with regard to engine test methods,
but in addition ILSAC GF-2 oils must meet the stricter Energy Conserving fuel efficiency requirements. Similarly, API
SL requirements as well as Energy Conserving requirements
must be passed before an engine oil can be designated as
ILSAC GF-3.
The appropriate test methods for engine oils must be conducted in accordance with the requirements outlined in the
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MANUAL
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Copper-Lead
Bearing
Wear,
Wear,
CHAPTER
ual No. 14. Parts other than piston skirts are rated by comparing the engine parts to color chips. Piston undercrown deposits axid ring land deposits Etre EJSO evaluated.
The extent of clogging of vEirious components is rated: oil
screen, oil ring, PCV (positive crankcase ventilation) valve,
and camshaft lobe orifice clogging. Oil screen clogging
should be n o greater than 20%. The n u m b e r of stuck rings
and hydraulic lifter plungers is recorded. There should be no
hot-stuck compression rings. Various wear measurements
are tciken, including: camshaft lobes, rocker arm, connecting
rod bearing, and cylinder bore. Piston ring gap increase is
also used as a measure of wear. Average cam wear should be
no greater than 127 /xm. Maximum cam wear should be no
greater t h a n 380 /am. The following oil analyses are conducted: iron, copper, and silicon in engine oil, kinematic
viscosity (ASTM D 445), and pentane insolubles in oil (ASTM
D 893 B).
Short-Trip-Service
Engine
Rusting,
ASTM
Sequence
IID
ASTM D 5844, Standard Test Method for Evaluation of Automotive Engine Oils for Inhibition of Rusting, is an engine
test conducted with a 1977 5.7L Oldsmobile engine. The test
uses leaded gasoline, and a warning message is provided that
indicates "The method may not be applicable for the evaluation of engine oils if unleaded gasoline is used." In Stage I (28
h) the engine speed is 1500 revolutions per min, engine load
is 25 brake horsepower (18.6 kilowatts) at an oil temperature
of 120F (48.9 C) in the filter block. In Stage II (2 h) coolant
temperature is increased. In Stage III (2 h) the engine speed
is 3600 revolutions per min, engine load is 100 brake horsepower (74.6 kW), and the oil temperature is 260F (126.7C).
Additional operating parameters are listed in the test procedure. Various engine c o m p o n e n t s are evaluated for such
measurements as rust formation on valve lifter bodies, valve
lifter plungers, valve lifter balls, oil p u m p relief veJve, and
pushrods. Lifter plunger sticking, oil p u m p relief valve sticking, and oil consumption are also measured.
Energy Conserving
Characteristics,
ASTM Sequence
VIA
In addition to the engine performance r e q u i r e m e n t s described above, ILSAC GF-2 oils must meet fuel efficiency requirements according to the test procedure described in
ASTM Standard D 6202 (Sequence VIA). In this engine dynamometer test, the fuel consumption associated with a test
oil is measured and compared to the fuel consumption when
using a standard reference oil. For the test oil to be called
"Energy Conserving," it must exceed the fuel efficiency of the
reference oil by a given percentage, based on its SAE viscosity grade. The m i n i m u m percent improvement for ILSAC GF2 oils is 1.4% for SAE OW-20 and 5W-20 viscosity grades,
1.1% for other OW and 5W multiviscosity grades, and 0.5%
for SAE l o w multiviscosity and all other viscosity grades.
API SJ oils are not required to meet fuel efficiency requirements, although oils satisfying the above Sequence VIA requirements can be designated as "Energy Conserving" in the
bottom half of the API (American Petroleum Institute) service symbol, which appears on many oil containers. American Petroleum Institute publication API 1509 provides information on this subject.
Engine
Oil
17: AUTOMOTIVE
LUBRICANTS
471
Volatility
Tendency
Content
Phosphorus in engine oil has been shown in numerous studies [6-8] to be related to poisoning of catalytic converters and
other emissions system components. For this reason, phosphorus content of ILSAC GF-2 and certain viscosity grades of
API SJ oils must remain below a designated value. Phosphorus content is measured either by ASTM D 4951, Standard
Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry or by ASTM D 5185, S t a n d a r d Test
Method for Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base Oils by Inductively
Coupled Plasma Atomic Emission Spectrometry.
Additional Requirements
Several additional requirements must be satisfied before an
oil can claim to be either ILSAC GF-2 or API SJ. These requirements include:
Flash Point either by ASTM D 93, Standard Test Methods
for Flash-Point by Penske-Martens Closed Cup Tester, minimum flash point of 200C or by ASTM D 92, Standard Test
Method for Flash and Fire Points by Cleveland Open Cup,
m i n i m u m flash point of 185C,
Gelation Index (a measure of low-temperature oil gelling
tendency) by ASTM D 5133, Standard Test Method for Low
Temperature, Low Shear Rate, Viscosity/Temperature
Dependence of Lubricating Oils Using a TemperatureScanning Technique,
472
HANDBOOK
gine oil (the same groupings of viscosity grade as were defined in the ILSAC GF-2 requirements for the Sequence VIA
Test, as described previously). Sequence VIB fuel efficiency
requirements apply only to ILSAC GF-3 oils, not to API SL
oils, although oils satisfying the Sequence VIB requirements
for GF-2 can use the "Energy Conserving" label of the bottom
half of the API service symbol, as was previously mentioned
under the topic "Energy Conserving Characteristics," Sequence VIA.
Bench and Other Test Requirements
Most of the same bench and chemical property requirements
that exist for ILSAC GF-2 and API SJ categories also exist for
ILSAC GF-3 and API SL (although in some cases the limits
associated with the tests for ILSAC GF-3 and API SL are different from those required for ILSAC GF-2 and API SJ).
These requirements include:
Volatility loss as determined either by ASTM D 5800 or by
ASTM D 6417,
Filterability criteria as measured by the Engine Oil Filterability Test and the Engine Oil Water Tolerance Test,
Foaming tendency by ASTM D 892 and D 6082,
Homogeneity and Miscibility by Federal Test Method 791c,
Method 3470.1,
Gelation Index by ASTM D 5133, and
Maximum phosphorus content as measured either by
ASTM D 4951 or by ASTM D 5185.
There are, however, two new bench test requirements for
ILSAC GF-3 and API SL oils: the Ball Rust Test and the
TEOST MHT-4 test.
Ball Rust Test
ASTM D 6557, Standard Test Method for Evaluation of Rust
Preventive Characteristics of Automotive Engine Oils, was
developed to replace the Sequence IID Engine Test, which
measures the ability of an oil to prevent rust and corrosion in
engines operating on leaded gasoline under short-trip driving
conditions. ASTM D 6557 is also known as the Ball Rust Test,
since it uses a steel ball (lifter check ball) as a test specimen
that is representative of a typical ferrous engine component.
A ball and a measured sample of an engine oil that is to be
evaluated are placed in a test tube. If more than one oil sample is to be tested, additional test tubes, each containing a ball
and an oil sample are prepared. The test tubes are placed in
a shaker in which shaker speed and temperature are controlled. Air and a corrosive fluid are fed into the test tube to
create a corrosive environment. The corrosive fluid consists
of representative samples of the type of chemicals that can be
generated during the combustion process in short-trip winter
driving. After 18 h, the steel test specimens (balls) are evaluated for the extent of rusting, using a computerized scanning
system with optical imaging. Excellent correlation between
results obtained in the Ball Rust Test and Sequence IID has
been achieved with a wide variety of oil compositions. However, the method indicates that, in comparison with the results of ASTM D 5844 (Standard Test Method for Evaluation
of Automotive Engine Oils for Inhibition of Rusting (Sequence IID), "correlation between these two test methods
has been demonstrated for most, but not all, of the test oils
evaluated."
CHAPTER
TEOSTMHT-4
A new version of the Thermo-Oxidation Engine Oil Simulation Test (TEOST), the MHT-4, was developed for ILSAC GF3 and API SL specifications. The TEOST MHT-4 test is intended to provide additional high-temperature piston deposit
control in m o d e m engines that are designed for improved
driveability and in addition must meet federal emissions and
fuel economy requirements.
D i e s e l E n g i n e Oil P e r f o r m a n c e C a t e g o r i e s a n d
Associated ASTM Standard Test M e t h o d s
When diesel engines are operated at high temperature, the
viscosity of the engine oil can increase due to oil oxidation
and nitration, base stock polymerization, evaporation of the
lighter ends of the oil, and accumulation of soot in the oil. As
was the case for gasoline-fueled vehicles, diesel engine oil additives can degrade during long-term use. If the engine oil degrades to the point at which it becomes acidic, acidic reaction
products that form on a metal surface can be scraped off by
moving components, resulting in undesirable wear. In addition, soot accumulation can adversely affect engine wear by
two fundamentally different mechanisms. Soot can interact
with a n d sequester a n engine oil's antioxidant/anti-wear
agent so that the anti-wear capability of the engine oil becomes diminished [13]. Soot can also abrade away a protective anti-wear film that has formed on heavily loaded regions
of an iron surface [3]. These oil-related concerns are addressed using various standard tests.
At the t i m e of this writing, there were five active API
(American Petroleum Institute) diesel engine oil performance categories, designated as API CF, API CF-2, API CF-4,
API CG-4 and API CH-4. Each of these categories has at least
two engine performance tests t h a t m u s t be conducted to
demonstrate compliance with category requirements. Various bench tests are also included. A complete description of
each of these categories, including engine and bench tests, as
well as associated test limits for each requirement, is documented in ASTM D 4485, Stcindard Specification for Performance of Engine Oils and in SAE J183, Engine Oil Performemce and Service Classification. It is anticipated that these
five categories will be reduced to three: API CF-2, API CG-4,
and API CH-4. Thus, API CF and API CF-4 will no longer be
used. A description of each of these diesel engine-oil performance categories is as follows.
APICF
API CF oils are intended for use in off-road indirect-injection
diesel engines using a broad range of fuel types, including
those with high sulfur content. The only ASTM Standard
test in the performance definition of this category is the CRC
L-38 Test (ASTM D 5119), which measures bearing weight
loss a n d oil deterioration, as described previously. NonASTM tests include the Caterpillar IM-PC test (PC stands for
Pre-Chamber), which measures piston deposits and ring
sticking in a single cylinder diesel engine.
API CF-2
API CF-2 oils are intended for use in two-stroke-cycle engines, which require cylinder and ring-face scuffing resistance and deposit control. ASTM standard test requirements
17: AUTOMOTIVE
LUBRICANTS
473
include the CRC L-38 (ASTM D 5119) test, which has already
been described, and the Detroit Diesel 6V92TA test (ASTM D
5862). ASTM D 5862, Standard Test Method for Evaluation
of Engine Oils in Two-Stroke Cycle Turbo-Supercharged
Detroit Diesel 6V92TA Engine, is a two-stroke cycle diesel engine test that measures such parameters as high-temperature
stability of engine oil, cylinder liner scuffing, piston ring face
distress, plugging of liner ports, and slipper bushing distress.
Removal of tin from the cylinder liner is also eveduated. Engine components are measured before and after the test to
determine the extent of wear or degradation. The test is conducted under two different modes of operation: torque mode
and power mode. In the torque mode, engine speed is 1200
revolutions per m i n and the oil gallery temperature is 102C.
In the power mode, the engine speed is 2300 revolutions per
min, at an oil gallery temperature of 111C. Additional parameters are listed in the test procedure. A non-ASTM Standard test requirement for this category is the Caterpillar IMPC method described under the API CF category.
API CF-4
The API CF-4 category describes the tests that are used for
high-speed service in four-stroke cycle diesel engines. The
category includes tests that m e a s u r e bearing weight loss,
ASTM D 5119 (the L-38 test, which measures oil degradation
and bearing corrosionincluding a mEiximum limit of 50 mg
bearing weight loss). Piston deposits, viscosity increase, and
brake specific oil consumption are rated according to the
Mack T-6 test. Average rate of kinematic viscosity increase in
the last 50 h according to the Mack T-7 test and oil consumption and wear in the Cummins NTC-400 test ctre also
measured. In addition, the Caterpillar IK engine test is used
to measure piston and ring groove deposits, piston scuffing,
ctnd oil consumption.
API
CG-4
API CG-4 oils are intended for use in high-speed, four-strokecycle diesel engines operating in both highway and off-road
conditions, with fuels in which the sulfur content may VEiry
from less than 0.05% sulfur by weight to less than 0.5 weight
% sulfur, as described in ASTM D 4485. These oils provide
effective control of deposits and wear in engines designed to
meet 1994 exhaust emission standards. ASTM Standard tests
include the Mack T-8 engine test (ASTM D 5967), ASTM Sequence HIE engine test (ASTM D 5533), CRC L-38 bearing
test (ASTM D 5119), the roller follower wear test (ASTM D
5966), and a corrosion bench test (ASTM D 5968). Foaming
tendency according to ASTM D 892 is also included. ASTM D
5533, ASTM D 5119, and ASTM D 892 are described previously in this chapter.
ASTM D 5966, Standard Test Method for Evaluation of
Engine Oils for Roller Follower Wear in Light-Duty Diesel
Engine, was developed to address soot accumulation in engine oil, which can contribute to engine wear [3,13]. This test
is conducted at 1000 revolutions per min and a m a i n oil
gallery temperature of 120C. Roller follower shaft wear is
evaluated. Kinematic viscosity at 100C cind soot content are
also monitored.
ASTM D 5967, Standard Test Method for Evaluation of
Diesel Engine Oils in T-8 Diesel Engine (the Mack T-8 Test),
eveJuates both viscosity increase and soot accumulation in
474
HANDBOOK
the engine oil of a Mack E7-350 diesel engine. Oil consumption is also monitored. The test is conducted at an engine
speed of 1800 revolutions per min, a fuel rate of 63.3 kg/hour,
an engine oil temperature of 100-107C, and an inlet manifold temperature of 43.3C. Additional test conditions are
listed in the test procedure. The viscosity should not increase
by more than 11.5 centistokes at a soot content of 3.8%.
ASTM D 5968, Standard Test Method for Corrosiveness of
Diesel Engine Oil, measures the extent to which non-ferrous
metals are susceptible to corrosion as a consequence of inappropriate engine oil formulation (rather than oil degradation
or contamination). Test coupons (lead, copper, tin, and phosphor bronze) are cleaned and placed in the test oil. Air is
allowed to flow into the oil for 168hat 121C. Test coupons
are evaluated for corrosion and discoloration, and the oil is
evaluated for the presence of metals that have entered the oil
as a consequence of corrosion of the metcil samples.
Non-ASTM tests used in defining the API (American
Petroleum Institute) CG-4 specification include the Caterpillar IN engine test, which measures piston deposits in a fourstroke-cycle, direct injection diesel engine operating on fuel
containing less than 0.05 percent sulfur by weight. API CG-4
also includes the Engine Oil Aeration Test (EOAT), which has
been correlated with oil aeration in diesel engines equipped
with hydraulically actuated, electronically controlled unit injectors.
API CH-4
API CH-4 oils are intended for use in high-speed, four-strokecycle diesel engines designed to meet 1998 exhaust emissions
standards. ASTM Standard tests include CRC L-38 (ASTM D
5119, Standard Test Method for Evaluation of Automotive
Engine Oils in the CRC L-38 Spark-Ignition Engine), ASTM
Sequence HIE test (ASTM D 5533), Mack T-8 (ASTM D 5967),
and a high temperature corrosion bench test (ASTM 5968)
were described previously.
The Mack T-9 (ASTM D 6483) is described below. The tests
use diesel fuels with sulfur content up to 0.5 weight %, as described in ASTM D 4485. Foaming tendency (ASTM D 892),
volatility (ASTM D 5800 or ASTM D 6417), and sheared viscosity (ASTM D 6278) requirements are also included.
ASTM D 6483 (Standard Test Method for Evaluation of
Diesel Engine Oils in T-9 Diesel Engines, known as the Mack
T-9 test) evaluates diesel engine oil for various performance
characteristics, including resistance to lead corrosion and
wear of piston rings and cylinder liners. The test uses a Mack
E7-350 V-MAC II diesel engine. The test starts with a onehour break-in, followed by a two-phase test that includes 75
h at 1800 revolutions per min and 425 h at 1250 revolutions
per min. Oil samples are taken during the testing and are analyzed for increase in viscosity and for weeir metals in the oil.
The extent of engine-component wear is also assessed. For
example, the maximum allowed cylinder liner wear is an average value of 25.4 \xxn at a soot content of 1.75%. The maximum allowed average-top-ring weight loss is 120 mg, and the
maximum allowed increase of lead content in the engine oil
is 25 parts per million.
Non-ASTM standard tests used in defining the API CH-4
category include the following. The Caterpillar IP engine test
measures piston and ring groove deposits in four-strokecycle, direct injection diesel engines calibrated to meet 1998
United States Federal Exhaust Emissions Standards with fuels containing less than 0.05% sulfur by weight. The Caterpillar IK engine test measures the same performance parameters as the Caterpillar IP engine test, but for engines in use
prior to 1989, using aluminum pistons and fuel that has 0.4
weight % sulfur. The Cummins Mil High Soot Diesel Engine
Test measures soot-related valve-train wear. Engine sludge
and oil filter plugging tendency are measured. The Engine Oil
Aeration Test (EOAT), mentioned in the API CG-4 specification, is also conducted.
Additional Tests Used to Describe Engine Oil
Performance and Properties
The use of a bench test, if it can be shown to correlate to an
engine test, can be considerably less labor intensive and less
costly than an engine test. Bench tests for engine oil are of
several types. Some, such as the Ball Rust Test, ASTM D 6557
(described previously), produce fundamental information
about a specific aspect of the protection provided by an engine oil. Other bench tests measure various properties of the
engine oil such as viscosity, alkalinity, acidity, extent of oil
oxidation, presence of oil additives, and the presence of oil
contaminants such as engine-wear debris or corrosion products. Many of these bench tests are included as part of the
specified analysis procedure for an engine test. In other
words, a bench test often provides necessary documentation
to evaluate the results of a dynamometer test. Various tests
that are used to ascertain the performance of automotive lubricants in general and engine oils in particular are described
in the following sections.
Engine Oil Acidity and Alkalinity
Automotive lubricants typically contain oil-soluble alkaline
agents that provide corrosion protection, since corrosion is
less likely to occur in a moderately alkaline environment.
Acids can be generated from fuel combustion or from oxidation of engine oil in hot spots. For example, if engine oil becomes acidic as a consequence of exposure to heat or if acidic
combustion by-products from the fuel condense in the engine
oil during short-trip, low temperature service, engine corrosion may occur. If oil alkalinity is too high, a lubricant or
other fluid may also become aggressive to a metal surface.
Several techniques are available to assess oil acidity and remaining alkalinity protection, for example:
ASTM D 664, Standard Test Method for Acid Number of
Petroleum Products by Potentiometric Titration
ASTM D 974, Standard Test Method for Acid and Base
Number by Color-Indicator Titration
ASTM D 1093, Standard Test Method for Acidity of Distillation Residues or Hydrocarbon Liquids
ASTM D 2896, Standard Test Method for Base Number of
Petroleum Products by Potentiometric Perchloric Acid
Titration
ASTM D 4739, Standard Test Method for Base Number Determination by Potentiometric Titration.
In each of these tests, a sample of the oil or residue of interest is titrated (that is, reacted) with the desired test
reagent. Different reagents used in the various tests yield different values for an acid number or base number. An investigator will have to determine which test best meets his needs.
3.1LV-6 engine
:i=^^
200
300
400
Distance on oil, l(m
500
600
25
Percent water
In engine oil,
Karl Fischer
method
JA N
'
11
MAR
FEB
'
APR
'
MAY
lUBSfuel65 % msthanol
+ 1 5 % gasoline
20
15
Engine
^
o
"
Fuel
Oil
3.1L MSSfuel A
'
<1
10
475
Ambient temperature
Near -20 C, 3-km trips
100
LUBRICANTS
4.5L gasoline B
4.5L gasoline B
1
'
200
400
600
800
1000
Distance traveled, km
FIG. 2Influence of type of fuel on the amount of water that can accumulate in engine oil during short-trip, cold-start driving, according to
ASTIM D 1744.
476
MANUAL
150
'
HANDBOOK
1
Viscosity of
engine oil at
40C, cSt
100
50
___x_ '
If the viscosity vEiries significantly with sheeu", different results may be obtained from viscometers of different diameter. ASTM D 446 gives specifications and operating instructions for glass kinematic viscometers.
ASTM D 4683 measures viscosity at high temperature and
high shear a n d carries the warning, "applicability to
petroleum products other than engine oils has not been determined." Engine oil at very low temperature can become
highly viscous, per ASTM D 4684 (which carries the same
warning as is found with ASTM D 4683). In ASTM D 4684, an
engine oil is cooled from 80C at a programmed rate to a fined low temperature (between -15C and -35C). Yield stress
and apparent viscosity are measured.
200
400
600
Distance on oii, Icm
800
1000
In addition to the changes in viscosity due solely t o temperature effects, operation at a given high temperature will
cause the oil's viscosity to increase (in comparison to viscosity of the fresh oil at the same temperature) due to oil oxidation and to evaporation of the lighter ends of the engine oil.
Various low-temperature viscosity cheinges can also be observed. Low engine-oil temperature causes an increase in viscosity. However, at low outside temperatures, hydrocarbon
fuel can condense in engine oil, which causes a decrease in
oil viscosity. Condensation of methanol (alcohol) fuel in engine oil formed an emulsion and caused a significant viscosity increase. An example of these opposite viscosity effects is
shown in Fig. 3, which is derived from information available
in Ref. 2.
Thus, fuel-in-oil measurements can provide information
about the nature of viscosity changes and the nature of contaminants in the engine oil. However, these effects only occur
if the engine oil remains at low temperature during short-trip
operation, otherwise once the oil t e m p e r a t u r e rises sufficiently, m u c h of the fuel will evaporate from the oil, and the
oil viscosity will revert to a more typical value.
Standard ASTM viscosity tests include:
ASTM D 445, Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of
Djoiamic Viscosity),
ASTM D 446, Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers,
ASTM D 4683, Standard Test Method for Measuring Viscosity at High Temperature and High Shear Rate by Tapered Bearing Simulator,
ASTM D 4684, Standard Test Method for Determination of
Yield Stress and AppcU^ent Viscosity of Engine Oils at Low
Temperature.
ASTM D 445 measures the time it takes for a liquid to flow
through a standard capilleiry tube. This test method has the
wzuning, "The result obtained from this test method is dependent u p o n the behavior of the sample cind is intended for
application to liquids for which primarily the shear stress
and shear rates are proportional (Newtonian flow behavior)."
1(
4I
Oxidation
induction
time by
3
differential
scanning
calorimetry,
natural
2
logarithm of
DSC
^ % v
1.
NS^ *
. No trailer
o\.
0 N
\ * ^^
o \
With trailer
NO
BP*
\ o
VNA
^-0
5000
10000
Distance on oil, km
0^^-
'
15000
CHAPTER
Even though this method was developed for greases, it can
be used for other lubricants. An example is found in Figure 4,
which shows differences in the rate of engine oil oxidation
between similar vehicles, driving over identical terrain, but
two of the vehicles were not pulling a trailer (dark circles),
and one of the vehicles pulled a 1000-kg trailer (open circles)
[14,15]. As can be seen, the constant-temperature version of
the differential scanning calorimetry technique (abbreviated
as "DSC") was able to document statistically significant differences in the chemical status of the engine oil from the vehicle that pulled the trailer. The natural logarithm of the DSC
value was plotted. This figure indicates that oxidative stability can be a reliable measure of severity of service. The theoreticcil explanation for this effect is provided in Ref. 14.
The various ASTM standard test procedures described in
this section list a great n u m b e r of related test methods. Referenced Documents from these test methods are provided in
Tables 2 and 3 at the end of this chapter, so that the reader
will have a comprehensive list of the various tests associated
with engine oil.
TRANSMISSION FLUIDS
Composition and Performance of
Transmission Fluids
Transmission fluids lubricate a vehicle's transmission. They
may be composed of synthetic or mineral oil. S5Tithetic oil
typiccilly shows enhanced resistance to deterioration from exposure to heat. However, synthetic and mineral oil both contain additives that help maintain the desired friction properties, minimize wear, and provide corrosion inhibition to the
transmission components. In addition, antioxidant additives
are required to prolong the life of the transmission fluid.
Maintaining stable friction properties is highly important,
since any change in shift characteristics or generation of
shudder (objectionable vibration) after prolonged or severe
use is sure to be noticed by a vehicle owner. To provide the
desired shift properties, one of the additives present in a
transmission oil is typically a long-chain hydrocarbon that
has a polar group on one end. The polar end group of the additive is attracted to the metal surface, and the long-chain hydrocarbon portion associates with the oil, thereby forming a
durable, low-friction oil film on the metal surface. Too m u c h
friction reduction will cause transmission components to
slip, b u t too little friction reduction will not allow the transmission to shift smoothly cind will cause wear.
In addition to appropriate friction characteristics, it is also
essential to reduce wear a n d promote long transmission life.
Wear protection is provided to a great extent by oil additives.
If suitable anti-wear additives were not present, there would
likely be excessive weeir of the transmission components under severe operating conditions. Thus, fluid degradation during prolonged service should not be extensive enough to comp r o m i s e transmission performance, a n d wear rates m u s t
remain low so that excessive loss of material does not cause
shift characteristics to deteriorate.
Various standard test methods are available to ensure sustained transmission performance. Tests for automatic transmission fluids include measurement of physical eind chemical properties: viscosity, flash point, pour point, corrosion
17: AUTOMOTIVE
LUBRICANTS
477
resistance, wear resistance, friction characteristics, and resistance to foaming. Additional tests measure performance
during selected duty cycles, as defined by the manufacturer.
For example, major automotive producers in North America
have their own specifications for transmission fluids. Thus,
in retail establishments that sell transmission fluids, one can
see labels on transmission fluid bottles indicating "meets the
specifications for XXX a n d YYY", in which XXX and YYY
represent the brand names of a specific automobile manufacturer. Transmission fluid test requirements published by a
given automobile m a n u f a c t u r e r include GM-6417M for
Dexron-III (General Motors) a n d Mercon-V (Ford).
A n u m b e r of standard ASTM tests for transmission fluids
are listed in the SAE International Surface Vehicle Information Report, SAE J311 (revised 2000-02): ASTM D 130 (Copper Strip Corrosion), ASTM D 665 (Rust Preventing Characteristics), ASTM D 892 (Foaming Characteristics, as
described previously in the Engine Oil section), ASTM D
1275 (Corrosive Sulfur in ElectriccJ Insulating Oils, which is
not listed in the 2001 ASTM a n n u a l book of standards),
ASTM D 1748 (Rust Protection by Metal Preservatives in the
Humidity Cabinet), and ASTM D 2882 (Wear Characteristics
of Hydraulic Fluids in a Constant Volume Vane Pump). Additional ASTM tests are also provided in the Annual Book of
ASTM Standards. The tests listed here are described below.
Referenced d o c u m e n t s in these transmission-related test
methods are provided in Tables 4 and 5 at the end of the
chapter.
478
MANUAL
HANDBOOK
ASTM D 5662, Standard Test Method for Determining Automotive Gear Oil Compatibility with Typical Oil Seal Elastomers, measures whether the properties (hardness, volume,
and elongation in a stretch test) of selected oil-seal elastomers (nitrile, polyacrylate, and
fluoroelastomer)
are
changed on exposure to automotive gear oils.
Additional transmission-related tests referenced in the
standard methods described here are listed in Tables 4 and 5
at the end of this chapter.
Properties,
Stability,
and
Contamination
CHAPTER
sured. The method indicates that "correlation between results from this test method and service performance has not
been established."
ASTM D 942 (Reapproved 1995), Standard Test Method for
Oxidation Stability of Lubricating Greases by the Oxygen
Bomb Method, measures the ability of a grease to resist oxidation in an oxidizing atmosphere at elevated temperature. A
sample of grease is oxidized in a sealed b o m b that is filled
with oxygen at 110 psi (758 kPa) at 99C. Pressure is recorded
during the test. The extent of oxidation is determined by measuring the decrease in oxygen pressure. The method carries
the notification that this test method "predicts neither the
stability of greases under dynamic service conditions, nor the
stability of films of greases on bearings and motor-parts. It
should not be used to estimate the relative oxidation resistance of different grease types."
ASTM D 1743, S t a n d a r d Test Method for Determining
Corrosion Preventive Properties of Lubricating Greases,
measures the ability of a grease to protect a bearing against
corrosion in the presence of water. A bearing is r u n for a
short time and is then exposed to water. After 48 h at 52C
and 100% humidity the bearing is inspected for corrosion.
In ASTM D 4048, Standard Test Method for Detection of
Copper Corrosion from Lubricating Grease, a copper strip is
immersed in a sample of grease and heated for a period of
time. Typical time and temperature conditions are 100C for
24 h. At the end of the test the copper strip is washed and
compared to copper strip standards to provide a measure of
the severity of corrosion. The method states, "no correlations
with actual field service, most of which are under djmamic
conditions, have been established. It does not measure either
the ability of the lubricant to inhibit copper corrosion caused
by factors other than the lubricant itself nor does it measure
the stability of the grease in the presence of copper."
ASTM D 1742, Standard Test method for Oil Separation
from Lubricating Grease During Storage, measures the tendency of a grease to separate into distinct fractions during
storage. A sample of grease is placed on a sieve and is subject
to 1.72 kPa (0.25 psi) at 25C for 24 h. The amount of matericJ that seeps into a beaker is weighed. The test represents
separation during storage rather than separation under dynamic operating conditions. The following warning is provided: "This test method is not suitable for greases softer than
NLGI No. 1 grade." In addition, the m e t h o d states, "this
method is not intended to predict oil separation tendencies of
the grease under dynamic conditions." The method does indicate oil separation that occurs during storage.
ASTM D 1404, Standard Test Method for Estimation of
Deleterious Particles in Lubricating Grease, measures the
presence of abrasive or inappropriate particles in a grease. A
small sample of grease is placed between two standard plastic plates, and pressure is applied to the plates. The presence
of inappropriate abrasive peirticles produces a characteristic
scratch pattern. The n u m b e r of such scratch patterns on the
plates is determined. "The significance of the n u m b e r of
scratches as far as correlation with field performance is concerned has not been established."
If a grease comes into contact with an elastomer, several effects may occur. Components of the grease may be sufficiently compatible with the elastomer that grease components enter the elastomer structure and cause the elastomer
17: AUTOMOTIVE
LUBRICANTS
479
and Penetration
Effects
The viscosity of the base oil in a grease has a significant influence on the properties of a grease. ASTM D 445 (mentioned previously) describes the measurement of the base oil
viscosity by determining the time required for the base oil to
flow through a calibrated glass tube.
The thickening agent in a grease uses surface tension and
molecular attractions to help hold the grease's oil in the place
in which it is supposed to provide protection. The thickening
agent can consist of fibers, platelets, or spheres, which are insoluble or only slightly soluble in the grease. Thickeners can
also be complex polymer-like chains such as complex
polyureas. ASTM D 1092, Standard Test Method for Measuring Apparent Viscosity of Lubricating Greases, determines
the viscosity of the grease over the range of 53 to 37.8C. A
sample of the grease is forced through a capillary, using a
floating piston that is controlled by a hydraulic system. Viscosity is calculated from the flow rate and the force developed in the system.
ASTM D 1263, Standard Test Method for Leakage Tendencies of Automotive Wheel Bearing Greases, measures the
leakage of a grease from a modified front wheel h u b and
spindle assembly. The wheel is rotated at a speed of 660 revolutions per min for 6 h at a temperature of 105C. The extent
of leakage is determined, and the condition of the bearing
surface is noted at the end of the test. The method carries the
notice that "it is not the equivalent of longtime service tests,
n o r is it intended to distinguish between wheel bearing
greases showing similar or borderline leakage."
A related leakage test is ASTM D 4290, S t a n d a r d Test
Method for Determining the Leakage Tendencies of Automotive Wheel Bearing Grease Under Accelerated Conditions. In
this test, grease is placed in a modified version of an auto-
HANDBOOK
CHAPTER
The following warning is listed, "Although this test method is
widely used for specification purposes, the significance of the
roll stability test has not been determined."
ASTM D 2266, Standard Test Method for Wear Preventive
Characteristics of Lubricating Grease (Four-Ball Method),
measures the ability of a grease to resist wear in sliding steelon-steel contacts. It does not address wear in materials other
than steel on steel, nor does it evaluate the extreme pressure
characteristics of a grease. In this test a steel ball is rotated
while in contact with three additional balls. The diameter of
the wear scar on each of the non-rotating balls is measured.
The test method indicates that "No correlation has been established between the four-ball wear test and field service."
ASTM D 2509, Standard Test method for Measurement of
Load-Carrying Capacity of Grease (Timken Method), uses a
steel cup that rotates against a steel block at a rotation speed
of 123.71 m per min. The m i n i m u m load needed to rupture
the lubricant film that lies between the rotating cup and the
block is determined. A determination is also made of the
m a x i m u m safe load such that the lubricant film will not be
ruptured by the rotating cup, and abrasion will not occur between the rotating cup and the block. The test procedure indicates that: "The test method is used widely for specification
purposes and is used to differentiate between greases having
low, medium, or high levels of extreme pressure characteristics. The results may not correlate with results from service."
ASTM D 2596, Measurement of Extreme Pressure Properties of Lubricating Grease (Four-Ball Method), determines
the load-carrying properties of lubricating grease. Two properties are measured: the diameter of the wear scar (for the
case in which welding or seizure does not occur) and the load
at which welding occurs. Two warnings are provided: 1) "The
results do not necessarily correlate with results from service"
and 2) "Lubricating greases that have as their fluid component a silicone, halogenated silicone, or a mixture comprising silicone fluid and petroleum oil, are not applicable to this
method of test."
ASTM D 3336, Standard Test Method for Life of Lubricating Greases in BeJl Bearings at Elevated Temperatures, evaluates the performance of lubricating greases operating at elevated temperatures (up to 371C) in ball bearings, at a speed
of 10 000 revolutions per min, but under light load. If the test
temperature is 149C or below, the test cycle is operated at
test temperature for 21.5 h per day, with 2.5 h of shut-down
per day in which heat is not applied. If the test temperature
is r u n at a temperature greater than 149C, the test is run for
20 h per day at the desired test temperature, with 4 h per day
of shut-down in which n o heat is applied. Tests are conducted until failure or until a specified n u m b e r of hours is
reached. The grease has failed the test when one of the following conditions has occurred:
Spindle output power increases to a value of three hundred
percent above the steady state condition at test temperature.
An increase in temperature of 15C over the test temperature occurs (but the daily start-up temperature rise is not
to be construed as a test failure).
There is loading of the test bearing or belt slippage at startu p or during the test cycle.
Hours to failure are plotted in terms of cumulative percentage of the tests conducted. Examples of these plots
(known as WeibuU plots) are provided as part of the test-
17: AUTOMOTIVE
LUBRICANTS
481
482
MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
CHAPTER
extent of corrosion of a copper strip, was described in the section on transmission fluids.
Test methods for gear oils are also available from CRC
(Coordinating Research Council). The CRC L-37 method is a
24-hour dynamometer test that is conducted at high torque
and low speed and that assesses gear distress. CRC L-42 is a
24-hour dynamometer test incorporating high speed shock
loading, designed to measure resistance to gear scoring. CRC
L-33 is a 7-day motored rust test in which geeirs are exposed
to humidity in an oven. CRC L-60-1 is a test for oxidation and
deposits, using motored gears over a period of 50 h.
Viscosity characteristics of axle lubricants are measured according to ASTM D 445, Standard Test Method for Kinematic
Viscosity of Transpsirent eind Opaque Liquids (the Calculation
of Dynamic Viscosity), as described under the section on engine oils. Low temperature viscosity is measured using ASTM
D 2983, Standard Test method for Low-Temperature Viscosity of Automotive Fluid Lubricants Measured by Brookfield
Viscometer. In this test, viscosity is measured in the temperature range from 5 to 40C, using a rotating spindle.
Axle Lubricants
An additional area of concern related to gear lubricants is the
topic of axle lubricants. Requirements for axle lubricants are
described in the American Petroleum Institute API-GL-5 requirements for gear lubricants. However, two of the tests
listed in API-GL-5 (CRC L-37 and CRC L-42) are not required
for axle lubricants. Desirable properties for axle lubricants
include viscosity in an appropriate range (for example, near
14 or 15 centistokes at 100C). Performance of an axle lubricant must not degrade excessively during service. The axle lubricant must not damage metal components, nor should the
metal components accelerate an axle lubricant's degradation.
In addition, axle lubricants must not damage seals. Desirable
axle-lubricant attributes include fuel efficiency, thermal
stability, long life, and appropriate limited-slip differential
performance.
Referenced documents related to geeir and axle lubricant
test methods are provided at the end of this chapter. Tables 8
and 9.
BRAKE FLUIDS
Brake fluid typically behaves like a hydraulic fluid, since fluid
power is used to apply force to the brakes, therefore generating enough friction to slow and stop the forward motion of
the vehicle. Fifty years ago, if water got into brakes during a
heavy rain, the brakes might not work properly, and an accident might result. Today, with better technology, such occurrences are rare. However, someone who is servicing a brake
system must make sure to instcill the appropriate brake fluid
for that brake, otherwise there is risk that the brakes will not
function as they should.
Two types of braking systems are typically used in vehicles:
drum brakes and disk brakes. In a d r u m brake, a drum rotates with the wheel. Curved brake shoes are inside the drum,
separated by a slight air gap from the drum. When a driver
steps on the brake, brake fluid, acting like a hydraulic fluid to
apply force where it is needed, is sent to the braking system
17: A UTOMOTIVE
LUBRICANTS
483
such that the brake shoes are pressed onto the rotating drum.
The friction of the shoe against the d r u m stops the wheel.
A disk brake has a metal disk, and flat shoes or pads are
pressed against the disk to provide the force to stop the vehicle, using the force supplied by the hydraulic action of the
brake fluid.
Thus, the motion of a braking mechanism is controlled by
a hydraulic system that includes a pump, a fluid, and lines
(tubes) that transmit the hydraulic force to the brake components. The brake fluid must not react with components of the
brake system, and it must be able to withstand wide variations in temperature while still performing effectively.
Requirements for the brake fluid are described in the 2001
SAE Handbook, Standards Development Program, Volume
2, Parts and Components and on-Highway Vehicles (Part I),
"Motor Vehicle Brake Fluid-SAE J1703 Jan95", page 25.49,
and "Borate Ester Based Brake Fluids-SAE J1704 Jan97",
page 25.59.
SAE J1703 and SAE J1704 specify such measurements as
boiling point, fluid stability, viscosity, reserve alkalinity, corrosion resistance, low-temperature fluidity, evaporation,
water tolerance, low temperature stability, resistance to oxidation, and effect on rubber materials such as seals. A number of standard ASTM methods related to these tests are
listed at the end of this chapter.
SOLID LUBRICANTS
Solid lubricants are used where it is important for the lubricant to stay in place. Solid lubriccints are typically composed
of a solid, a binder, and additives such as corrosion inhibitors
or solvents. Examples of c o m m o n solid lubricants include
molybdenum disulfide, graphite, a n d polytetrafluoroethylene (PTFE) or other fluorine-containing polymers. Molybden u m disulfide and graphite have a chemical structure that is
like flat plates such that an upper plate can easily slip eilong
the surface of the next plate beneath it. PTFE has a chemical
structure that typically does not attract or hold a variety of
common fluids such as water or oil, as witnessed by the fact
that the fluid tends to bead u p on the PTFE surface, rather
than spreading over the surface. In contrast, if a drop of oil
touches an iron surface, the oil spreads over the surface.
Solid lubricants typically have a temperature range over
which they are effective. Above the optimum reinge, they may
degrade chemically or physically. For example, according to
information in the Tribology Data Handbook, molybdenum
disulfide has a n u p p e r t e m p e r a t u r e limit in the range of
400C, but it can withstand high loads [16]. Graphite can
withstand 650C and moderate loads.
If PTFE (polytetrafluoroethylene) is used in a high-temperature application, care must be taken to ensure that the temp e r a t u r e does not exceed the point at which PTFE is no
longer stable. On the other hand, use of low-friction materials is an advantage with regard to fuel conservation in automotive vehicles.
ASTM D 2714, Standard Test Method for Calibration and
Operation of the Falex Block-on-Ring Friction and Wear
Testing Machine, provides a test method for determination of
friction coefficient of a solid lubricant. Friction coefficient is
defined as the ratio of the friction force, F, that resists movement to the normal force, N, that presses the two bodies to-
484
MANUAL
HANDBOOK
gether. A steel test ring rotates against a steel test block. The
specimen assembly is immersed in the lubricant. A normEil
load of 65 kg is applied. The velocity of the test ring is 7.9
m/min. The test method contains the warning that "The user
of this test method should determine to his or her own satisfaction whether results of this test procedure correlate with
field performance or other bench test machines. If the test
conditions are changed, wear values can change and relative
ratings can be different."
485
TABLE 2Referenced documents in ASTM standard test methods related to engine oil.
ASTM No.
C 1109
D 16
D56
D86
D91
D92
D93
D97
D117
D 129
D 130
D 140
D 156
D235
D240
D287
D323
D341
D381
D445
D446
D482
D524
D525
D613
D664
D850
D873
D892
D893
D974
D 1078
D1093
D1133
D1193
D 1217
D1250
Analysis of Aqueous Leachiates from Nuclear Waste Materials Using Inductively Coupled Plasma-Atomic Emission
Spectrometry
Definitions of Terms Relating to Paint, Varnish, Lacquer, and Related Products
Flash Point by Tag Closed Tester
Distillation of Petroleum Products
Acidity of Hydrocarbon Liquids and Their Distillation Residues
Flash and Fire Points by Cleveland Open Cup
Flash Point by Penske-Martens Closed Tester
Pour Point of Petroleum Products
Guide to Sampling Test Methods, Standard Practices, and Guides for Electrical Insulating Oils of Petroleum Origin
Sulfur in Petroleum Products (General Bomb Method)
Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
Practice for Sampling Bituminous Materials
Saybolt Color of Petroleum Products (Saybolt Chromometer Method)
Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Dry Cleaning Solvent)
Heat of Combustion of Liquid HydrocEirbon Fuels by Bomb Calorimeter
API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method)
Vapor Pressure of Petroleum Products (Reid Method)
Viscosity-Temperature Charts for Liquid Petroleum Products
Existent Gum in Fuels by Jet Evaporation
BCinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
Ash from Petroleum Products
Ramsbottom Carbon Residue of Petroleum Products
Oxidation Stability of Gasoline (Induction Period Method)
Cetane Number of Diesel Fuel Oil
Acid Number of Petroleum Products by Potentiometric Titration
Acidity of Hydrocarbon Liquids and Their Distillation Residues
Oxidation Stability of Aviation Fuels (Potential Residue Method)
Foaming Characteristics of Lubricating Oils
Insolubles in Used Lubricating Oils
Acid and Base Number by Color-Indicator Titration
Distillation Range of Volatile Organic Liquids
Acidity of Hydrocarbon Liquids and Their Distillation Residues
Kauri-Butanol Value of Hydrocarbon Solvents
Specification for Reagent Water
Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
Standard Guide for Petroleum Measurement Tables
(continues)
D1310
D 1319
D 1353
D1480
D1481
D1552
D2170
D2171
D2422
D2500
D2509
D2622
D2699
D2700
D2709
D2782
D2887
D2896
D2982
D3120
D3231
D3237
D3244
D3338
D3339
D3525
D3606
D3829
D3941
D4052
D4057
D4175
D4177
D4206
D4294
D4307
D4485
D4626
D4628
D4636
D4683
D4684
D4737
D4739
D4741
D4863
D4927
D4951
D5119
D5133
D5134
D5185
D5186
D5290
D5302
D5480
D5481
D5533
D5800
D5844
5862
5966
5967
5968
6074
6082
6202
D
D
D
D
D
D
D
E
E
E
E
E
E
E
6278
6299
6300
6335
6417
6483
6557
1
29
77
128
135
178
191
E 270
E 300
E 344
E 355
E 380
E 473
E 502
E 594
E 691
E 1119
E 1500
G 40
487
TABLE 2(continued).
Test Method or Document Title
Evaluation of Engine Oils in Two-Stroke Cycle Turbo-Supercharged 6V92TA Diesel Engine
Evaluation of Diesel Engine Oils for Roller Follower Wear in Light-Duty Diesel Engine
EvcJuation of Diesel Engine Oils in the T-8 Diesel Engine
Evaluation of Corrosiveness of Diesel Engine Oil
Guide for Characterizing Hydrocarbon Lubricant Base Oils
High Temperature Foaming Characteristics of Lubricating Oils
Measurement of the Effects of Automotive Engine Oils on the Fuel Economy of Passenger Cars and Light-Duty Trucks
in the Sequence VIA Spark Ignition Engine
Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus
Applying Statistical Quality Assurance Techniques to Evaluate Anals^ical Measurement System Performance
Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
Determination of High Temperature Deposits by Thermo-Oxidation Engine Oil Simulation Test
Estimation of Engine Oil Volatility by Capillary Gas Chromatography
Evaluation of Diesel Engine Oils in the T-9 Diesel Engine
Evaluation of Rust Preventative Characteristics of Automotive Engine Oils
Specification for ASTM Thermometers
Standard Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
Inspection and Verification of Thermometers
Maximum Pore Diameter and Permeability of Rigid, Porous Filters for Laboratory Use
Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
Practice for Dealing With Outlying Observations
Specification for Apparatus for Microdetermination of Carbon a n d Hydrogen in Organic and Organo-Metallic
Compounds
Terminology Relating to Liquid Penetrant Examination
Practice for Sampling Industrial Chemicals
Terminology Relating to Thermometry and Hydrometry
Gas Chromatographic Terms and Relationships
Use of the International System of Units (SI) (The Modernized Metric System)
Terminology Relating to Thermal Analysis
Selection and Use of ASTM Standards for the Determination of Flash Point of Chemicals by the Closed Cup Method
Testing Flame Ionization Detectors Used in Gas Chromatography
Conducting an Inter-Laboratory Study to Determine the Precision of a Test Method
Specification for Industrial Grade Ethylene Glycol
Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs
Terminology Relating to Wear and Erosion
Military Specification
SAE (Society of Automotive
Engineers) Standards
489
TABLE 4Referenced documents in ASTM standard test methods for transmission fluids.
ASTM No.
A108
A 109
A 240/A 240 M
B224
D91
D130
D235
D396
D412
D445
D471
D512
D516
D664
D892
D893
D975
D 1193
D1217
D 1401
D1480
D 1481
D 1655
D 1838
D2170
D2171
D2240
D2422
D3603
D4057
D4175
D4177
D5182
D5579
D5662
D5704
D5760
D6074
El
E77
E527
G40
ASTM Adjuncts
ISO
SAE Standard
491
D88
D95
D97
D130
D 156
D217
D235
A 240/A 240M
Saybolt Viscosity
Water in Petroleum Products and Bituminous Materials by Distillation
Pour Point for Petroleum Oils
Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
Saybolt Color of Petroleum Products (Saybolt Chromometer Method)
Cone Penetration of Lubricating Grease
Specifications for Mineral Spirits (Petroleum Spirits) Hydrocarbon Dry Cleaning Solvent
Specification for Heat-Resisting Chromium and Chromium-Nickel Stainless Steel Plate, Sheet, and Strip for
Pressure Vessels
Rubber ProductsChemical Analysis
Specification for Acetone
Vulcanized Rubber and Thermoplastic Elastomers-Tension
BCinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
Rubber PropertyEffect of Liquids
Sediment in Crude Oils and Fuel Oils by the Extraction Method
Dropping Point of Lubricating Grease
Specification for Isopropyl Alcohol
Rockwell Hardness of Plastics and Electrical Insulating Materials
Cone Penetration of Petrolatum
Evaporation Loss of Lubricating Greases and Oils
Distillation Range of Volatile Organic Liquids
Specification for Reagent Water
Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
Flash Point and Fire Point of Liquids by Tag Open-Cup Apparatus
Nonvolatile Matter in Volatile Solvents for Use in Paints, Varnish, Lacquer, and Related Products
Cone Penetration of Lubricating Grease Using One-Quarter and One-Half Scale Cone Equipment
Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
Density and Relative Density (Specific Gravity) of Viscous Materieds by Lipkin Bicapillary Pycnometer
BCinematic Viscosity of Asphalts (Bitumens)
Viscosity of Asphalts by Vacuum Capillary Viscometer
Rubber Property-Durometer Hardness
Dropping Point of Lubricating Grease Over Wide Temperature Range
Cloud Point of Petroleum Oils
Evaporation Loss of Lubricating Greases Over Wide Temperature Range
Calibration and Operation of the Falex Block-on-Ring Friction and Wear Testing Machine
Practice for Rubber-Materials, Equipment, and Procedures for Mixing Standard C o m p o u n d s and Preparing
Standardized Vulcanized Sheets
Practice for Rubber-Preparation of Pieces for Test Purposes from Products
Practice for Utilization of Test Data to Determine Conformance with Specifications
Life Performance of Automotive Wheel Bearing Grease
Terminology Relating to Petroleum, Petroleum Products, and Lubricants
Elastomer Compatibility of Lubricating Greases and Fluids
Determining the Leakage Tendencies of Automotive Wheel Bearing Grease under Accelerated Conditions
Low-Temperature Torque of Grease-Lubricated Wheel Bearings
Classification of and Specification for Automotive Service Greases
Oxidation Induction Time of Lubricating Greases by Pressure Differential Scanning Calorimetry
Determining Extreme Pressure Properties of Lubricating Greases Using a High-Frequency, Linear Oscillation
(SRV) Test Machine
Measuring Friction and Wear Properties of Lubricating Grease Using a High-Frequency, Linear Oscillation (SRV)
Test Machine
Corrosion-Preventive Properties of Lubricating Greases in Presence of Dilute Synthetic Sea-Water Environments
Guide for Characterizing Hydrocarbon Lubricant Base Oils
Corrosion-Preventive Properties of Lubricating Greases Under Dynamic Wet Conditions (Emcor Test)
Oil Separation from Lubricating Grease (Conical Sieve Method)
Practice for Evaluating Compatibility of Binary Mixtures of Lubricating Greases
Specification for ASTM Thermometers
Specification for Wire-Cloth Sieves for Testing Purposes
Inspection and Verification of Thermometers
Calibration of Thermocouples by Comparison Techniques
Temperature-Electromotive Force (EMF) Tables for Standardized Thermocouples
Practice for Preparation and Use of Freezing Point Reference Baths
Specification for Sheathed Base-Metal Thermocouple Materials
Specification for Metal-Sheathed Base-Metal Thermocouples
Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
Terminology Related to Corrosion and Corrosion Testing
ASTM Adjunct: Copper Strip Corrosion Standard, Adjunct PCN 12-401300-00
Test Methods for Rating Motor, Diesel, and Aviation Fuels; Motor Fuels (Section I), Reference Materials and
Blending Accessories (Annex 2), Reference Materials (A2.7), and Table 32; (Specification for ASTM Knock Test
Reference Fuel, n-heptane)
D297
D329
D412
D445
D446
D471
D473
D566
D770
D785
D937
D972
D 1078
D 1193
D 1217
D 1310
D 1353
D1403
D 1480
D 1481
D2170
D2171
D2240
D2265
D2500
D2595
D2714
D3182
D3183
D3244
D3527
D4175
D4289
D4290
D4693
D4950
D5483
D5706
D5707
D5969
D6074
D6138
D6184
D6185
E 1
E 11
E77
E220
E230
E563
E585
E608
E691
G 15
Adjunct
ASTM
Standard 4. Tolerance Definitions and Gaging Practices for Ball and Roller Bearings
Military Standard
NLGI (National Lubricating Grease Institute)
SAE (Soc. Automotive Engineers) Standard
493
ASTM No.
B16
D96
D 130
D235
D329
D341
D396
D412
D446
D471
D484
D892
D975
D 1193
D 1217
D 1480
D 1481
D1655
D1796
D1838
D2170
D2171
D2240
D2266
D2509
D2670
D2783
D4175
D5182
D5579
D5662
D5704
D5760
D6074
E 1
E 128
G40
ASTM
Adjuncts
Specification for Free-Cutting Brass Rod, Bar, and Shapes for Use in Screw Machines
Water and Sediment in Crude Oil by Centrifuge Method (Field Procedure)
Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Drycleaning Solvents)
Specification for Acetone
Viscosity-Temperature Charts for Liquid Petroleum Products
Specification for Fuel Oils
Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic ElastomersTension
Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
Rubber Property-Effect of Liquids
Specification for Hydrocarbon Drycleaning Solvents
Foaming Characteristics of Lubricating Oils
Specification for Diesel Fuel Oils
Specification for Reagent Water
Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
Density and Relative Density (Specific Gravity) of Viscous Materials by Lipkin Bicapillary Pycnometer
Specification for Aviation Turbine Fuels
Water and Sediment in Fuel Oils by Centrifuge Method (Laboratory Procedure)
Copper Strip Corrosion by Liquefied Petroleum (LP) Gases
Viscosity of Asphalts (Bitumens)
Viscosity of Asphalts by Vacuum Capillary Viscometer
Rubber Property-Durometer Hardness
Wear Preventive Characteristics of Lubricating Fluid (Four-Ball Method)
Measurement of Load-Carrying Capacity of Extreme Lubricating Grease (Timken Method)
Wear Properties of Fluid Lubricants (Falex Pin and Vee Block Method)
Measurement of Extreme Pressure Properties of Lubricating Fluids (Four-Ball Method)
Terminology Relating to Petroleum, Petroleum Products, and Lubricants
Evaluating the Scuffing (Scoring) Load Capacity of Oils
Evaluating the Thermal Stability of Manual Transmission Lubricants In a Cyclic Durability Test
Determining Automotive Gear Oil Compatibility with Typical Oil Seal Elastomers
Evaluation of the Thermal and Oxidative Stability of Lubricating Oils Used for Manual Transmissions and Final Drive
Axles
Specification for Performance of Manual Transmission Gear Lubricants
Guide for Characterizing Hydrocarbon Lubricant Base Oils
Specification for ASTM Thermometers
Maximum Pore Diameter and Permeability of Rigid, Porous Filters for Laboratory Use
Terminology Relating to Erosion and Wesir
Three Glossy Prints of Test Blocks Showing Scars (D 2780)
ASTM Copper Strip Corrosion Protection
495
MNL37-EB/Jun. 2003
Metalworking and
Machining Fluids
Syed Q. A. Rizvi:\
a component or apart and primarily involves two types of operations: those that produce metal debris and those that produce no debris. The former type is classified as metal removal
operations and the latter type is classified as metal forming
operations. Cutting and grinding are examples of the first
type and drawing, stamping, and bending are examples of the
second type. All metalworking operations involve bringing
two solids, a tool and a work piece, together to create a new
part or a shape. The process involves high friction, high temperatures, and tool wear; and it is the job of the lubricant, or
the metalworking fluid, to control them. Metalworking fluids
accomplish this by providing cooling, lubrication, and protection against corrosion. Therefore, they improve the efficiency of the operation, and hence increase productivity.
FUNDAMENTAL CONCEPTS
Lubrication
Friction is c o m m o n to all surfaces in contact and is usually
represented by the friction coefficient, signified by the symbol /JL. The coefficient of friction (/x) is a unit-less ratio that
equals 0/N, where 0 represents the frictional force experienced by the two contacting bodies in motion and N represents the n o r m a l force pressing the same two bodies together. Its value ranges from zero (0) to one (1). The higher
the value, the higher the frictional force or the resistance of
the contacting bodies towards motion. Under boundary lubrication conditions, ^l approaches 1.
Minimizing friction is one of the fundamental functions of
a lubricant. If friction is not controlled, it can lead to wear
and surface damage, and ultimately to catastrophic failure of
the equipment. Because of a generally direct correlation between friction a n d wear [1,2], p r o p e r lubrication of the
equipment is important if its integrity is to be preserved over
its designated lifetime. However, it is important to note that
the correlation between friction and wear is a function of the
system and is not always direct [3].
In lubricant-related applications, we are concerned with
three types of friction, that is, the solid friction, fluid friction,
and internal friction [12]. The main function of a lubricant is
to minimize solid friction, which it achieves by forming a
fluid film between two contacting (often metal) surfaces.
Usually, a fluid's internal friction is not of any major concern
' Research and Development Manager, Lubricant Additives Division, King Industries, Inc., Science Road, Norwalk, CT 06852.
497
Copyright'
2003 by A S I M International
www.astm.org
HANDBOOK
Lubricant
Firm
W^Y^/.iA^^.i'V^A^lU*^
FLUID-FILIVI LUBRICATION
Surfaces well separated by
the bulk lubricartt film
LubricantFilm
MIXED-FILM LUBRICATION
Both the bulk lubricant and
the boundary film play a
role
BOUNDARY LUBRICATION
Performance essentially
depends upon the quality of
the boundary flim
(A)
ratio of ZN/P relates directly to oil film thickness (p), but inversely to coefficient of friction (/U,). This implies that high lubricant viscosity (Z), high equipment speed (N), and low
equipment load (P) will allow the formation of a thick lubricant film, 2ind hence the equipment will encounter little or no
friction. Conversely, low lubricant viscosity, low equipment
speed, and high equipment load will create a situation where
film thickness will be inappropriate and the equipment will
encounter high friction. The initial drop in the coefficient of
friction, shown in the figure, while moving from fluid-film to
mixed-film lubrication, reflects a decrease in viscous drag due
to a decrease in lubricant viscosity and or equipment speed.
Mechanical equipment experiences three types of lubrication environments: fluid-film, boundary, and mixed-film.
These are depicted in Fig. 1, Part B [6]. Fluid-film lubrication, also known as hydrodynamic lubrication, is of the most
desirable type. This type of lubrication depends upon the viscosity of the lubricant and is effective only when the load in
the contact zone is low. Under these circumstances, the sliding surfaces are separated by a lubricant film several times
the thickness (2-100 ;nm) of the surface roughness.
Another type of hydrodynamic lubrication, referred to as
elasto-hydrodynamic lubrication or EHD [7-9], commonly
occurs in parts with rolling motion. In this type of lubrication, the lubricant is exposed to high contact pressures and
undergoes a large viscosity increase. See Viscosity section
and Fig. 4. This results in an extremely rigid lubricant film
(0.01-5.0 /xm thick), which causes elastic deformation of the
surfaces in the lubricating zone. Elasto-hydrodynamic lubri-
cation is depicted in Fig. 2. The crosshatched area in the figure indicates solid lubricant film that causes elastic deformation of the metal surfaces.
Boundary lubrication represents the other extreme of the
lubricating environment. Under this kind of lubrication, high
loads and very slow speeds produce extreme pressures that
can lead to a lack of effective lubrication, and hence promote
maximum metal-to-metal contact. The lubricant film thickness in this type of lubrication is in the order of 0.0-2.0 fjun.
If not controlled, the resulting dry metallic friction will cause
extensive wear and ultimately total seizure. Reactive chemicals, called antiwear and extreme pressure agents, provide
protection in this kind of lubricating environment. Mixedfilm lubrication falls between the two extremes mentioned
above and contains the characteristics of both the fluid-film
lubrication and the boundary lubrication. There are regions
of no metal-to-metal contact and of metal-to-metal contact.
Metalworking operations are designed to have at least
some metal-to-metal contact. This is because total separation
of surfaces will make the process inefficient. For example, in
metal removal operations, separation will lead to poor
tool-work piece contact, which will interfere in chip formation. In metal forming operations, this will lead to low friction and hence loss of control. This implies that in metalworking, the lubricant must be designed to perform in
mixed-film and boundary lubrication regimes. In general,
metal removal operations require boundary lubrication and
metal forming operations require mixed-film lubrication.
Metal removal operations, therefore, involve little or no lu-
CHAPTER
Mutually Flattened
Areas Under Load
18: METALWORKING
Metal Strip
AND MACHINING
FLUIDS
499
Elastlcally Deformed
Areas
t
(A
M
E
E
Naphthenic Oil
(0
o
o
(A
Paraffinic Oil
m
E
c
'2.
Temperature ( C)
FIG. 3Viscosity-temperature relationship.
such as upsetting. The film thickness increases due to fast approaching surfaces and the lubricant viscosity increases because of an increase in pressure. Both factors hinder lubricant flow out of the contact zone, which results in a squeeze
film. Deformation of the work piece during the operation results in a flatter surface, thereby making the squeeze film
thinner. The thickness of the squeeze films depends on lubricant viscosity, speed, and load (force) in the same way as that
of the wedge films, but for the reasons described.
Lubrication regime defines a lubricant's ability to support
load (modify friction and reduce metal transfer) and can be
determined by taking into account film thickness and combined surface roughness. The ratio of the two, represented by
A, equals film thickness (p) divided by the combined roughness of the surfaces (S), or p/5. The combined roughness is the
roughness amplitude of two surfaces relative to their average
levels. The value of A equal to 0.5 implies boundary regime;
the value of A between 0.5 and 3.0 implies mixed film regime;
HANDBOOK
Solid
Paraffinic Oil
Naphthenic Oil
0
20
40
60
80
100
120
140
and the value of A greater than 3 implies fluid-iilm or hydrodynamic regime [10]. Unlike metal removal operations that
primarily involve boundary lubrication regime, metal forming operations start in the boundary regime but move into
mixed-film and hydrodynamic regimes as the operation picks
up speed. Lubricant properties, such as viscosity and the
presence of film-forming additives play a role in boundary
and mixed-film regimes. Film-forming additives include friction modifiers, antiwear agents, and extreme pressure
agents. These additives protect surfaces against extensive
friction and wear. They do so by forming low shear protective
films either via physical adsorption, chemical adsorption, or
through chemical reaction. See the Film-forming Agents section for further details.
Viscosity
The role of viscosity in forming effective lubricating films
makes it one of the most important properties of a fluid [11].
Viscosity is defined as a fluid's resistance to flow and is primarily a consequence of the internal friction of the fluid [12].
The viscosity is of two tjfpes: absolute or dynamic viscosity
and kinematic viscosity. Absolute viscosity is commonly expressed in poise (P) or Pascal-seconds (Pa-s) [1 Pa-s =10^
centipoise (cP)]. Kinematic viscosity is measured under the
accelerating influence of gravity and equals absolute viscosity of the fluid divided by its density. It is expressed in centistokes (cSt), or square meters per second (m^/s) [1 m^/s =10*
centistokes (cSt)]. Absolute viscosity is often not used for
metalworking fluids, but kinematic viscosity is. Previously
used units of kinematic viscosity, Saybolt Universal Seconds
AND MACHINING
FLUIDS
501
502
MANUAL
HANDBOOK
HjO
HoO
OIL
"^,
.~N<00~>
IL ./wOO'^^'^^
OIL
^^2*^
'VwO
0~v
'^2*'
OIL
OIL
OIL
HoO
(a)
(b)
It is important to periodically check the organic (oil) content of the emulsion by breaking it. An acid or a salt, such as
sodium chloride, is used for this purpose. Alternatively, one
can use a refractometer to determine the oil content. If the oil
content is too low, it may be appropriate to top u p the fluid
with fresh concentrate. Since contaminants, such as tramp
oils, metal debris, and microbes, can destroy the integrity of
emulsions, they should either be removed or controlled.
Tramp oils are removed via skimming and metal debris is removed via filtration. As mentioned above, microbes are controlled by the periodic addition of the antimicrobial agents.
Foaming is another problem (ASTM D 892) with emulsions
that relates to the presence of emulsifiers. Foaming not only
leads to poor lubrication, but it also impairs the fluid's heat
transfer properties. While new emulsions are more stable
than old emulsions, the lubricating ability (ASTM D 2782, D
2783, D 4172, and D 5619) of emulsions improves with use.
This is because debris resulting from metalworking operations and the decomposition products from additives, especially EP agents, tend to destabilize emulsions via nucleation.
Ultimately, a complete breakdown of emulsion occurs and a
new batch must be used. The life of an emulsion during use
is called its "batch life." In general, less stable emulsions have
a shorter batch life.
While emulsions contain a variety of chemicals (discussed
in the Additive section), the chemical types that are critical to
their formation and stability are emulsifiers and coupling
agents. Emulsifiers are key to the formation of emulsions,
and coupling agents help improve their stability. Emulsifiers
are surfactants that reduce surface tension of the oil-water
CHAPTER
interface, thereby promoting miscibility and leading to colloidal dispersions. In many cases, a combination of emulsifiers is used and its selection depends upon the type of base
oil to be emulsified and the nature of other additives present
in the formulation [10].
Emulsions are made by mechanically mixing the organic
phase t h a t comprises additives and emulsifier/s, called a
"concentrate," with water. Since the amount of water in water-based fluids can be as high as 95%, its quality not only determines initial stability of the emulsion but also its "batch
life." The presence of greater than 200 p p m calcium or magnesium carbonate (ASTM D 511 and D 513) can lead to emulsion stability problems. And the presence of chloride and or
sulfur levels (ASTM D 512 and D 516) of greater than 150
p p m will promote corrosion, instability, and rancidity. Soft
water of less than 50 p p m hardness (ASTM D 1126), on the
other hand, leads to foaming in many formulations. While
regular water is usually acceptable, the use of distilled, deionized, or reverse osmosis water is recommended if problems are encountered.
Emulsion appearance can vary from transparent to milky
white, depending upon the droplet size. Table 2 shows emulsion appearance as a function of the droplet size. Oil-in-water emulsions with droplet sizes of approximately 0.1-0.2 um,
sometimes referred to as microemulsions, are preferred in
some metalworking applications. This is because their
smaller droplet size makes them both kinetically and thermodynamically more stable. Macroemulsions with droplet
sizes in the range of 0.2-10 u m are only kinetically stable.
This means that microemulsions prefer the dispersed form
and are therefore less likely to phase separate. Of course, the
droplet size depends upon factors such as the nature of the
oil and the amount and the type of emulsifier used. Despite
greater kinetic and thermodynamic stability, pH (ASTM D
1293), oil-water ratio, and temperature have a profound effect on the stability of microemulsions. The larger droplet
size and the tendency to coalesce are not always undesired.
Hence, m a c r o e m u l s i o n s are often used in m a n y oncethrough applications, where immediate breakdown is desired to release oil for superior lubrication. The same properties are useful for effluent treatment.
As mentioned earlier, emulsions for metalworking use are
usually produced prior to use by mechanically mixing the additive concentrate with water. The concentrate comprises oil,
emulsifier/s, and a variety of additives. The concentrate-towater ratio in such dilutions is between 1:10 (10%)-1:60
(1.5%). However, this ratio is changed if the operation requires a greater degree of cooling or more lubricity. Metalworking fluids for operations requiring more cooling contain
a higher percentage of water than those requiring more lubrication. Microemulsions are stable (ASTM D 3342, D 3707,
and D 3709), are resistant to microbial attack (ASTM D
3946), and are effective coolants. These attributes are primarily due to their low organic content and high emulsifier
18: METALWORKING
Appearance
Milky white
Blue white
Translucent to semi-transparent
Transparent to translucent
FLUIDS
503
Oils
(Macroemulsions)
AND MACHINING
Fluids
(Micellar
Solutions)
504
MANUAL
HANDBOOK
Polar Group
Nonpolar Group
(Hydrophilic)
(Lipophilic)
H,0
H,0
^im
H,0
Micelle
FIG. 6Micellar structure of emulsifier.
ply solutions of organic additives in water. Since most organic materials are hard to dissolve in water, high polarity of
additives is necessary for solubility. Soaps and other surfactants are often added to facilitate solubilization. Because synthetic fluids are oil-free, they have poor lubricating ability
but excellent cooling ability. These fluids are therefore ideal
for high speed machining (metal removal) operations that
generate a substemtial a m o u n t of heat. In these operations,
these fluids are more effective than straight oils. Synthetics
contain fatty amines, fatty amides, or fatty carboxylic acid
salts for rust inhibition (ASTM D 665) and TEFLON and
poly(alkylene glycols) for lubricity. Since these fluids are solutions and not emulsions, they do not suffer from destabilization problems and are useful for high-speed machining
applications. Higher stability is due to their small micelle size
(which also makes them appear cleeir) and low organic content. The micelle size in these fluids typically ranges between
0.005 and 0.015 um. The fluids that do not contain any metal
or amine carboxylates eire suitable for use in combination
with h a r d water.
Synthetics cem be formulated to shed t r a m p oil, i.e. undesirable contaminant oil, for easy skim-off. These fluids cire resistant to bacterial degradation (ASTM D 3946) because of
low organic content and have good work piece visibility because of clarity. The disadvantages include reduced lubricity
due to the absence of petroleum oils; tendency to leave hard
crystalline residues; a n d high alkalinity, higher cost, a n d
Fluids
(Microemulsions)
threading, reaming, boring, and sawing. The primary functions of the lubricant are to cool and to facilitate debris removal. Metal forming fluids Eire lubricants that are used in
operations where metal in the work piece is plastically deformed to obtain the desired shape. Such operations involve
molding of metal by the process of bending, stretching, Eind
pounding. The primary function of a lubricant in these operations is to reduce friction. Lower friction helps in increasing
tool life and in lowering energy usage. Metal forming operations include hot rolling, cold rolling, foil rolling, forging,
wire drawing, tube drawing, deep drawing, ironing, extrusion, and spinning.
Heat removed has an effect on surface finish and cold welding of the tool to the work piece, which affects tool life. The
frictional heat generated during some metalworking operations, depending u p o n meted hardness, can reach temperatures of 1000C or higher. In addition, extensive cutting pressures at points of contact can lead to specific surface loads of
u p to 5000 N/mm'^. Both these factors can cause local welding during cutting. Shearing of welded spots will not only increase the roughness of surfaces, but it will also expose fresh
surfaces that are more prone to welding. Consequently, additional frictional heat will be generated. The function of the
fluid is to dissipate this heat and reduce the number and the
size of the welding spots. Lubrication effectiveness depends
upon the properties of the oil and the presence or absence of
the friction reducing additives. Cooling ability, on the other
hand, is a function of the amount of water present in the lubricant.
506
MANUAL
HANDBOOK
Lubricant
Lubricant
Timken IVIachine
Four-ball EP Machine
Lubricant
SAE Machine
FIG. 7Film-forming test machines.
AND MACHINING
FLUIDS
507
Helicai Gears
Test Geais
Hydrostatic Pressure
Hydrostatic Pressure
Spur Gears
Ryder Machine
Test Gears
I X
Locl(ed-up Torque
Coupling
Spur Gears
Gleason Machine
FIG. 8Test elements of Ryder and Gleason machines.
Extreme pressure agents used in metal removal fluids include chlorine, sulfur, and phosphorus compounds. Filmforming additives create physical and chemical protective
films. For materials of moderate hardness and for operations
involving high speeds, friction reducing agents provide the
necessary performance. These chemicals react with metal either at ambient temperature or at high temperatures to form
metal carboxylate films (see the Film-forming Agents section
for a detailed discussion). However, for difficult-to-cut materials and operations involving high pressures and slow
speeds, extreme pressure agents are needed. These additives
form protective films via chemical reaction.
The selection of a proper lubricant depends upon the nature of the metal and the severity of the cutting operation. In
general, operations that employ low cutting speeds place a
higher demand on the lubricant than those that employ high
cutting speeds. Figure 9 shows the relative severity of different cutting operations and the demand they place on the lubricant [10,18].
Tool Wear
Besides the severity of the machining operation, tool wear is
also a function of the quality of the cutting fluid and the
machinability of the metal. Cutting fluid is essential to mini-
508
MANUAL
HANDBOOK
BROACHING
Attribute
TAPPING
Carbon steel
THREADING
High-speed
steel (HSS)
GEAR SHAPING
REAMING
Cast alloys
DRILLING
Cermets
MILLING
TURNING
FIG. 9Relative severity of metal-removal operations.
Ceramics
Diamonds
(Mg) and its alloys < zinc (Zn) and its alloys
< bronze < copper (Cu) < carbon steel < alloy steels
< stainless steel < nickel (Ni) alloys
< titanium
CHAPTER
TABLE 4Machining characteristics of machined metals.
Machined Metal
Steels
Free Machining
Alloy steels
Stainless steel
Cast Iron
Gray cast iron
Malleable cast iron
Nodular iron
White cast iron
Wrought iron
Aluminum and its alloys
Magnesium and its alloys
Characteristics
Free machining
Good machinability
18: METALWORKING
AND MACHINING
FLUIDS
509
heavy tool wear. Therefore the lubricants for these operations require the use of extreme pressure additives [19a]. A
new technique, called dry machining, is presently being explored. The purpose is to eliminate purchase, handling, use,
and disposal costs. Since this technique does not use any lubricant, it involves high temperatures. Thus far, the technique has been applied to boring operations. Efforts are underway to extend it to drilling operations [19b].
The depth of cut and surface finish are additional considerations for fluid selection. Low-speed operations where cuts
are deep and good work piece finish is important; the lubricity of the fluid is critical. The use of straight oils is therefore
appropriate. For high-speed operations that involve shallow
cuts, quick heat dissipation is desired. This makes microemulsions or micellar solutions the lubricants of choice.
In most cases, the fluid is applied under pressure into the cutting zone, which is to reduce friction, minimize metal transfer, and maximize cooling.
Metal Forming Fluids
These fluids are used for operations that depend on plastic
flow of the metal. Such operations include rolling, extrusion,
drawing (drawing tubes, tube bending, deep drawing, wire
forming), forging, and sheet metal forming. Some of these
operations involve both ambient temperatures (cold working) and high temperatures (hot working). Metal forming
processes can be distinguished as being steady-state or nonsteady-state [16], each type with different lubrication requirements. In steady-state processes, such as rolling, it is
possible to lubricate the surface of the work piece during its
approach to the deformation zone. However, in non-steadystate processes, such as sheet metal forming, the lubrication
is not usually possible because of the nature of the operation,
and one must depend upon the pre-applied lubricant film.
Some processes, such as long billet extrusion, have cheiracteristics of both; that is, n o lubricant application during certain parts of the operation and lubrication during other parts
of the operation.
The primary functions of a lubricant during metal forming
operations are to reduce friction, which lowers energy consumption; and to minimize wear, which increases tool life.
Friction reduction, in addition, facilitates the release of the
forged part from the die and improves surface finish of the
work piece. However, too m u c h friction reduction is undesired because it can lead to slippage and hence make the operation inefficient.
Common metal forming lubricants include:
mineral oilscompounded oils (blends of mineral oils and
fatty oils)
synthetic oils and estersfatty acids and their derivatives
lanolin, tallow, and paraffin waxesaqueous solutions and
emulsions
polymer
solutionsdispersions
containing graphite,
molybdenum disulfide (M0S2), salts, glass, bentonite, lime,
mica, and talc
Additives for these lubricants include fatty acids and fatty
compounds, extreme pressure agents (sulfurized and sulfochlorinated fats and oils), emulsifiers, coupling agents, inorganic solids, and dispersants.
510
MANUAL
HANDBOOK
Miscellaneous Fluids
Metal Protecting
Fluids
Fluids
Lubricants
These lubricants are used to lubricate slideways and the accompanying pneumatic equipment. Slideways are guiding
surfaces on the bed of a machine along which a table or a carriage moves. Since surfaces that slide over each other are flat,
the area of contact is large. This leads to increased adhesive
wear. These devices in addition experience motion of varying
speeds, which causes sticking and slipping of the sliding surfaces. After wear-in, opposing surfaces form an even closer
fit, which squeezes out and wipes away any lubricant that is
in the path of motion. Essentially, a boundary lubrication
condition exists. This type of lubrication to a degree is by design; otherwise, excess lubricant would form a hydrodynamic
wedge that will interfere with the motion of the plane.
BoundEiry lubricated surfaces will adhere to each other, especially during slow speed operations. Adhesion occurs when
the static friction either equals or exceeds the force of motion. If adhesion is followed by movement due to the applied
force, the p h e n o m e n o n is called stick-slip. Regular occurrence of stick-slip causes not only vibration Eind noise but
also damage to the work piece, tool, and rider and way.
Slideway lubricants perform at extreme t e m p e r a t u r e s ,
high loads, moisture, and poor ambient air quality. They
must therefore possess both the EP activity EUid the rust and
corrosion-inhibiting properties. These lubricants are formulated with friction reducers, primarily fatty carboxylic acid
derivatives that minimize stick-slip, and extreme pressure
agents that control wear damage resulting from boundary lubrication conditions. Operation at extreme t e m p e r a t u r e s
leads to oxidative breakdown of the lubricant. This must be
avoided; otherwise, poor lubrication and corrosion will result. This is accomplished by the use of oxidation inhibitors.
It is important to note that stick-slip control requires combining proper machine design and superior lubricant quality.
Since the oil is removed due to the wiping action of the
slide, lubricant is supplied at different points along the slide
route. Suspended metcJlic fines or chips in the lubricant can
lead to scratching, gouging, or abrading of the ways. The use
of a properly formulated lubricant can minimize this type of
damage, as well as control friction, chatter (noise), and stickslip. Despite the fact that lubrication is often once through.
a n oil circulating system may also b e used to deliver the lubricant at different points along the slide.
FLUID COMPOSITION
Metalworking fluids are composed of a base fluid and a collection of chemicals. While base fluid makes u p the bulk of
the formulation, it lacks the properties necessary to act as an
effective lubricant. Hence, chemical compounds, called additives, are used to either fortify the base fluid's existing properties or add new properties [20]. Because of the diversity of
lubrication requirements in metalworking operations, the
type and the quantity of additives differ from operation to operation. The quality and quantity of additives cdso depend
upon the type and properties of the base fluid.
Base Fluid
The base fluid in metalworking lubricants can be biological
(animal or vegetable) in origin, petroleum-based (mineral
oil), synthetic-based, or water. Structures of some of the
basestocks used to formulate metalworking fluids are shown
in Fig. 10. The detailed description of these basestocks is provided in Chapters 7 and 10 of this manual.
Straight oils use severely refined and hydrotreated mineral
oils and synthetics, such as polyalphaolefins (PAOs), polybutenes, ethylene oxide-propylene oxide polymers (polyalkylene glycols or PAGs), and organic esters. For water-based
fluids, naphthenic oils are preferred because of ease of emulsibility and because of their superior viscosity-pressure relationship (discussed earlier). For straight oils, however, paraffinics are the base oils of choice. Synthetic basestocks are less
popular than mineral oils, primarily due to their higher cost.
However, the use of these stocks is increasing in fluids where
tailored properties are desired and petroleum basestocks are
not effective.
Polyalkyleneglycols, prepared by polymerizing ethylene
oxide-propylene oxide (EtO/PrO) mixtures [21], are extensively used in metal removal lubricant formulations. Desirable properties Eire obtained by controlling molecular weight,
altering terminal groups, and the EtO/PrO ratio. Higher
molecular weight materials have higher viscosities a n d
higher EtO/PrO ratio products have higher water solubility.
One can even alter the EtO/PrO ratio to devise materiEils that
are water-soluble at low temperatures but are water-insoluble at high temperatures. This property is useful in formulating fluids that are clear during circulation but separate
polyalkylene glycol (and additives) at the hot tool-work piece
interface during use.
Polyisobutylenes, obtained by polymerizing isobutylene
[21], have the tendency to depolymerize at high temperatures. This makes them useful in rolling and drawing oils for
ferrous and nonferrous metals, where petroleum oil derived
lubricants cause staining during subsequent annealing process. Polyalphaolefins, often not used in metalworking fluids,
possess certain attributes that make t h e m desirable. These
include effectiveness over a wider temperature range and
lower hydrocarbon (HC) emissions t h a n petroleum oils of
similar viscosities. Polyalphaolefins are also highly resistant
to oxidative and thermal degradation.
H2
/C>^
H2
^C^
H2
/ ^ \
H,
H,
^C
H,
FLUIDS
511
Paraffinics
CH,
CH
H,C.
^CH,
^CH,
H,C
H3C'
H2
C^
H2
CH.
CH,
H2
,C^
H2
/^"^
AND MACHINING
CH3
H2
H2
H2
I
H2
^ C ^ ^C^
^O^
CH.
^C~^
CH
CH
CH
CH
CH
CH3
Naphthenics
CH3 HoCs. ^^''2
CH
/
H,C\
H2C
CH
\
H2C
Crl2
A
HoC
CHo
\
CH3
CH,
/
H,C
CH3
CH, C H -(-CH2 C H
-cac
CH3
Polyisobutene
-^CHj
-CH,
//
CH20C^
II
RO C(CH2)n C O R
R=C8 TO C-13
' ,
-^
CH3CH2C CH2OC R
CH2OC
RO
(CH2 C H 0 ) n H
R=C5 TO C10
//
R
Polyol Ester
R=C2 TO C3
Polyalkylene Glycol
FIG. 10Basestocks used in metalworking fluids.
Additives
Additives used in metalworking fluids can be broadly classified into chemically inert and chemically active. Chemically inert additives primarily alter the physical properties
of the fluid, such as lubricity and surface tension. Such additives include emulsifiers, coupling agents, friction reduc-
512
HANDBOOK
ers, rust and corrosion inhibitors, foam inhibitors, and antimicrobial agents. Chemically active additives, on the other
hand, alter the chemical properties of the fluid, such as oxidation susceptibility. This group of additives includes some
friction reducers, extreme pressure/antiwear agents, and
oxidation inhibitors. Common types of additives that are
typically used in metalworking fluids are provided in Table
5. Their chemistry and mode of their action are also summarized.
Emulsion
Promoters
Control
Prevent
Control
Control
Metal passivators
Couplers
Emulsifiers
Odor masks
Thickeners
Corrosion and rust inhibitors
Suppress odor
Improve viscosity
Control oxidative and corrosive damage to
metal surfaces and tools
Oil-based fluids
Antifoam agents
Anti-misting agents
Corrosion and rust iniiibitors
Demulsifiers
DispersEints
Extreme pressure/lubricity agents
Odor masks
Thickeners
Solid lubricants
Function
bacteria-derived acidity
foam
fungal growth
microbial growth
Prevent foam
Suppress mist formation
Control oxidative and corrosive damage to
metal surfaces and tools
Facilitate water separation and facilitate
removal of tramp oil via skimming
Prevent agglomeration of material particles
that result during cutting and grinding
Form heat-resistant chemical films that
reduce friction
Suppress odor
Improve viscosity
Improve film strength
Typical Compounds
Amines and inorganic bases
Silicones, silicates, and stearates
Sodium omadine
Triazines, omadine, phenol, oxazolidines,
and imidazolines
Triazoles
Glycols, glycol esters, and alcohols
Sodium and lithium sulfonates;
poly-ethoxylated phenols, alcohols and
acids; metal and amine carboxylates
(soaps of fatty acids)
Fatty acids, fatty amides, fatty esters, and
fatty acid salts (soaps); phosphates; sulfur
and chlorine containing compounds
Natural and synthetic aromatic compounds
Polyacrylate esters and glycol esters
Carboxylic acid salts, amides, and amines
Silicones, polymethacrylates, and stearates
Polyisobutenes and other natural and
synthetic polymers
Metal sulfonates and phosphates; organic
acids and esters; and triazoles
Cationic and non-ionic polymeric surfactants
Polyamides and metal sulfonates
Fatty acids, fatty amides, fatty esters, and
fatty acid salts (soaps); phosphates; sulfur
and chlorine containing compounds; basic
sulfonates
Natural and synthetic aromatic compounds
Polyacrylate esters
Graphite, molybdenum disulfide,
Poly(tetrafluoroethylene)-PTFE
(TEFLON)
NON-IONIC
-P
RCs
R0{CH,CH,0),CH,CH20H
^CHjCHjOH
RN,
CH2CH2OH
Polyethoxylated Alcohol
(Hydroxyalkyl Ether)
Dialkanolamjde
,p
RC^
0(CH2CH20),CH2CH20H
CHjOH
I
CHOH
Fatty Diethanolamine
AND MACHINING
FLUIDS
0(CH2CH2O)xCH2CH2OH
CHjOH
CH20-C-0leyl
Glycerol Monooleste
(GMO)
/
H3CCHI
\ OH
CHjOH
CH2OH
Alkylphenol Ethoxylate
/
HjC
ANIONIC
00
OCH3
I
.0.
Rct0
O NHECHjCHjOH],
H,C^
Sodium
Carboxylate
^^^^^ Alkyll^nzenesulfonate
OH
I
,0
\ ^ C ^
H H,
H,C.
OH,
\
CH,
CH2OCH3
OH
Propylene Glycol
Ethylene Glycol
"^"^cPwa
513
CH,
t?
OH
Isononanoic Acid
514
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
Lubrication is necessary to facilitate the counter movement of two sliding surfaces. This function, which is usually
performed by the base fluid, can be enhanced by the use of
high viscosity oils, friction modifiers, or extreme pressure
(EP) and antiwear (AW) agents. Since water is a poor lubricant, the lubricity in water-based fluids is achieved by the use
of friction modifiers, also called the lubricity agents, and or
EP agents. These additives improve lubrication ability of the
metalworking fluids by forming m o n o m o l e c u l a r physical
and chemiccJ films at the tool-work piece interface, which
minimize metcJ-to-metal contact.
Film-forming agents are extremely surface active because
of a high polar-nonpolar ratio. The polar-nonpolar ratio in
additives is discussed in detail in Chapter 9 on Additives and
Additive Chemistry. These additives typically contain hydrocarbon groups of 10-18 carbon chain size and very polar
functional groups. Therefore, they, have the tendency to separate on surfaces, where they interact by a physical or a
chemical m e c h a n i s m . Modes of interaction of additive
molecules with surfaces [23] are depicted in Fig. 13.
Physical adsorption, or physisorption, is a weaker association of the additive with metal than chemical adsorption, or
chemisorption, which in turn is weaker than chemicsd reaction. During adsorption, a n additive molecule generally
keeps its structural integrity and involves no bond breakage
or bond formation. This is t5rpical of additives, such as natural fats and oils, which have a low reactivity towards metals.
However, when the temperature reaches beyond a certain
threshold temperature, these additives desorb and the fluid
loses its friction-reducing properties. The result is wear damage. Chemical adsorption, on the other hand, requires some
Additive (Molecule
Metal Surface
Physisorption
Chemisorption
o o o o o o
o o o o o o
Chemical Reaction
FIG. 13Modes of additivesurface interactions
>
,C^OCH,
Rc;
< .
\ ;cocHa
OR'
Alkyl Carboxylate
or Vegetable Oil
R' Methyl or Higher Alltyl G r o u p
R ^ Fatty Hydrocarbon Chain
H,
H,
II
C
CH2 H2C
/\
II
HO-J-CHjCHjo4-4-CH2CHojH
Pentaerythritol Carboxylate
J'"
NECHjCHjOHJz
Dialkanolamide
HNECHjCHjOHh
0
Triethanolamine Salt of a CarboxylJc Acid
400-
O
S_-35C
3
(U 30C
Q.
0)
I-
msm
C 250
_o
^
o
c
,3
'B20C
o
O
IJI.hBdd
150
Temperature [2]
FIG. 15Extreme Pressure (EP) protection versus conjunction temperature.
TABLE 6Effective temperature range of lubricity agents and
EP/AW agents.
Additive Type
Effective
Temperature Range
< 200C
180^50C
200-700C
600-1000C
516
HANDBOOK
Dispersants
Corrosion
These additives are of two types: film-formers axid acid (corrosive component) neutralizers. Film-formers protect against
corrosion by forming physical films on metal surfaces. Acid
neutralizers control corrosion by neutralizing acidic species
either present in a lubricant or produced during use. The selection of these additives depends upon the fluid type and the
metal to be protected. For straight oils, overbased metal sulfonates are used to protect against iron corrosion (ASTM D
665 and D 4627).
Anti-misting
Agents
Inhibitors
P1B-X^^.._
/
NCHjCHzNHCHjCHjtvr
Polyisobutenylsuccinimide
Agents
Metal Salicylate
.SOjJxM
R
R
(S),
M = Ca, Ba, Na
X = 1 or2
>
Alkylbenzenesulfonate
CH=CH
CH2COOR"
Sx
R C H r CH
Alkyl polysulfide
R = C4 and higher; n = 2-4
CHzCOOR'
(ROJJR:
Dlalkyl Hydrogen
Phosphite
Metal Dithiocarfoamate
M = Zn (zinc), Sb (antimony)
.^'
\.
(RO),P(OH)y- RNH2
(R0)2 P
Zn
Amine Phosphates
X, y = 1 o r 2
SO,
M . M (CO3)
Basic Alkylbenzenesulfonate
FIG. 16Structures of common EP agents.
AND MACHINING
R
Neutral Calcium Sulfonate
II
SO,
RCH COH
CH-COH
II
Ca. xCaCOs
2
-LR
O
Alkenylsuccinic Acid
II
ROPOH . R'NHj^CHjCHjOH
OR
RN,
CH2CH2OH
II
ROPOH . R'NH,"
Dlethanolamine
OH
RS.^/*\,^SR
\\
//
NN
Dimercaptothiadiazole
Derivative
517
Ca
Polyethoxylated Phenol
FLUIDS
Alkylbenzotriazole
AII<ylammoniun
Phosphates
518
MANUAL
HANDBOOK
Inhibitors
These additives are used in lubricants to minimize deterioration of the organic component due to oxidative attack. If not
controlled, oxidation will lead to acidic products that tend to
form sludge and corrode metal surfaces. For a more detailed
discussion on oxidation, consult Chapter 30 of this treatise.
Because many metalworking operations involve high temperatures a n d metal debris, the rate of oxidation is even
faster. This makes the need for these additives even more
FORMALDEHYDE-RELEASE AGENTS
eH,CH,OH
Hj
H2
HOHjCHjC^
2-{Hydroxymet)iylamino)ethanol
CH2CH2OH
CH3
H3C-C-NCH2OH
:?;>
^ N ^ O
CHjOH
1,3-dJ (hydroxymethyl)-5,5dimethyl-2,4-dioxoimidazole
Oxazolidine
OTHERS
HC
\\
NH
NH.
HC-C,
isothiazolone
BenzoisothiazoUnone
a:
/>-SH
^S
BenzotFiazole
0
Sodium pyrithione
Sodium omadine
H^N-V*"^
Br
Br
N
3
2,4,5-Trichlorophenol
2,2-Dibronio-3-nitrilopropionafnide
CH,
I
SiO
CH,
I ^
Si
CH3
CH3
'/<
^
CH3
Dimethylsiloxane Polymer
Arylamine
2,6-Di-t-butyl-4-niethylphenol
HO(CH2CH20)xCH2CH20[CH2CH(CH3)0]yCH2CH(CH3)OH
.CHzCOOH
N.
CH2COOH
^CHzCOOH
N,
'CH2COOH
Ethylenediaminetetraacetic Acid
Agents
Lubricant Formulations
E a c h metalworking operation places a different d e m a n d
on the lubricant. A lubricant must therefore possess specific
properties to perform effectively. The properties that fulfill
the c o m m o n needs of most operations include cooling, lubrication, w e a r control, a n d protection against corrosion.
Metcdworking fluids, like other lubricants, are obtained by
blending base fluid and additives. These fluids must meet
performance specifications, which for these fluids are primarily established by OEMs and end-users. Table 7 provides
the additive composition of metal removal fluids and Table 8
provides the additive composition of metal forming fluids
and miscellaneous others. In Tables 9 and 10, additives are
listed in the form of formulations. Table 9 presents formulations based on the base fluid and Table 10 presents formulations based on the fluid function.
Solids
Water-soluble
cutting oil
Grinding oil
Lapping oil
Honing oil
(precision
grinding)
Punching lubricants
(emulsifiable and
nonemulsifiable
minereil, and solid
dispersion type)
Composition"
Mineral oil; friction reducer (fatty acids,
their metal salts and esters); extreme
pressure agent (chlorinated isobutylene,
dibenzyl sulfide, organic phosphates).
Water; corrosion inhibitor (sodium or
potassium nitrite; mono-, di-, or
tri-ethanolamine); emulsifier (non-ionic
surfactants; natural and synthetic fatty
acid soaps; polyalkylene glycols).
Water; mineral oil; friction modifier;
extreme pressure/antiwear agent;
anti-misting additive.
Mineral oil; dispersant; lapping agent.
Mineral oil; friction reducer (fatty acids and
triglycerides); extreme pressure agent
(chlorinated isobutylene, dibenzyl sulfide,
organic phosphates).
Mineral oil; friction reducer (fatty oils,
graphite, mos2, mica, or talc); extreme
pressure agent (organophosphorus,
organosulfur, and organohalgen
compounds).
Composition"
Water; mineral oil (primarily naphthenic); emulsifier; coupling agent; corrosion inhibitor
(alkanolamides); antimicrobial agent (triazines); friction reducer (fatty acid derivatives); anti-misting
additive (polyisobutylenes); and extreme pressure agent (organophosphorus compounds).
Mineral oil (kerosine cut); friction reducer (dodecanol, fatty acids and esters); and extreme pressure agent
(organophosphorus, organosulfur, and organohalgen compounds).
Water; mineral or fatty oil; friction reducer (fatty alcohols, acids and esters); emulsifier; coupling agent;
corrosion inhibitor (alkanolamides, sulfonates); foam inhibitor (ethoxylated fatty alcohols);
antimicrobial agent (triazines); and extreme pressure agent (organophosphorus, organosulfur, and
organohalgen compounds).
Water; friction reducer/EP agent ( o r g a n o p h o s p h o r u s c o m p o u n d s , polyalkylene glycols); corrosion
inhibitor (fatty amines).
Mineral oil; friction reducer (animal or vegetable oils); lubricant carriers* (phosphoric acid, oxalic acid,
lime); extreme pressure agent (organic chlorides)
Mineral oil; friction reducer (animal or vegetable oil); lubricant carrier (phosphates, oxalates, lime);
extreme pressure agent (organic chlorides);
Mineral oil; friction reducer (animal or vegetable oil); corrosion inhibitor; sdhesion improver
(polymethacrylates); extreme pressure agent (organophosphorus, organosulfur, a n d organohalgen
compounds).
Mineral oil; friction reducer (alksdi metal soaps of fatty acids, fatty animal and vegetable oils); lubricant
carrier (phosphoric acid, oxalic acid, lime); extreme pressure agent (organophosphorus, organosulfur,
and organohalgen compounds).
Mineral oil; lubricant carrier (zinc phosphate); a n d extreme pressure agent (organosulfur a n d
organohalgen compounds).
Mineral Oil; oxidation inhibitor (alkylphenol); quenching p r o m o t e r (high molecular weight hydrocarbons).
Mineral oil; emulsifier; oxidation inhibitor; quenching promoter (high molecular weight hydrocarbons).
Mineral oil; emulsifier; oxidation inhibitor; quenching promoter (high molecular weight hydrocarbons);
antimicrobial agent; corrosion inhibitor.
Mineral oil; corrosion inhibitor
Mineral oil; emulsifier; water; plasticizer (ethyl cellulose or cellulose acetate); micronized waxes;
corrosion inhibitor (alkali and alkaline earth natural metal sulfonates; fatty carboxylates; naphthenates;
and extensively oxidized hydrocarbons, both neutral and overbased, amino alcohols and triazoles)
Mineral oil; friction modifier (fatty acid derivatives); antiwesir agent; oxidation inhibitor
Semisynthetic fluid
Synthetic fluid
Approximate Composition
Extreme pressure agent (20.0-35%)-chlorinated wax a n d sulfurized fat mixture; corrosion inhibitor
(1.0-2.0%)-alkanolamine; lubricity agent/friction modifier (10.0-20.0%)-soap or lard oil
Extreme pressure agent (25.0-30.0%)-chlorinated wax a n d sulfurized fat mixture; corrosion inhibitor
(4.0-6.0%)-alkanolamine; lubricity agent/friction modifier (10.0-20.0%)-soap o r lard oil; foam
inhibitor (0.5-1.0%)-polyacrylate; buffer (4.0-6.0%)-diethanolamine o r triethanolamine; biocide
(1.0-2.0%)-triazine; emulsifier (4.0-6.0%)-soap.
Extreme pressure agent (10.0-20.0%)-chlorinated wax o r sulfurized olefins; corrosion inhibitor
(0.5-1.0%)-alkanolamine or triazole; friction modifier (5.0-10.0%)-carboxylic acid derivative.
Extreme pressure agent (10.0-15.0%)-chlorinated wax or sulfurized olefins; corrosion inhibitor/buffer
(4.0-6.0%)-alkanolamine; lubricity agent/friction modifier (5.0-10.0%)-carboxylic acid derivative;
foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier (5.0-10.0%)-soap.
Extreme pressure agent (4.0-6.0%)-chlorinated wax or sulfurized olefins; corrosion inhibitor/buffer
(5.0-10.0%)-alkanolamine; lubricity agent/friction modifier (5.0-8.0%)-carboxylic acid derivative;
foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier (5.0-10.0%)-soap
or petroleum sulfonate.
Extreme pressure agent (2.0-3.0%)-sulfurized olefins or zinc dialkyl dithiophosphate; corrosion
inhibitor/buffer (5.0-10.0%)-alkanolamine; lubricity agent/friction modifier (4.0-6.0%)-carboxylic
acid derivative; foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier
(5.0-10.0%)-soap or petroleum sulfonate.
Corrosion inhibitor (2.0-3.0%)-neutral metal sulfonate mixture.
Corrosion inhibitor (0.5-1.0%)-amine carboxylate and amine borate mixture; lubricity agent/friction
modifier (0.5-1.0%)-phosphate ester; buffer (5.0-10.0%)-alkanolamine; biocide (1.0-5.0%)-triazine.
Oxidation inhibitor (0.1-0.5%)-phenol and arylamine mixture; speed improver (1.0-10.0%)-calcium
sulfonate.
Corrosion inhibitor (1.0-2.5%)-alkanolamine; foam inhibitor (0.5-1.0%)-polyacrylate; buffer
(5.0-10.0%)-alkanolamine; biocide (2.0-3.0%)-triazine.
Water-Based Fluids
Corrosion Tests
GM Quenchometer (ASTM
D 3520)
Cooling curve analysis (ASTM
D 6200)
Emulsion stability
characteristics-(ASTM
D 1401, IP 263)
Moderate Timken aquarium test
Lubrizol centrifuge procedure
Other Tests
Cooling curve analysis (ASTM
D 6482 and D 6549)
standards contain these tests, as summarized in Table 13. Details of these tests are available in books on ASTM, IP, and
DIN Standards [13,14,24]. It is important to point out that
the tests across standards do not always match. They may differ because of disparity in hardware, test method, or the way
they are performed.
Purpose
Measures fluid's non-ferrous compatibility.
Measures the ability of inhibited mineral oils to aid in preventing the rusting of ferrous
metals in the presence of water.
Measures corrosion protection of aqueous cutting fluids.
Evjiluates rust inhibition properties of aqueous cutting fluids.
Cup appearsince indicates non-ferrous corrosion properties.
Measures ability of preservative oils to protect metal parts from rusting under conditions
of high humidity.
Steel part corrosion protection measured after exposure to 5% salt spray for 24 h.
Measures anti-rust properties of metal preservative fluids on steel panels. Considered more
severe than ASTM D1748 humidity test.
Evaluates anti-wear and anti-weld properties of lubricants.
Measures abrasion resistance and load carrying capacity of lubricants.
Evaluates extreme pressure and anti-weld properties of lubricants.
Measures load carrying capacity and wear properties of lubricants.
Determines foaming characteristics of lubricating oils at specific temperatures.
Determines relative stability of lubricants in contact with hot metal surfaces.
Measures separation of oil and water from emulsion over time.
Measures emulsion stability in water.
Measures foam, bacteria, fungus, and odor over time in controlled aqueous environment.
Visual determination of fluid color based on colorimetric readings.
Determines heat removal speed of a quench oil.
Evaluates fluid efficiency by measuring torque required during tapping operation in steel.
Evaluates fluid efficiency by measuring torque required during threading operation on cast
iron or stainless steel.
Measures static and dyneimic coefficients of friction in slideway lubricants.
Determines compatibility of lubricants with Bijur setup (specific to Bijur filter design)
Evaluates fluid efficiency by measuring torque required during tapping operation in steel.
Evaluates friction generated in a drawing process.
Measures load-carrying properties of lubricants.
ASTM Designation
ISO Designation
IP Designation
DIN Designation
D 97-96a
3016-1994
15/95
D 130-94
2160-1998
154/95
DIN- ISO
3016:1982-10
51 759
D 445-97
3104-1994
71/97
D 665-98
7120-1987
135/93
51 585 A-HE
D 892-98
6247-1998
51 566 E
Edition 12/83
D 974-97
6618-1997
146/82
312/74
139/98
D 1401-98
6614-1994
D 1479
(Discontinued)
D 1500-98
51 550
51599
290/84
2049-1996
196/97
D 1748-83
366/84
51359
D 2266-99
239/97
51 350 Part 5
226/91
DIN-ISO
2909:1997-10
D 2270-93
2909-1981
D 2782-94
51 434 Part 2
51350
Part 2
D 2783-88
293/97
D 2983-87
267/84
D 3601-88
312/74
D 4172-94
293/97
D 4627-92
287/94
125/82
51 360 Part 2
D 5182-97
334/93
51 354 Part 2
D 5293-99-
383/94
51 395-1
Dynamic Test
51 350 Part 3
Settling
Dehydration
Reprocessed Oil
Fine Solids
Fillratlon
Dehydration
/ \
^~^
Fine Solids
Clay/Alkali
Treatment
Water Washing
/
-Acidic Contaminants
Water
Heating/Distillation
/
Additive Blending
Clay Treatment
Reclaimed Lubricant
REFERENCES
[1] Bartenev, G. M. and Lavrentev, V. V., "Friction and Wear of Polymers," Elsevier Publishing, NY, 1981, p. 203.
[2] Fein, R. S., "Boundary Lubrication," CRC Handbook of Lubrication,
Theory and Practice in Tribology, Vol. 11, Theory and Design, Richard
E. Booser, Ed., CRC Press, Boca Raton, FL, 1983, pp. 49-67.
[3] Samuels, L. E., Doyle, E. D., and Turley, D. M., "Sliding Wear
Mechanisms," Fundamentals of Friction and Wear of Materials,
Papers presented at the 1980 ASM Materials Science Seminar, Pittsburgh, PA, October 4-5, 1980, David A. Rigney, Ed., ASM International, Materials Park, OH, 1981, pp. 214-216.
[4] Sargent, L. B., Jr., "On the Fundamental Nature of Metal-Metal
Adhesion," ASLE Transactions, Vol. 21, 1978, pp. 285-290.
[5] Larsen-Basse, J., "Basic Theory of Solid Friction," American Society of Metals Handbook, Friction, Lubrication, and Wear Technology, Scott D. Henry, Ed., Vol. 18, ASM International, Materials
Park, OH, 1992, pp. 27-38.
[6] Schiemann, L. F. and Schwind, J. J., "Fundamentals of Automotive Gear Lubrication," SAE Paper 841213, Fuels and Lubricants
Technology: An Overview, SP603, Society of Automotive Engineers, Warrendale, PA, October 1984, pp. 107-115.
[7] Fundamentals of Tribology, N. P. Suh and N. Saka, Eds., the MIT
Press, Cambridge, MA, 1980.
[8] Wedeven, L. D., "What is EHD?" Journal of the American Society
of Lubrication Engineers, Vol. 31, June 1975, pp. 291-296.
[9] Dowson, D. and Higginson, G. R., Elasto-hydrodynamic
Lubrication: The Fundamentals of Roller and Gear Lubrication, Pergamon
Press, Oxford, England, 1966.
[10] Laemmle, J. T., "Metalworking Fluids," American Society of Metals Handbook, Friction, Lubrication, and Wear Technology, Scott
D. Henry, Ed., Vol. 18, ASM International, Materials Park, OH,
1992, pp. 139-149.
[11] Rein, S. W., 'Viscosity-I," Lubrication, Vol. 64, No. 1,1978, pp. 1-12.
[12] Klamann, D., "Tribology and Tribotechnology," Chapter 2, Lubricants and Related ProductsSynthesis. Properties. Applications. International Standards, Verlag Chemie, Hamburg, 1984, pp. 4-25.
[13] "Petroleum Products and Lubricants," Annual Book of ASTM
Standards, ASTM International, West Conshohocken, PA.
MNL37-EB/Jun. 2003
Petroleum Waxes
G. All Mansoori, ^ H. Lindsay Barnes,^
and Glenn M. Webster^
try as a gelling agent for organic solvents and as a raw material used in lipstick formulations for t h e cosmetic market.
C a m a u b a wax is recognized generally a s safe by the United
States Food and Drug Administration.
Candelilla wax is harvested from the shrubs Eurphorbiea
antisiphilitica, E. cerifera, and Pedilanthus pavonis in Mexico
and southwest Texas. The candelilla wax is recovered after
the entire mature plant is uprooted and immersed in acidified boiling water. During the immersion, the candelilla wax
floats to the surface and is skimmed off. The primary market
for candelilla wax is cosmetics where it is a component in lipstick formulations. The chemical composition of c a m a u b a
and candelilla wax is listed in Table 2.
Synthetic waxes are derived from either the Fischer-Tropsch process [7] or by ethylene based polymerization processes [8]. The Fischer-Tropsch (F-T) process originated in
Germany in the 1920s and is illustrated schematically in E q
1. The F-T process was developed to synthesize hydrocarbons
and oxygenated compounds from a mixture of hydrogen and
carbon monoxide. During World War II, the F-T process was
used by Germany to produce fuels from coal-derived gas. The
first commercial plant in South Africa started in 1955 at
Sasolburg, using coal as a feedstock. The so-called Sasol process is illustrated in Fig. 1 [9]. This plant produces waxes, fuels, pipeline gases (i.e., ethylene, methane), and other products using a fixed bed catalyst F-T process. During the F-T
process, carbon monoxide, which is generated from coal
gasification, is reacted u n d e r fixed-bed conditions using
high-pressure at approximately 220C in the presence of a n
iron catalyst to p r o d u c e synthetic hydrocarbon waxes, as
shown in Eq 1. Typical reaction products that may be derived
from the F-T process are listed in Table 3.
2nH2 + nCO -> C Hzn + nH20
525
Copyright'
2003 by A S I M International
(1)
www.astm.org
526
HANDBOOK
Amount in wt. %
Product
Paraffins (i.e., methane, ethane, propane,
and butane)
Olefins (i.e., methylene, ethylene, propylene,
and butylene)
Gasoline (Cs-Cn)
Diesel (C12-C18)
Ci9 to C23
Medium Wax (C24-C35)
Hard Wax (>C35)
Water soluble non-acid chemicals
Water soluble acids
7.2
5.6
18.0
14.0
7.0
20.0
25.0
3.0
0.2
Component
Monoesters
Fatty alcohols
Free fatty acids
Hydrocarbons"
Resins
Moisture and inorganic residue
%)
Candelilla (wt. %)
83-88%
2-3
3-4
1.5-3.0
4-6
0.5-1
28-30%
2-3
7-9
49-57
4-6
2-3
"Hydrocarbons commonly found in carnauba and candelilla wax are principally hentriacontane (C31H64) and tritriacontane (C33H68).
iWolecular Weight
Melting Points, C
500-1200
900-3000
85-110
90-125
500-4000
85-130
1000-3000
90-130
POWER
PLANT
COAL
SIEAM
1
GASmCAHOM 4
''
OXYGEN
PLANT
AIR
AE GON N,
nrr^f
RAW CAS
FDBinCAIION
CO, + H,S-*
OSOTE
PflTAR NAPHTHA
PURE GAS
FT
PROCESS
AI.COHOLS KErroms
LA.
F T WATER
WORK-UP
WATER
SEPARATION
FHACnOHAIION
GASES
NAI>^HA
CRYOGENIC
SEPARATION
WATER
praancATioN
WAX
DISCUSSION
Classification of Crude Oils and Chemical
Structure of Ingredients
Cj/Ci
CH
EIHYL0IE
PLANT
REFORMING
on.
rt:o,
PHACnONAnON
OUCOMEBISAHON
OILS
STEAM O2
CHj
CjHj
CHAPTER
19: PETROLEUM
WAXES
527
Base Oil
Wax Content
Asphalt
API Gravity"
Paraffinic base
Naphthenic base
Intermediate base
Asphaltic base
Yes
No
No
No
Yes
Yes
Yes
Yes
<10%
No
<6%
0%
Low
Low
Low
High
No
No
Yes
Yes
>40
<33
33-40
<10
E-1519
D-2864
D-8
D-1079
"American Petroleum Institute gravity is an arbitrary scale expressing the density of liquid petroleum products. The measuring scale is calibrated in terms of
degree API ("API) and can be calculated in terms of the formula: "API = 141.5/(SG'-[60''F]) 131.5 where SG'' stands for liquid specific gravity with respect to water. The higher the value of API gravity, the more fluid the liquid.
D 2425
D 2549
D 2786
D 2887
D 3239
D 3279
talline wax. Those formed from naphtenes are known as microcrystalline wax. A hydrocarbon in pure state has definite
boiling and freezing (or melting) points, which can be measured in the laboratory [16]. Knowing the intermolecular energy parameters or critical properties cuid acentric factor
and/or refractive index of hydrocarbons, one can predict their
boiling point using vapor pressure correlations or equations
of state as discussed in Section I of this report. However, such
methods are not capable of predicting pure hydrocarbon
freezing points. There are other methods that can be used to
predict hydrocarbon and wax freezing (melting) point, which
include but are not limited to variational statistical mechanical theory [17] and cell-lattice theories [18].
Waxy Crude
Oil
A waxy crude usually consists of: (a) a variety of light and intermediate hydrocarbons (paraffins, aromatics, naphtenic,
etc.); (b) wax as defined above; and (c) a variety of other
heavy organic (non-hydrocarbon) compounds, even though
at very low concentrations they include resins, asphaltenes,
diamondoids, organometcillics, etc. When the temperature of
a waxy crude oil is lowered to its cloud point, first the heavier fractions of its weix content start to freeze out. Upon lowering of the temperature of a crude oil to its pour point al-
y^'.-'
To predict the deposition as a function of time, principles of energy and mass conservation, the laws of diffusion, and the principles of phase transitions need to be considered [21,22]. In order to prevent or remediate arterial blockage/fouling and
facilitate the production of regular waxy crudes, many issues
must be underteiken: (a) detailed fluid properties characterization, (b) production scheme alternatives, (c) retrograde condensation and deposition behavior prediction, (d) onsets of deposition studies, (e) equipment and facility options, (f) design
and use of chemical anti-foulants and/or pour-point depressants and blending alternatives, (g) performance specification
and maintenance planning, and (h) transportation, storage,
and blending studies [23,24].
Petroleum Refining
Crude oil is first desalted if salty, deasphalted if asphaltenic,
and dewaxed if highly waxy, before it is distilled in an atmospheric distillation unit to separate light ends (gases), naphtha, gasoline, jet, kerosene, gas oil distillate, and residuum
(resid) (see Fig. 3). The residuum (resid) remaining after the
atmospheric distillation is then further fractionated in a vacuum distillation unit into fractions that are distinguishable
by viscosity for further processing into lubricating oil base
stocks. Wax is concentrated in the distillate stream and the
residuum fraction is used to produce the base oils for lubricant formulation. Both the distillate and residual lube fractions (stock) contain undesirable constituents such as aromatics that must be removed by extraction to jdeld base oils
that are thermally stable with a sufficiently high viscosity index'' product. The distillate fraction is extracted with a sol* Viscosity Index is defined as V.I. = (/XL ~ hiodKlJ'i. ~ MH)- wiiere /AL
is the viscosity at 100F of the zero-V.I. oil, /U-H is tiie viscosity at
100F of the 100 V.I. oil, and /itx is the viscosity at 100F of the unknown (test) oil. See ASTM D 567 and D 2270 for further detail. A
measure of the magnitude of viscosity changes in lubricating oils
with changes in temperature. The higher the viscosity index number,
the more resistant the oil is to change in viscosity.
s' X Dewaxed
iDeasphaltingp
Asphalt
FIG. 3Schematic illustration of various possible locations of wax production in
petroleum refining.
OflyWax
Receiving
Product Shipped
ik
ik
Blended
Product
Oily Wax
Storage
f .Ciystallization
Sulvent
Blending &
Packaging
Mditives
Decoloiid]^
&
Deodortdng
FntratiDn
Snlinnt
Recnwer;
Wax
&
Solvrait
StmagB
PrnductllAx
FIG. 4Solvent dewaxing process for tine removal of wax from lubricating oil slacltwax basestocks.
50
4030
20
100
-101
-20
-30
-401
-50
30
OaPbaaie
Spanition
40
50
60
70
80
90
% MEK Content in Dewax Solvent
100
60
55
50
15.6
12.8
10.0
Wax
Yield
(%)
Wax Melt.Point
(ASTM D 127)
(F)
CC)
62
67
72
141
139
137
60.6
59.4
58.3
Wax Needle
Penetration
@ yy-F (25c)
(ASTM D 1321)
11
13
16
' FDA regulations for waxes, 21 CFR 172.886 and 21 CFR 178.3710.
Alkanes
No. of
C Atoms
Mol. Wt
Melting Ft
(K)
Latent Heat
of Fusion
(kJ/kg)
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Eicosane
Heneicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriacontane
Dotriacontane
Tri triacontane
Tetratriacontane
Pentatriacontane
Hexatriacontane
Heptatriacontane
Octatriacontane
Nonatriacontane
Tetracontane
Dotetracontane
Tritetracontane
Tetrateracontane
Hextetracontane
Octatetracontane
Pentacontane
Hexacontane
Heptacontane
Hectane
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
42
43
44
46
48
50
60
70
100
16
30
44
58
72
86
100
114
128
142
156
170
184
198
212
226
240
254
268
282
296
310
324
338
352
366
380
394
408
422
436
450
464
478
492
506
520
534
548
562
590
604
618
646
674
702
842
982
1402
90.68
90.38
85.47
134.79
143.45
177.83
182.55
216.37
219.65
243.50
247.55
263.55
267.75
278.95
283.05
291.25
295.05
301.25
305.15
309.75
313.35
317.15
320.65
323.75
326.65
329.45
331.95
334.35
336.35
338.55
341.05
342.85
344.55
346.25
347.85
349.35
350.85
352.15
353.45
354.65
357.32
358.65
359.55
361.45
363.45
365.15
372.15
378.65
388.40
58
95
80
105
117
152
141
181
170
202
177
216
196
227
207
236
214
244
222
248
213
252
234
255
238
250
235
254
239
252
242
266
256
268
257
269
259
271
271*
272
273
273*
274
276
276
276
279
281*
285*
Solid at
298 K
485.4
514.6*
544.3
570.7*
598.1*
625.0*
651.4*
670.4*
677.8
728.1*
752.8*
777.2*
801.2*
824.5*
867.4
871.0*
887.4
916.0
937.5*
959.1*
980.4*
1001*
1022*
1062*
1085*
1102*
1140*
1177
1213*
1380*
1526*
1869*
Liquid at
353 K
Boiling Pt
(K)
0167.2
195.4
225.0
254.2
284.5
314.5
345.0
376.0
406.9
438.5
470.0
501.5
534.3
564.4
618*
658*
698*
739.0
772.0
805.0
815.9
870.0
928*
937.0
1001*
1037*
1073*
1095
1113
1149
1210*
1206
1276*
1305*
1341*
1411
1435
1465*
1495*
1553*
1595
1665*
1916*
2131*
2598*
116.6
184.6
231.1
272.7
309.0
341.9
371.6
398.8
424.0
447.3
469.1
489.5
508.6
526.7
543.8
560.0
575.2
589.5
603.1
617.0
629.7
641.8
653.4
664.5
675.1
685.4
695.3
704.8
714.0
722.9
731.2
740.2
748.2
755.2
763.2
770.2
777.2
784.2
791.2
795.2
804.2
813.2
818.2
829.2
838.2
848.2
888.2
919.2
935.2
(*)Predicted value.
(a) X 200
X 1000
(b)
533
FIG. 8An atomic force microscope image of the spiral growth of paraffin crystal (measuring approximately 15 microns across). Inset shows orthorhombic arrangement (0.49 nm x 0.84 nm) of chain ends of one of the crystal terraces (courtesy of Professor M.J. Miles).
X 1000
(a) X200
(b)
FIG. 9A scanning electron microscopic illustration of a microstructural characterization of a refined paraffin wax (a. = 200 X; b = 1000 X).
Paraffin Wax
Intermediate
Microcrystalline
Petrolatum
110-155
320^50
Plates
White
150-165
450-550
Needles
WhiteYellow
140-195
450-700
Needles
WhiteDark Brown
110-180
450-700
Needles
WhiteDark Brown
Crystal Structure
ParafBn waxes exhibit several crystalline structures depending on their carbon chain length. Odd n u m b e r carbon chains
between C19 and C29 exhibit an orthorhombic type crystal
structure. Even numbered carbon chains between Cjg and
C26 exhibit a triclinic structure. Even n u m b e r e d carbon
chains between Cjg and C36 exhibit a monoclinic structure.
All paraffins with carbon chains between C20 and C36 have a
distinct transition point (change in crystal form) lower than
the temperature at which they solidify. The transition point
occurs when the wax crystal structure rotates from a hexagonal to o r t h o r h o m b i c form as the wax solidifies from a
molten state. Paraffins with carbon atom chains above C37 do
not exhibit a transition point due to the wax solidifying directly into a n o r t h o r h o m b i c crystal structure. Microcrystalline and intermediate type waxes do not exhibit any transition point because they contain higher a m o u n t s of
branched alkanes.
Because of the steric effects caused by the arrangement of
atoms in the molecule there is a difference between alkanes
with odd and even numbers of carbon atoms. The even-num-
HANDBOOK
bered homologs have higher latent heat than the odd-numbered homologs. Humphries [29] showed that alkanes with an
even number of carbon atoms (between 20 and 32) and alkanes with odd number of carbon atoms (higher than 7) exhibit
a lattice transition in the solid state. The even-numbered carbon atom alkanes exhibit this transition closer to their melting point than the odd-numbered alkanes, as demonstrated in
Fig. 10. The boiling point of normal-alkanes for the temperature range on the figure are sJso shown in Fig. 10.
The lattice transition in alkanes is accompanied by the release of heat of transition. Generally, lattice transition occurs
in the solid state at about 2-5K below the melting point. The
difference between the transition temperature and melting
temperature becomes smaller with increasing molecular
weight and finally disappears for alkanes with more than 36
carbon atoms [25,28] as demonstrated in Fig. 10. The heat associated with this solid-solid transition is subtracted from the
lattice heat of melting. Figures 11 and 12 show variations of
the latent heat of melting, melting point, and density of normal alkanes versus increasing number of carbon atoms in
their structure. According to these figures, while the melting
point and density versus the number of carbon atoms have
500
'
25
30
35
Number of carbon atoms
40
FIG. 10Variation of meiting point (MP), transition temperature (TrT), and boiling point
(BP) of normal alltanes with their number of carbon atoms [28].
1 .
3
_^-<TyOO-C/-
non
cS
g250 o>
I
Si
S200
O o9?fm
AAI&OO"
"O
r,
"
QRRF"^^^
)00
9NM
rtAl i t " 1
wX* *
sw-
_i
150 -
f
6
100 -
20
40
60
80
100
Number of carbon atoms
FIG. 11Variation of the latent heat of melting of normal alkanes with the number of carbon atoms in alkanes and exhibition of the steric effect [28].
1000
400
a
u
800 11
3
>
600
400
200
20
40
60
80
^0
.100
WAXES
535
it is necessary to be able to predict thermodynamic properties of wax. In this section we present five equations of state,
which are used for prediction of molar volumes, vapor pressures, and supercritical solubilities of alkanes [32].
The simplest and one of the most widely known equations
of state is that of van der Waals. However, this equation of
state is not accurate enough to predict thermodynamic properties of most fluids. Inspired by the van der Waals model, investigators have proposed several equations of state through
the years. Almost every equation of state has been claimed to
Table 10Chemical composition and
thermophysical properties of Suntech PI 16
Paraffin Wax [30].
Hydrocarbon
Weight -%
n-C-20
n-C-21
n-C-22
n-C-23
n-C-24
n-C-25
n-C-26
n-C-27
n-C-28
n-C-29
n-C-30
n-C-31
n-C-32
Melting range
Heat of fusion
Liquid specific heat
Solid specific heat
Liquid thermal conductivity
Solid thermal conductivity
Liquid density
Solid density
Liquid viscosity
Molecular weight
2.0
5.5
14.0
23.0
22.0
14.0
6.5
3.0
2.5
2.0
1.7
1.5
1.3
316-329K
266 kJ/kg
2.51kJ/kgK
2.95 kJ/kgK
0.24 W/mK
0.24 W/mK
760 kg/m^
818kg/m^
1.90kg/ms
332 g/mol
20 21.22 23 24 25 26 27 28 29 30 31 32
Number of carbon atoms
FIG. 13The distribution of n-alkanes in Suntech P116
paraffin wax as a function of the number of carbon-atoms
[28].
536
MANUAL
A-. . " . - V
' -'i*.- T i ; : -
' >
HANDBOOK
fr^,
- . .
2 =
'ivX
v-V yb
(2)
where a=naaR^
Tj^-^'^ / Pc and 6 = c = rij, ^ i? T,. / P^.
Parameters {1^, ^b, y, V> and ^ ^re component-independent
constants, while a a n d j3 are component-dependent constants, and their numerical values for various equations of
states are given in Table 11. In extending the equations of
state to mixtures, parameters a, b, and c are replaced with Um,
b, and Cm with the following expressions (mixing rules):
(4)
'^yAi
For the RM equation there is another alternative in extending it to mixtures by replacing Tc and Pc with Tcm and Pcm as
given below:
(b)
..
RM-2: T,m =
{^yiyiTl^pMy^yiyiT,i,pX
Rfn = YI,yiyiR%
i J
be superior in some respects to the earlier ones. The RedhchKwong (RK) equation that is a modification of the van der
Waals equation, was a considerable improvement over other
equations of relatively simple forms at the time of its introduction. In the Soave-Redlich-Kwong (SRK) equation, the
temperature-dependent term of a/T"-^ of the RK equation is
replaced by a function denoted by a that depends on the
acentric factor of the compound and temperature. The PengRobinson (PR) equation is another cubic equation of state involving acentric factor. Riazi and Mansoori [33] modified the
parameter h of the RK equation by introducing a function,
denoted by '?, that depends o n the refractive index of the compound. They showed that the resulting equation is quite accurate in the prediction of hydrocarbon densities. MohsenNia et al. [34] proposed that the 3M equation in which the
repulsive part of the RK equation is modified based on the
statistical mechanics improved the thermodynamic predictions appreciably. This equation is shown to be more accurate for heavy hydrocarbon phase behavior calculation than
most of the other equations of state. RK and 3M equations
are two-constant-parameter equations of state, while the RM,
RK
MMM
RM
PR
SRK
0
1
0
0.5
0.42748
0.08664
1
1
1.3191
1
0
0.5
0.487480
0.064462
1
1
0
1
0
0.5
0.42748
0.08664
1
0
1 -H V2
0
0
0
0
0.42748
0.08664
1 -V2
A
0
e
0.45724
Oa
0.07780
ftfa
a
PR
CSRK
1
1
PRM
/3
apR = [1 + (0.37464 + 1.524226M - 0.26992m^)(l - T?')]^
CSRK = [1 + (0.48508 + 1.55171a) - 0.156132)(1 - T-^)T
(fe)-' = 1+ [0.02[1 - 0.92 exp(-l,000 \T, - I|)] - 0.035 (T, - 1)]{R*-1)
CHAPTER
lowing form [32]:
In <AF = (1 + y)
-InZ-
dinbmVdtii
CnRT'^^^"^
Uffj
dtli
+ XCm)
K = y [ ( l + 2fv)l(l
1 d{nc)
1 d(rp-a)
ir, - \)cRT^'^^^
WAXES 5 3 7
ln(i; - bm/v)
{v + TprnXv
19: PETROLEUM
Cm
2fv)r
(8)
(6)
where
drii
fv = ^SGv [0.466590/ri'2
+ (-0.182421 + 3.0172/r^'^)ASGv]
ASGv = exp [4(SG2 - SG^)] - 1
^^
d{nbm)
a(nc,n) L
The critical pressure (in psia) is given by the following expression [37]:
for 3M:
1 din^dm)
n
anj
-V
=
2 >
^(nb,)
an;
(9)
where
V.77.V
M^l^yih - YLyiythj + ^
bu
+ 36.1952a2 + 104.193a^)2
J_ d{n a^)
J-
-J
^ ^ RTO-SI^Y
V T^ IP - - T
T vT
IP
^ cm / , Yi^ cii'^ ci
'
\ /
/
d{nbm)
d(ncm)
/ o,
9/3 V v v
T- /D ^
= (-li + n - ^ j \ l l yffi TclPciij
drii
dm
(10)
T=l-T/Tc,
(11)
where
To calculate liquid molar volume and vapor pressure using equations of state, t h e data of critical temperature a n d
pressure, acentric factor, a n d molar refraction are needed.
The experimental critical properties of n-alkanes u p to C24
are available in the literature [35,36], while those of n-alkanes higher t h a n C24 c a n b e estimated using correlations.
The critical temperature (in degrees Rankine) can be written as [37]:
r , = r [ ( l + 2fr)/(l - 2 / r ) ] '
(7)
where
JT = ASGr [-0.362456/7^'^
+ (0.0398285 - 0.948125/4'2)ASG7-]
ASGr = exp [5(SG - SG)] - 1
Tt = Tb (0.533272 -t- 0.191017 X 10"^ Tb + 0.77968
X 10"^ Ti -0.284376 X l O " ' " Tl + 0.959468 X 10^^ T^ " )
SG" = 0.843593 - 0.128624a - 3.3615a^ - 13749.5a'^
and where subscript T refers to t e m p e r a t u r e , subscript c
refers to the critical conditions, superscript o refers to the ref-
W= (-logP)7-^=o.7 - 1
and
a{ca) = - 6 . 1 5 5 9 - 4 . 0 8 5 5 & ;
fo(w) = 1.5737 - 1.0540(0 - 4.4365^:10^^^(0))
c(w) = - 0 . 8 7 4 7 - 7.8874W
d{(,}) = (-0.4893 - 0.9912W + 3.15510^)''
The above equation is quite accurate for calculation of vapor pressure provided the acentric factor and critical properties of a fluid a r e available. The molar refractions of wax
compounds needed in the RM equation of state are available
in Ref. 36.
The accuracy of molar volumes of saturated liquid wax
components, molar volumes in sub-cooled and supercritical
conditions a n d vapor pressures calculated using various
equations of state are reported in Tables 12-14, respectively.
According to these tables the three-constant RM equation of
state is quite satisfactory for molar volume prediction while
the SRK is accurate for vapor pressure prediction of wax.
In Fig. 15 the solubility of n-tritriacontane (n-CaaHgg) in supercritical carbon dioxide is depicted along with the predictions obtained from various equations of state. According to
n-CsHis
M-C9H20
n-CioH22
n-CiiH24
n-Ci2H26
"-C13H28
n-Ci4H3o
W-C15H32
"-C16H34
M-Ci7H36
H-C18H38
M-C19H40
ra-C2oH42
M-C22H46
ra-C24H5o
n-C28H58
Tr Range
RK
3M
RM
PR
SRK
0.71-1.00
0.48-0.99
0.33-0.99
0.35-0.98
0.36-0.96
0.47-0.99
0.39-0.99
0.41-0.99
0.41-0.99
0.42-0.98
0.43-0.98
0.55-0.78
0.54-0.89
0.56-0.80
0.54-0.85
0.58-0.82
0.56-0.81
0.59-0.83
0.55-0.84
0.56-0.85
0.57-0.85
0.55-0.81
0.56-0.82
0.58-0.84
19.5
4.5
10.3
11.2
13.3
16.8
19.9
22.3
24.7
26.8
29.9
31.1
35.3
37.6
42.8
45.8
49.7
56.2
59.5
63.5
67.9
57.6
66.2
62.9
36.5
8.8
13.9
11.8
10.8
9.0
7.5
6.9
7.4
6.9
7.8
10.5
10.5
14.7
16.5
21.4
24.1
26.9
32.9
35.5
39.0
42.9
31.8
39.2
36.4
19.7
19.5
4.5
6.4
3.9
3.0
2.4
2.2
1.4
1.2
0.8
0.7
0.3
0.4
0.2
1.2
1.2
1.8
3.9
4.0
4.4
4.8
4.5
2.9
11.2
3.6
4.7
8.6
6.0
5.3
3.6
3.4
2.2
2.7
4.2
5.1
7.0
7.4
10.1
11.4
15.0
16.7
19.7
24.3
26.9
29.6
32.2
25.1
31.1
27.7
13.8
14.7
4.5
9.2
9.2
10.3
12.5
14.8
16.0
17.7
18.7
20.8
21.3
24.3
25.8
29.9
31.8
35.1
40.3
43.1
46.1
49.0
40.6
47.2
43.1
26.1
Overall
TABLE 13The average deviations of various equation of state in predicting molar volumes of liquids in sub-cooled and
supercritical conditions compared with experimental data.
AAD%
Experimental Data
Compound
Tr Range
Pr Range
RK
3M
RM
PR
SRK
Ref
CO2
CH4
C2H6
C3H8
M-C4H10
W-C5H12
n-C6Hi4
n-C7Hi6
n-C9H2o
W-C11H24
M-C13H28
n-CnH36
W-C20H42
M-C30H62
Overall
0.7-2.2
0.5-2.6
0.3-2.3
0.2-1.9
0.3-1.7
0.4-0.7
0.4-0.7
0.6-1.1
0.5-1.0
0.5-0.9
0.4-0.9
0.4-0.8
0.4-0.8
0.4-0.8
1.0-13.6
0.0-15.2
0.0-14.3
0.0-16.5
0.0-18.5
0.0-71.3
0.0-332
1.8-183
2.2-218
2.6-259
3.0-303
4.1^10
5.0-500
6.8-682
5.0
2.0
3.8
5.9
8.4
11.2
14.7
14.5
18.8
25.1
32.3
48.5
59.9
62.7
22.3
4.8
11.1
11.2
9.6
8.4
7.6
5.8
5.6
3.1
3.1
7.9
19.8
28.6
28.9
11.1
5.0
2.0
1.7
1.8
1.6
0.8
2.0
2.3
2.2
2.6
3.2
7.2
9.9
6.8
3.5
2.9
7.4
5.6
4.2
3.8
2.5
2.5
3.3
5.1
10.4
16.7
31.0
41.1
43.5
12.8
6.1
2.4
4.1
5.9
7.9
9.4
12.6
13.5
17.1
23.1
30.1
45.9
57.1
59.8
21.0
447
459
474
533
638
880
510
70
66
70
70
60
50
50
4377
a
b
c
d
e
f
f
f.g
S
S
s
s
s
s
WAXES
539
TABLE 14The average deviations of various equations of state in predicting vapor pressures of pure compounds
compared with the experimenteJ data.
AAD%
Compound
CO2
CH4
C2H6
C3H8
n-C4Hio
n-CsHn
n-C6Hi4
n-CyHie
n-CgHis
n-C9H2o
f3-CioH22
n-CiiH24
n-Ci2H26
n-Ci3H28
n-Ci4H3o
W-C15H32
-Cl6H34
n-Ci7H36
n-CisHss
?2-Ci9H40
n-C2oH42
ra-C22H46
n-C24H5o
n-C28H58
M-C29H60
n-C3oH62
M-C32H66
n-C33H68
Experimental Data
Tf Range
RK
3M
RM
PR
SRK
Ref
0.71-1.00
0.48-0.99
0.33-0.99
0.35-0.98
0.36-0.96
0.47-0.99
0.39-0.99
0.41-0.99
0.41-0.99
0.42-0.98
0.43-0.98
0.55-0.78
0.54-0.89
0.56-0.80
0.54-0.85
0.58-0.82
0.56-0.81
0.59-0.83
0.55-0.84
0.56-0.85
0.57-0.85
0.55-0.81
0.56-0.82
0.58-0.84
0.54-0.84
0.54-0.84
0.55-0.85
0.55-0.85
19.1
17.2
11.5
19.8
43.2
63.4
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
-2100
4.0
50.0
36.3
39.5
32.4
19.2
15.8
11.0
18.5
33.2
51.4
81.7
89.9
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
>100
-650
19.1
17.2
11.9
8.3
7.0
9.9
16.5
20.7
28.9
33.3
37.4
37.7
31.7
28.8
30.3
23.4
29.3
23.9
30.2
30.4
33.0
69.1
79.4
57.9
82.5
75.8
61.5
56.9
35.4
0.8
0.7
3.0
3.0
5.6
0.8
3.1
2.4
2.7
2.1
3.1
6.6
2.9
3.3
5.8
4.0
5.6
6.2
9.2
10.4
8.8
18.6
24.7
33.9
42.5
44.5
48.9
51.8
12.7
0.5
2.9
2.6
1.9
1.9
1.5
1.9
1.2
1.2
1.5
1.2
4.4
0.4
0.5
2.5
0.6
0.9
1.6
3.0
3.6
2.4
1.2
1.5
1.7
2.7
2.7
3.2
3.9
2.0
47
84
114
101
130
91
88
80
87
82
86
27
40
27
42
27
45
43
44
42
42
21
22
23
12
12
12
12
1483
a
b,c
b,d
b,e
b,f
b,h
b,h
b,h
b,h
c,h
b,g,h
b
b,g,h
b
b,g,h
b
b,g,h
b
b,g
b,g
b,g
b,g
b,g
b,g
b
b
b
b
Overall
" Angus et al.. 1979.
'' Frenkel et al. , 1997a.
= Goodwin, 1974.
'' Goodwin and Roder, 1976.
" Goodwin and Haynes, 1982.
' H a y n e s and Goodwin, 1976.
^ Morgan and Kobayashi, 1994.
' Salerno et al. , 1986.
this figure, the 3M and RM equations aire capable of predicting supercritical solubilities accurately. In all these cases the
unlike-interaction parameter,fcy,is best fitted to experimental data. Table 15 shows the interaction parameters of various equations of state for a number of systems at various
temperatures along with the AAD%. According to this table,
the 3M equation of state gives the least value of AAD%.
Differential Scanning Calorimetry
When a solid is heated, it may absorb heat resulting in a temperature increase or a structural change (phase transition)
such as a solid to liquid or a transition from one crystalline
form to another. These transitions may be endothermic (absorb heat) or exothermic (emit heat) depending on the thermal process that is occurring. These thermal processes may
be quantitatively measured by differential scanning
calorimetry (DSC).
DSC analysis is performed by heating two small sample
pans, one containing the material being analyzed and the
other empty and used as a reference. The analysis concept is
that the two sample pans are maintained at a very small temperature difference ( 0.01C). Each pan is heated with two
heaters; a main heater and an auxiliary heater. After begin-
540
/tr-s-S^*-"
-5
-6
^-7
j
1
0-9
-11
-12
HANDBOOK
/
/
RK
Pr
4
/--rrQjQ.oo
-5
-6
Ss
-n
-12
-13
PR
M-~-.
Pr
Pr
Heat X Temperature
Ttime X Mass
Q J^ ~0M
(12)
Typically, the actual units of \Hf&re (joules Kelvin seco n d s " ' g r a m s " ' ) . Typically, the APUM is divided by the
heating rate (K/s) of the DCS experiment used to collect the
data. This will simplify the expression to yield the specific
heat of melting:
Q.T
APUM
Heating Rate
e.M
X
e
Q_
(13)
trace shown by Fig. 17 demonstrates the decrease in crystallinity as the melting point of the wax increases. The thermal analysis procedure for this work was started at - 50C for
o p t i m u m crystallization of the wax. The wax sample was
heated at a controlled rate to +150C. The point at which
there is a deflection in the base line is the temperature that
the wax begins to melt. The point at which the peak scan returned to the base line is the temperature the wax sample is
completely melted. The peak area represents the amount of
energy used to melt the wax sample and is calculated as described above. In addition, an estimate on the expected melting point can be distinguished. The experienced technologist
could tell by looking at the shape of a DSC trace if the wax is
a paraffin, intermediate, or microwax. Paraffin waxes typically exhibit sharp peaks as shown in Fig. 16a, DSC peak
shapes for intermediate waxes are less sheirp as shown in Fig.
\6b, and microwaxes exhibit even less sharp peaks, typically
like the peak shown in Fig. 16c.
It should be noted that there is a characteristic small transition peak in the DSC trace for a macrocrystalline paraffinic
wax as illustrated in Fig. 16fl. The transition that is indicated
is a solid-solid phase change (orthorhombic to hexagonal
C2H6 - ra-C33H68
CO2 - n-C28H58
C 0 2 - M-C29H60
CO2 - -C3oH62
CO2 - n-C32H66
CO2 - n-CjsHfts
AAD%
kyi
T
[K]
P
[bar]
RK
3M
RM-2
308.2
308.2
308.2
313.2
308.2
313.2
318.2
319.2
308.2
313.2
318.2
307.2
308.2
313.2
318.2
318.6
323.4
325.2
308.2
318.2
308.2
318.2
308.2
318.2
328.2
308.2
318.2
328.2
56-240
65-240
66-200
66-136
66-240
66-200
80-240
80-136
65-240
65-202
65-240
123-181
80-240
90-275
100-250
119-284
125-327
121-284
100-240
100-240
90-250
105-250
120-240
140-240
140-240
120-240
140-240
140-240
-0.4638
-0.4146
-0.4777
-0.4738
-0.5124
-0.5011
-0.5248
-0.4872
-0.4632
-0.4459
-0.4506
-0.3458
-0.3161
-0.2910
-0.2915
-0.3067
-0.2973
-0.2946
-0.2751
-0.1961
-0.3254
-0.3125
-0.4140
-0.3913
-0.3777
-0.3461
-0.3384
-0.3057
-0.2099
-0.1618
-0.2066
-0.2137
-0.2259
-0.2264
-0.2438
-0.2241
-0.1933
-0.1845
-0.1918
-0.0936
-0.0901
-0.0835
-0.0867
-0.0859
-0.0869
-0.0867
-0.0530
-0.0540
-0.1141
-0.1197
-0.1500
-0.1462
-0.1345
-0.1051
-0.1043
-0.0990
0.0807
0.1215
0.1025
0.0901
0.1020
0.1050
0.0966
0.1087
0.1100
0.1433
0.1433
0.2487
0.2477
0.2532
0.2504
0.2531
0.2552
0.2540
0.2782
0.2789
0.2481
0.2439
0.2448
0.2483
0.2596
0.2825
0.2832
0.2878
PR
SRK
RM-1
RK
3M
RM-2
PR
-0.0553
-0.0131
-0.0571
-0.0517
-0.0707
-0.0658
-0.0762
-0.0565
-0.0286
-0.0240
-0.0203
0.0110
0.0296
0.0365
0.0359
0.0347
0.0385
0.0321
0.0645
0.0818
0.0327
0.0273
-0.0162
-0.0035
0.0044
0.0262
0.0280
0.0428
-0.0189
0.0260
-0.0206
-0.0139
-0.0297
-0.0263
-0.0347
-0.0157
0.0137
0.0193
0.0228
0.0507
0.0708
0.0765
0.0746
0.0736
0.0764
0.0690
0.1075
0.1451
0.0779
0.0700
0.0316
0.0426
0.0477
0.0754
0.0872
0.0876
-0.1283
-0.0701
-0.1121
-0.1233
-0.1214
-0.1131
-0.1142
-0.1219
-0.0779
-0.0580
-0.0530
0.0211
0.0194
0.0286
0.0232
0.0278
0.0314
0.0287
0.0670
0.0672
0.0084
-0.0005
-0.0139
-0.0092
0.0104
0.0496
0.0494
0.0557
46.2
53.1
25.0
13.9
46.
24.4
45.2
23.6
50.2
39.6
45.7
51.0
52.3
46.7
64.7
53.7
62.5
64.2
71.8
81.2
69.6
67.5
59.5
67.3
57.5
68.4
65.0
67.4
60.0
27.0
29.9
22.8
30.8
43.0
34.5
17.7
37.4
34.4
21.5
24.2
7.5
18.3
25.0
13.4
8.2
5.8
7.3
21.5
22.2
17.1
8.3
8,1
6.7
9.2
25.0
22.9
18.5
20.3
14.4
23.9
57.2
29.7
56.2
40.2
22.8
39.3
50.7
28.9
28.0
34.4
35.0
44.5
31.0
33.2
28,9
22,6
12,9
6,9
28,8
28.7
24.1
22.3
27.1
11,3
4,8
3,5
28,3
38,
48.
22.
18.
41.
20.
32.
28.
43.
25.
42.
45.
49.
39.
47.
45.
53.
45.
67.
76.
66.
57.
54.
55.
40.
64.
61.
60.
46.
Overall
" Kalaga and Trebble, 1997.
' Moradinia and Teja, 1986.
" Suleiman and Eckert, 1995
' Moradinia and Teja, 1988.
" McHugh et al., 1984
^Reverchon et a ., 1993.
^ Chandler et al., 1996.
S5.0
sao
7SJ>
fata
^
TOO
2\SC
55.syc
SISJ
1316.99
2IB.99
sg s ^*'
&o1 *"35,BJM
Z5JI
"T
I
soo
-2SJ)
TSJ
IOOLO
12M
1500
Tenq>a-^iire(<0
XI
^xsrc
TS3yC
PCA
6ssn
Am I13&63
rtH 17172
H e i ^ 43Jf7
4M-
S, 4 M -
*
s
1-:
..
3W1-
-1S.0
25,0
5IU
1
7U
TemperatnTO (Q
lOOJ)
1
125,0
151
Teiiii)eratiire('C)
FIG. 16The heat of fusion (AHr) calculation from the DSC melting transition peak by
measuring the total area under the peak, (a) paraffin, (b) intermediate, (c) microwax.
1
-50.0
-25.0
r
ao
25.0
50.0
75.0
1
lOaO
r
125.0 150.0
Temperature (Q
FIG. 17The heat of fusion (AH) calculation from the DSC
melting transition peak by measuring the total area under the
peak of several paraffins demonstrating the decrease in crystallinity as the melting point of the wax increases.
crystal structure). As the wax crystal continues to absorb energy, a larger peak is recorded and then actucil melting occurs
with a return to the base line as the temperature continues to
increase.
In addition, there is a bimodality indicated in the DSC
trace peak shapes for intermediate (Fig. 16b) and microciystalline (Fig. 16c) waxes. Bi-modal shape is related to the
breadth of the wax composition. Bimodal peak shape is not
related to transition. The apparent bimodality indicates that
the wax has not been made as a narrow distillation cut. The
melting point of wax is in the DSC area that the curve begins
to return to the base line (downward slope) as the temperature increases. The squat DSC peak shape of the microwax
shown in Fig. 16c indicates that it is less crystalline and has
a broader melting. The apparent bimodality of the microwax
is related to the different melting fractions that appear in this
particular wax.
Determination of the heat of fusion of a wax is of practical
significance for a n u m b e r of reasons. For example, the
changes of shape of a DSC trace to that of known waxes may
indicate that a wax has been contaminated or altered. This
may be confirmed by comparing the heat of fusion of a previously purchased paraffin wax with the suspect wax. For example, a historical value for heat of fusion of a wax may be
200 J/g and a newly purchased paraffin wax may have a heat
of fusion of 180 J/g. This variation confirms that the two
waxes exhibit different properties.
Another application of the heat of fusion could be for the
comparison of properties of nominally similar waxes offered
by two different suppliers. The higher the heat of fusion, the
more crystalline the wax is. For some applications, like candles, high crystallinity is desirable to aid in the mold release
properties due to shrinkage upon cooling. Low crystalline
waxes do not shrink as m u c h as high crystalline products.
ASTM Test Method D 4419 has been developed to characterize petroleum waxes and measurement of their transition t e m p e r a t u r e s by Differential Scanning Calorimetry
(DSC). Figures 16a, 16b, and 16c are DSC endothermic
scans of a paraffin, intermediate, and microcrystalline wax.
Effect of Additives
In the petroleum wax industry, it is often necessary to use additives to improve the processability of wax or wax mixtures
by modifying their physical properties. This may be accomplished by the addition of additives that may include stearic
acid, polyethylene, ethylene-vinyl acetate copol5'mer or a Fischer-Tropsch wax. For example, stearic acid may be added to
a paraffin weix to increase firmness, reduce melting point, aid
in mold release, prevent candles from losing their shape in
warm weather, etc. Polyethylene is another additive that may
be used. Polyethylene m a y b e added to a paraffin wax to
harden the wax structure, modify burning rate, and improve
strength and gloss. In addition to physical property modification, additives also could alter the microstructure of waxes
as demonstrated by Fig. 14.
Property
Determination
'MtanaxfabMaa Wax.
PuraRn WiuE
I
I
Tnutskkai Point-^ \ p
(b)
Time-*
. Tim*-*
FIG. 18(a) Apparatus for ASTM Test Method D 87. Cooling curve for: (b) a paraffin wax,
(c) for intermediate wax, microwax, petrolatum, or waxes containing a higfi percentage
(>50%) of branched alkanes
(c)
543
544
MANUAL
HANDBOOK
Iticxmo couple
Lead-
Ifi-Iluorocarbon
Boldsr Adapter
exSO nun Test Tiibe ,
Aluminum Heating
Bloek
50x50x50 nm
(2x2x2 in).
0.020 i n (H)
Metal Sheathed
Tbexnocouple Probe
r~^~^
Auotransotner
TO 110
AC
Outlet
IFE-Sluorocarbon
Disk Centering
Guide
(a)
50 mg
Wax Sample'
Temperature
solidification
Point
llOV
30-Hatt
Cartridge Heater
(b)
FIG. 19(a) Apparatus for determination of melting (solidification) point (cooling curve)
of non-paraffin type waxes used in ASTM Test Method D 3944; (d) A typical cooling curve
for melting (solidification) point measurement of non-paraffin type waxes.
DmKnsionsmmches(mS&r,
(a)
To Sccorder
^
6 jt SO vm
T e s t Tubs
0 . 0 2 0 I n c h O.D.
Metal Sheathed
Thermocouple
1 / 8 " Thick
I?-n.iwrc"bcm
Diak Cant-tnc
Quid*
(b)
35 X 52 ran.
Vial
used. (ISO 3841 or BS 4695 are also used for cooling curve
determination.)
Test Method D 127 may also be used to determine the
"drop melting point" of a wax. The drop melting point is defined as that temperature where the Wcix becomes sufficiently
fluid to drop from the thermometer being used for making
the determination under prescribed test conditions.
Test Method D 127 is commonly used for non-paraffin type
waxes and paraffin wax blends. These include paraffin/microcrystalline wax blends and paraffin/additive blends that
may contain polyethylene, ethylene-vinyl acetate copolymer,
or a Fischer-Tropsch wax. Test Method D 127 is used to determine the melting characteristics of petrolatums and other
high viscosity petroleum waxes.
Capillary/liquid bath
Capillary/metal block
Kofler hot bar
Differential thermal analysis & differential
scanning calorimetry
Freezing temperature
Pour point
Test Procedure
ASTM E 1
DIN 53181
DIN 53736
ASTM D 3451
ASTM E 473
ASTM E 537
BS 4633
BS 4695
DIN 51421
DIN 53175
ISO 1392
JIS K 00-65
NFT60-114
NFT20-051
ASTM D 97
ISO 3016
546
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
4*^-MkUk
3U-3iJ0lIlu
aiiLO- aiAU).
CORK '
OOOUWr LEVEL-
JMnr
I
MMMC
-rP ini
547
VISCOMETER
TMEKMOMmn
auui IN HomzoNDU.
PLMC WITH C i N I U
OF SPINOLC
aoncM or luiwii
M> HTTOKOrtUMO
MCK
x_x
"
which a standard needle penetrates into the wax under defined conditions using a penetrometer such as the one illustrated schematically in Fig. 23.
To measure the hardness of a wax, Test Method D 1321, the
Needle Penetration Method is commonly used. This method
is based on a standardized needle penetrating into the wax
surface at a specific temperature. The smaller the numerical
value obtained from this test, the harder the wax is. The hardness of the wax can be indicative of undesirable blocking tendency for wax-coated paper. (Note: Test Method D 1321 is
similar to Test Method D 937, which is a cone penetrometer
HANDBOOK
Sample
Reference
Resistance
Thermometer
Heater
(a)
Resistance
Thermometer
Heater
AT-Signal
Nitrogen
First-Order Transition:
Apex
Second Order-Transition:
Apex - Tjj^
Onset
End
(b)
T.-^,,*..,. -r-
FIG. 24(a) Differential scanning calorimetry (DSC) experimental set up; (b) Schematic
of petroleum wax DSC curve (heating cycle) sample determined to have soiid-liquid and
solid-solid transitions. This figure is similar to Fig. 16a.
CHAPTER
changes when exposed to elevated temperatures in the presence of oxygen due to oxidation. Waxes can degrade in the
presence of heat and oxygen. The degradation process involves breaking a bond between a carbon and a hydrogen
atom to make a free radical. The free radicals quickly form
peroxides initially and further react to form acids. The
changes in composition can possibly be detected by testing
for color a n d odor. Antioxidants are added to p e t r o l e u m
waxes to chemically stabilize them from the heat degradation
process [41].
Color - Test Methods D 156 and D 1500The color of
petroleum waxes can indicate the degree of refinement or
possible contamination. Color is not always a reliable parameter for determining quality and should be used judiciously as a specification. There are two methods for determining the color of petroleum waxes: Test Methods D 156
and D 1500, and both are subjective and measure the empirical value based on visual observation of the wax in the
molten state.
Test Method D 156 is the Saybolt Chronometer Method for
quantifying the color of petroleum products such as a
petroleum wax. Saybolt color is an empirical definition of the
color of a clear petroleum liquid based on a scale of 16
(darkest) to +30 (lightest). The number is derived by finding
the height of a column that visually matches the appropriate
one of three glass standards and referring to Table 1 of Test
Method D 156. This is done using a Saybolt chronometer (see
Fig. 25), which consists of a sample and standard tubes, optical system, light source, and ASTM color standards.
While Test Method D 156 is used to determine the degree
of whiteness of a wax, Test Method D 1500 is used to measure
the color of waxes that have a tint darker than off-white. Test
Method D 1500 is conducted using a standard light source,
with liquid sample placed into a standard glass container
(sample jar) (see Fig. 26) and compared with colored glass
disks ranging in value from 0.5-8.0 with 0.5 increments.
Carbonizable Substances - Test Method D 612Test Method
D 612 is applicable to paraffin waxes for pharmaceutical use
as defined in the United States National Formulary. Molten
wax is treated with sulfuric acid and the acidic layer is compared visually with a colorimetric reference standard to determine if it passes the conformance criteria for refined wax
using the color comparator shown in Fig. 27.
Peroxide Number - Test Method D 1832Waxes are heat
sensitive and they are susceptible to the action of the oxidation process. The detection of peroxides is the first indication
that a wax has begun to deteriorate in terms of oxidation stability. Petroleum waxes should not have any measurable peroxide values. Deterioration of petroleum wax results in the
formation of peroxides a n d other oxygen-carrying compounds that will oxidize potassium iodide. Peroxide content
is reflected by the peroxide n u m b e r that is defined as the milliequivalents of constituents per 1000 g of wax that will oxidize potassium iodide.
Odor - Test Method D 1833In some end-use applications,
such as food packaging, the intensity of the odor is an important characteristic. Odors can be an indication of the degree
of refining, contamination, or oxidation. Test Method D 1833
describes how to rate the odor intensity based on a subjective
evaluation using a multiple-member test panel. This test is
conducted by preparing odor test specimens from petroleum
19: PETROLEUM
WAXES
549
wax and placing approximately 10 g of thin shavings on odorfree paper or glassine. Individual test specimens are then evaluated for odor by each panel member and assigned a number
according to the odor scale shown in Table 18 that best fits the
intensity of the odor. As an alternative procedure, the wax
shavings are placed in bottles with each panel member making an odor determination between 10 and 60 min after the
shavings are placed into the bottles. The average of the panel
ranking is reported as the odor rating of the sample.
Composition by Gas Chromatography-Test Method D 5442
Test Method D 5442 is applicable to petroleum derived waxes,
including blends of waxes. This test method covers the quantitative determination of the carbon n u m b e r distribution of
petroleum wEixes in the range of n-C17 through n-C44 by gas
chromatography using internal standardization. In addition,
the content of normal and non-normal hydrocarbons for each
carbon n u m b e r is also determined. Material with a carbon
number above n-C44 is determined by difference from 100
mass % and reported as C 45 +. (Note: Standard Practice E 260
provides further information on gas chromatography and
Standard Practice E 355 provides information relating to gas
chromatography terms and relationships.)
Test Method D 5442 is not applicable to oxygenated waxes,
such as synthetic polyethylene glycols (i.e., Carbowax), or
natural products such as beeswax or c a r n a u b a . This test
method is not directly applicable to waxes with oil content
greater t h a n 10% as determined by Test Method D 721.
Functional
Property
Determination
HMDU
NOTC-HiUHLE It FMTOltD T O V
0 Suae
m j
0
0
0
(i)
0
0
oouw
couM oovn
mm uiw
nacMw
(iMm
T mm
suun oi*x
WTAININt iHM
UTHADML (LTCntlfK
MUUM seMovia
0 UtlX
X) t n i m *
LS 0 WATT soil. MMTHI
SCOTIOH "A-A"
Adapter
FIG. 25ASTM Standard Test Method D156 Saybolt Chromometer and artificial daylight
lamp.
FIG.
26Standard
glass sample jar used
in Test Method D 1500
to measure the color of
waxes.
e-i'*Mo/es
Section
Plan
A-A.
T l 3 STOPPER
SiaTlSNECK
m
A
-i-n-j. T
Elevation
I Hi
I h !
"5
-i
i li
!l< '
$>!$
End
Elevation
ISLi
I402MM
Appnox.
CAPACITY
TO STOPPER
late TO {SA ml
145H5.0
MM 0.0.
WALL"
I.ZOIMM
AVER
TEST TUBE
FIG. 27Color comparator used in Standard Test Method D 612 for measurement of carbonizable substances in paraffin waxes for pharmaceutical use.
552
MANUAL
HANDBOOK
Vacuum
'
J J t j
J J
l^L
'^-
Specimen Holder
Porou* Plate
f^\\
>.Specimen
ViU.:.v.M>'.'-.-..!.-.vA-.X!-'.J-; L
rf
J ^JJ
^^*/J
Total Wax Content - Test Method D 3344Many of the functional properties of a wax-treated paperboEird are dependent on
the amount of wax that is present. Test Method D 3344 determines the total amount of wax in a sample of wax-treated corrugated paperboard by extraction. It is applicable to specimens
that have been waxed by either impregnation (saturation) operations or coating operations, or combinations of the two.
Weight of Wax Applied During Coating - Test Method D
3708Test Method D 3708 is used to determine the weight of
a hot melt coating applied to corrugated board by curtain
coating. This method is intended for use as a routine process
control in the plant. The a m o u n t of wax applied is determined by attaching a folded sheet of paper to production corrugated board, running the combination through the curtain
coater, and subsequently determining the applied weight of
wax on the sheet of paper.
Blocking Point - Test Method D 1465The blocking point of
a wax is defined as the lowest temperature at which a film
(15)
K S I S MDI
( r i s r K *i
13 MM ^ l / r i h
(AM. Tm4l lor 13 mm d / T }
60 g of Sand
Stopcock
Size I H
Specimen
FIG. 30Apparatus for measuring abrasion resistance of wax coatings in Standard Test lUlethod D 3234.
Acknowledgments
The authors thank Dr. George Totten for his helpful advice
and guidance in the preparation of this chapter and Dr. Sony
Oyekan, Dr. Chen-Hwa Chiu, Dr. Sang J. Park, and Mr.
Adrian D'Sousa for their technical assistance.
D 721
D 937
D 938
D 1168
D 1298
ASTM STANDARDS
D 1223
No.
D 87
D 97
D 127
D 156
D 287
D 445
D 612
Title
Test Method for Melting Point of Petroleum Wax
Test Method for Pour Point of Petroleum Products
Test Method for Drop Melting Point of Petroleum
Wax Including Petrolatum
Test Method for Color, Saybolt, of Petroleum
Products
Test Method for Gravity, API, of Crude Petroleum
and Petroleum Products (Hydrometer Method)
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids
Test Method for Carbonizable Substances in
Paraffin Wax
D 1321
D 1465
D 1500
D 1832
D 1833
D 1834
D 2423
D 3 706
D 3708
D4419
D 5442
E 1
E 260
E 355
E 473
E 537
OTHER STANDARDS
No.
BS 4633 & 4634
BS 4695
DIN 53175
DIN 53181
Title
Method for the determination of crystallizing point. Method for the determination of melting point and/or melting
range
Method for d e t e r m i n a t i o n of melting
point of petroleum wax (cooling curve)
Binders for paints, varnishes and similar
coating materials; determination of the
solidification point (titer) of fatty acids
(method according to Dalican)
Binders for paints, varnishes and similar
coating materials; determination of the
melting interval of resins by the capillary method
ISO 1392
ISO 2207
ISO 3016
ISO 3841
JIS K 00-64
JIS K 00-65
NFT60-114
NFT20-051
REFERENCES
1] Hackett, W. J., Maintenance Chemical Specialties, Chemical Publishing Co., Inc., NY, 1972.
2] Warth, A. H., Chemistry and Technology of Waxes, Reinhold Publishing Corp., NY, 1956.
3] Bennet, H., Industrial Waxes, Vol. 1, Chemical Publishing Company, Inc., NY, 1963.
4] Puleo, S. L., "Beeswax," Cosmetics and Toiletries, Vol. 102, Allured Publishing CompEiny, Inc., Chicago, 1987.
5] Warth, A. H., Chemistry and Technology of Waxes, Reinhold Publishing Corp., NY, 1956.
6] Letcher, C. S., "Waxes," Kirk-Othmer: Encyclopedia of Chemical
Technology, Vol. 24, 3'''' ed., 1984, pp. 466-481.
7] Dry, M. E., "Sasol's Fischer-Tropsch Experience," Hydrocarbon
Processing, August, 1982, pp. 121-124.
8] Erchak, Jr., M., "Process for the Oxidation of High Molecular
Weight Aliphatic Waxes and Product 880kb, U. S. Patent
2,504,400, Washington DC, April 18, 1950.
9] Haggin, J., "Fischer-Tropsch: New Life for Old Technology,"
Chemical and Engineering News, October 1981, pp. 22-32.
0] Caraculacu, A., Vasile, C, Caraculacu, G., "Polyethylene Waxes,
Structure, and Thermal Characteristics," Acta Polymerica, Vol.
35, No. 2, 1984, pp. 130-134.
1] Brooks, B. T., Boord, C. E., Kurtz, S. S., and Schmerling, L., The
Chemistry of Petroleum Hydrocarbons, Vol. 1, Reinhold Publishing Corp., NY, 1954.
2] Gruse, W. A., Chemical Technology of Petroleum, 2'' ed., McGraw-Hill Company, NY, 1942.
3] Mazee, W. M., "Petroleum Waxes," Modem Petroleum Technology, 4"" ed., 1973, pp. 782-803.
4] Vasquez, D. and Mansoori, G. A., "Identification and Measurement of Petroleum Precipitates," Journal of Petroleum Science
and Engineering, Vol. 26, Nos. 1-4, 2000, pp. 49-56.
5] Misra. S., Baruah, S., and Singh, K., Paraffin Problems in Crude
Oil Production and Transportation: A Review, SPE Production
and Facilities, Society of Petroleum Engineers, Richardson, TX,
Feb. 1995, pp. 50-54.
6] Holder, G. A. and Winkler, J., "Wax Crystsillization from Distillate Fuels," Journal of the Institute of Petroleum, Vol. 51, No. 499,
1965, pp. 228-243.
7] Mansoori, G. A. and Canfield, F. B., "Variational Approach to
Melting," Journal of Chemical Physics, Vol. 51, No. 11, 1969, pp.
4967-4972.
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
Minimization and Phase Rule," Chemical Engineering Communication, Vol. 54, 1987, pp. 139-148.
Hartono, R., Mansoori, G. A., and Suwono, A., "Prediction of
Molar Volumes, Vapor Pressures and Supercritical Solubilities
of Alkanes by Equations of State," Chemical Engineering Communications, Vol. 173, 1999. pp. 23-42.
Riazi, M. R. and Mansoori, G. A. "Simple Equation of State Accurately Predicts Hydrocarbon Densities," Oil & Gas Journal,
1993, pp. 108-111.
Mohsen-Nia, M., Modarress, H., and Mansoori, G. A., "A Simple
Cubic Equation of State for Hydrocarbons and Other Compounds," SPE Paper No. 26667, Proceedings of the 1993 Annual
SPE Meeting, Society of Petroleum Engineers, Richardson, TX,
1993.
Nikitin E. D., Pavlov, P. A., and Bessanova, N. V., "Critical Constants of n-Alkanes with from 17 to 24 Carbon Atoms," Journal
of Chemical Thermodynamics, Vol. 26, 1994, p p . 177-182.
Frenkel, M., Gadalla, N. M., Hall, K. R., Hong, X., and Marsh, K.
N., TRC Thermodynamic
Tables-Hydrocarbon;
Non-Hydrocarbon, R. C. Wilhoit, Ed., Thermodynamic Research Center, The
Texas A & M University System, College Station, TX, 1997.
Twu, C. H., "An Internally Consistent Correlation for Predicting
the Critical Properties and Molecular Weights of Petroleum and
Coal-Tar Liquids," Fluid Phase Equlibrium, Vol. 16, 1984, pp.
137-150.
Edalat, M., Mansoori, G. A., and Bozar-Jomehri, R. B., "Vapor
Pressure of Hydrocarbons, Generalized Equation," Encyclopedia of Chemical Processing and Design - 61, Marcel Dekker, Inc.,
NY, 1997, pp. 362-365.
Letoffe, J. M., Claudy, P., Garcin, M., and Voile, J. L., "Evaluation of Crystallized Fractions of Crude Oils by Differential Scanning Calorimetry, Correlation With Gas Chromatography,"
Fuel, Vol. 74, No. 1, 1995, pp. 92-5.
Braun, R., "Limits in Differential Thermoanalysis of Wsixes,"
Fette Seifen Anstrichm, Vol. 82, No. 2, 1980, pp. 76-81.
Handbook on Antioxidants and Antiozonants, Goodyear Chemicals, Akron, OH, 1977.
Wink, W. A., Delevanti, C. H., and Van den Akker, J. A., Instrumentation Studies LXXVII, Study on Gloss I, A Goniophotometric Study of High Gloss Papers, TAPPI, Technical Association of
the Pulp and Paper Industry, Vol. 35, December 1953, p. 163A.
Tomsic, J., Dictionary of Materials and Testing, 2"^ ed., SAE International, Warrendale, PA, 2000, p. 205.
MNL37-EB/Jun. 2003
Lubricating Greases
Thomas M. Verdura, ^ Glen Brunette, ^ and Rajesh Shah~
' Retired, General Motors NAO Research and Development, Warren, MI.
^ CITGO Petroleum Corporation, Oklahoma City, OK.
^ Koehler Instrument Company Inc., Bohemia, NY.
COMPOSITION
Greases are composed of a lubricating fluid, a thickener, and
usually performance enhancing additives. A complete discussion of the many variations of grease formulations and manufacturing process would require far more space than allotted for this work. Extensive discussion on grease chemistry
and manufacturing process has been published [1-4]. Therefore, only a n overview of the most common grease types and
methods has been presented.
The lubricating fluids t h a t c a n b e thickened to form
greases vary widely in composition and properties and are a n
extremely important component of the grease. Lubricating
fluids can account for as m u c h as 95% of a grease. By iar, the
largest volume of greases in use today consists of those made
with petroleum oils thickened with soaps. Many types of
petroleum oils are used, including naphthenic, paraffinic, hydrocracked, and hydrogenated. The viscosity of the oil used
also varies. Oil blends with a viscosity between an ISO 100
and 220 are most common, however, for specialized greases,
the oil viscosity can be lighter or much heavier. In addition to
petroleum oils, other lubricating fluids such as vegetable oils,
silicones, synthetic hydrocarbons, and others can be used. Of
the synthetic fluids used in grease manufacturing the most
common type is poly(alpha)olefin (PAO). Because it is more
expensive, its usage is small compared t o petroleum oil.
Greases made with PAO as the lubricating fluid can provide
good performance over a wide-temperature range.
Many products have been used as thickeners for grease.
Soaps were the first thickeners used and still have the widest
557
Copyright'
2003 by A S I M International
www.astm.org
S Lithium soaps
0 Calcium soaps
H Aluminum soaps
H Sodium and other
soaps
g^o m Clay & other non-soaps
B Polyurea
FIG. 1Worldwide grease production by thickener type
(1999 NLGI Survey).
application (see Fig. 1). Some of the other thickeners that
have been employed include polymers, clays, silica gel, and
pigments.
Soaps are present in greases in the form of fibers. The
structure and size of these fibers, i.e., thickness and length,
depend on the metallic moiety and the conditions u n d e r
which they are formed. In general, soap fibers can vary from
about l-100^lm in length with about a 10 t o l length-to-diameter ratio. Large, coarse fibers do not absorb fluids as well
as fine, closely knit fibers. Thus, a higher percentage of thickener is required for coarse fiber soaps to make greases having the same consistency as those made with fine fiber soaps.
Non-soap thickeners are generally smaller, even colloidal,
and have either a spheroidal or plate like structure.
Soap thickeners are formed by neutralization reaction of
an acid and base to form a salt and water as a byproduct.
When the acid is a fatty acid, its salt is called a soap, and the
reaction is Ccilled saponification. If the acidic component has
a narrow range of moleculcir weight, as in fatty acids, a simple soap is made, e.g., lithium stearate. Reacting the metallic
base with two dissimilar acids of widely different molecular
weight will form a complex soap, e.g., calcium stearate acetate. Mixed-base greases consist of a mixture of two or more
different thickener systems, such as sodium-calcium or alum i n u m complex-clay.
The natural fatty materials used for soap formation can be
of animed or vegetable origin. Beef tallow and its derivatives
are the major source of animal fatty materials. The reaction
product with beef tallow derivatives Eind lithium hydroxide is
lithium stearate soap. Castor oil derivatives are the m a i n
source of vegetable oil fatty materials. Because the acids derived from castor oil have a hydroxyl group (OH) on the 12'''
carbon of the acid molecule, the reaction product with castor
oil derivatives and lithium hydroxide is lithium 12-hydroxystearate soap. Although the resulting soap is named according to the acid most prevalent, the natural occurring fatty
acids are actually mixtures of similar acids (in the form of a
glyceride) with slightly different molecular weights. The type
of fatty materials used affects the properties of the soap and
the grease. Greases made from castor oil derivatives Eire more
work stable and have higher dropping points than greases
made from beef tallow derivatives due to the hydrogen bonding at the hydroxyl group. The use of mixtures or blends of
fatty materials can obtain improved cost, oil separation,
worked stability, or other properties.
GENERAL CHARACTERISTICS
Describing the general characteristics of a grease based on
the thickener type is difficult because the base oil components and the performance additives used effect the characteristics of the grease as m u c h or more than the thickener
type. Therefore, assigning characteristics to a grease based
on thickener t5^e has limited value, however, some characteristics inherent to the thickener tjfpe are discussed below.
The reader should be aware that some of the weaknesses of a
thickener type can be improved and some of the strengths of
a thickener type can be degraded with the inclusion of performance additives.
Aluminum Soap Greases
Aluminum soap greases are usually made with preformed
soap unlike most other thickeners that Eire made in situ. Alum i n u m distearate is the m o s t c o m m o n conventional alum i n u m soap used to make grease. It is dissolved in hot oil in
a mixing grease kettle, and the hot mixture is poured into
pans to gel and cool. The cooling rate affects the final consistency. The final product is a smooth, transparent grease with
a tendency to thin when worked but with excellent water resistance. Aluminum soap greases are used as thread and way
lubricants. The poor work stability of aluminum-soap
greases is used to advantage in electrically conducting conveyers of electroplating systems; the grease thins down during use, allowing good electrical contact in the track rollers
while still providing good lubrication.
GREASES
559
560
HANDBOOK
Description
LA
LB
GA
GB
GC
D-217
0-566"
D-1264
D-1742
D-1743
D-2266
D-2596
D-3527
D-4170
D-4289
D-4290
D-4693
Penetration
Dropping Point
Water Washout
Oil Separation
Rust Protection
4 Ball Wear
4 Ball EP
High Temperature; Life
Fretting Wear
Elastomer Compatibility
Leakage
Low Temperature Torque
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
GREASES
561
ASTM Worked
Penetration at 25C
000
00
0
1
2
3
4
5
6
445-475
400-430
355-385
310-340
265-295
220-250
175-205
130-160
085-115
562
MANUAL
Roll
Stability
HANDBOOK
Flow Properties
The consistency of a grease is a critical p a r a m e t e r which
helps define the ability of a grease to perform under given operating conditions. Consistency, as measured by penetration,
is affected by temperature. But the penetration test is not
suitable for determining the minor, yet sometimes significant, changes in consistency as the grease approaches temperatures at which phase changes in the thickener occur.
Penetration is basically a flow measurement; in addition,
there are other flow-measurement tests that can be utilized to
evaluate this property at other conditions.
Flow Properties
at High
Temperatures
Viscosity
Grease is by nature a non-Newtonian material. It is characterized by the fact that flow is not initiated until stress is
applied. Increases in shear stress or pressure produce disproportionate increases in flow. The term apparent viscosity
is used to describe the observed viscosity of greases; it is
measured in Poises in D 1092, Test for AppEirent Viscosity of
Lubricating Greases. Since apparent viscosity varies with
both temperature and shear rate, the specific temperature
and shear rate must be reported along with the measured
viscosity.
In this test, a sample of grease is forced through a capillary
tube by a floating piston actuated by a hydraulic system using a two-speed gear p u m p . From the predetermined flow
rate cind the force developed in the system, the apparent viscosity is CcJculated using the classic Poiseuille equation. A series of eight capillaries and two p u m p speeds provide 16
shear rates for the determination of apparent viscosities. The
results are expressed in a log-log graph of apparent viscosity
as a function of shear rate at a constant temperature, or apparent viscosity at a constant shear rate as a function of temperature.
This apparatus also has been used to measure the pressure
drops of greases u n d e r steady-flow conditions at constant
temperature. Such information can be used to estimate the
pressure drop or required pipe diameters in distribution systems. Also, apparent viscosity data are useful for evaluating
the ease of handling or pumping at specified temperatures of
dispensing systems; it is often used to evaluate pumpability
at low temperatures. (The NLGI can provide a group of
charts that relate pressure drop, apparent viscosity, shear
rate, and pipe-flow data.) Apparent viscosity also is used to
provide an indication of the directional value of starting and
running torques of grease-lubricated mechanisms. Specifications may include limiting values of apparent viscosity for
greases to be used at low temperature.
Currently an ASTM Round Robin is being conducted to
rewrite the U.S. Steel Grease Mobility test method under the
aegis of ASTM. The Low Temperature grease mobility test
method utilizes only one capillary tube, maintained at various temperatures. The amount of grease collected in a specific time (gms/minute) is measured and used as an indication of the mobility of the grease. The test is easier to conduct
CHAPTER
t h a n ASTM D 1092, and uses axi apparatus similEir to the apparent viscosity test method.
Low-Temperature
Torque
(Ball
Bearings)
Torque
(Tapered Roller
Bearings)
20: LUBRICATING
GREASES
563
Point
HANDBOOK
ture Range, the sample is introduced into a preheated environment so that the heating rate is controlled more uniformly. In both tests, the difference in temperature between
the grease in the cup and the environment are taken into account when calculating the dropping point of the grease.
Some greases containing non-soap thickeners may not separate oil or melt.
Cooperative testing indicates that dropping points by
Methods D 566 and D 2265 generally agree up to about 260C
(500F). In cases where results differ, there is no known significance.
The dropping point is useful (1) in establishing bench
marks for quedity control, (2) as an aid in identifying the type
of thickener used in a grease, and (3) as an indication of the
maximum temperature to which a grease can be exposed
without complete liquefaction or excessive oil separation.
(For simple soap greases, the maximum usable temperature
is about 20-30C lower than the dropping point. For complex
soap grease, the maximum usable temperature is limited by
the base oil characteristics, and under dynamic conditions
seldom exceeds 175C. Some complex soap greases will tolerate intermittent operation at higher temperatures, and although they may liquefy somewhat, their structure will reform as the temperature is reduced.)
Greases normally do not perform satisfactorily at temperatures near or above the dropping point; other factors are involved. High-temperature performance can depend on the
application method and frequency, whether a softened
grease is retained at the point of application by proper seals,
and whether the high temperature is continuous or intermittent. High temperature stability and evaporation properties
of the grease also can affect performance.
Dropping point is most useful as a quality-control tool. Unless correlation has been established, dropping point has no
direct bearing on service performance. Performance at high
temperature would be better evaluated with one of the performance-type tests or by actual experience.
Evaporation Loss
Exposure of a grease to high temperatures can cause evaporation of some of the liquid lubricant, thus causing the remaining grease to become drier and stiffer or leading to other
undesirable changes in the grease structure. Greases containing low-viscosity oils for good low-temperature performance may be susceptible to evaporation losses at higher
temperatures. Evaporation also can cause problems where
vapors may be hazardous or combustible, or interfere with
operations. In most applications, even high-temperature applications, evaporation is not a serious problem because of
effective sealing. However, when it is necessary to evaluate
evaporation loss, two ASTM test methods are available.
Evaporation Loss of Greases and Oils
D 972, Test Method for Evaporation Loss of Lubricating
Greases and Oils, determines mass evaporative losses from
greases or oils at any temperature in the range of 100-150C
(210-300F). A weighed sample of lubricant is placed in an
evaporation cell in an oil bath at the desired test temperature.
Heated air at a specified flow rate is passed over the sample
surface for 22 h, after which, the loss in sample mass is determined.
GREASES
565
566
MANUAL
HANDBOOK
Bearings
Grease
Life
Timken
Method
Wheel Bearing
Pressure
Pressure
Four-Ball
Test
CHAPTER
that the load carrying capacity of the grease has been exceeded.
The significance of this test is that it is a rapid method that
can be used to differentiate a m o n g greases having low,
medium, or high levels of extreme pressure properties. It is
widely used for specification purposes, b u t the results may
not correlate with service performance. Because of their poor
lubricity, some lubricating greases containing a silicone or a
halogenated silicone fluid component are not suitable for
testing by this test method.
Wear Preventive
Characteristics
of
Grease
ASTM D 2266, Test Method for Wear Preventive Characteristics of Lubricating Grease (Four-Ball Method) is used to determine the wear-preventive characteristics of greases in sliding steel-on-steel applications. This test does not distinguish
between EP and non-EP greases.
As in D 2509, a four-ball configuration is used, but there
are few other similarities as the apparatus and operating conditions are conspicuously different. Wear prevention qualities are evaluated from the diameters of the wear scars that
occur on the stationary balls during the test.
The test is significant because it can be used to determine
the relative wear-preventing properties under the test conditions, so it is useful for grease development. D 2266 is widely
used in grease specifications, but its actual usefulness is suspect because of the following limitations. If test conditions
are changed, the relative ratings may change.
1. Wecir characteristics are not predicted for metal combinations other than AISI (American Iron and Steel Institute)
E52100 steel unless non-stcindard balls of other materials
are used.
2. No differentiation can be made between extreme pressure
and non-extreme pressure greases.
3. No correlation can be inferred between the results of the
test and field service unless such correlation has been established.
Fretting
Wear
20: LUBRICATING
GREASES
567
A related, but somewhat different, phenomenon often accompanies fretting wear. False brinelling is localized fretting
wear that occurs when the rolling elements of a bearing vibrate or oscillate with small amplitude while pressed against
the bearing race. The mechanism proceeds in stages: 1) asperities weld, are torn apart, and the wear debris which is
subsequently formed is oxidized; 2) due to the small-amplitude motion, the oxidized detritus cannot readily escape, and
being abrasive, the oxidized wear debris accelerates the wear.
As a result, wear depressions are formed in the bearing race.
These depressions are often polished and appear similar to
the Brinell depressions obtained with static overloading,
hence the term, false brinelling. D 4170 cannot distinguish
between false brinelling and fretting wear. If false brinelling
does occur, it is included in the determination of fretting
wear when bearing race mass losses are measured.
This test correlates with the fretting performance of
greases in wheel bearings of passenger cars shipped long distances. D 4170 also has been used to predict grease performance in automobile drivelines. It is used for specification
purposes and is one of the performance tests required by D
4950.
Oscillating
Motion
Wear (SRV)
Test
A high load, high frequency, low amplitude, high speed reversal test, using the SRV (Schwingung, Reibung, Verschleiss) a p p a r a t u s simulates high-speed vibrational or
start-stop motions that occur in many mechanisms. Two procedures, using a ball-on-disk configuration, have been developed: [ASTM D 5706 (EP Test) and ASTM D 5707 (Wear)]
one to measure wear-protection qualities and coefficient of
friction, and the other to measure the ability of a grease to
carry loads under extreme pressure. (This apparatus can use
other configurations to suit different applications.) Both procedures have been correlated with grease performance in automotive driveline mechanisms and are used in grease specifications for these applications. These procedures can be
used to evaluate lubricants and materials for other applications of similar motion.
Corrosion
Copper
Corrosion
HANDBOOK
bricating film. ASTM D 1264, Test for Water Washout Characteristics of Lubricating Greases, evaluates the resistance of
a lubricating grease in a bearing to washout by water.
This test method uses a standardized bearing, available
from ASTM. It is a 204K Conrad-type, ball bearing equipped
with shields but without seals. The bearing is packed with 4g
of test grease then rotated at 600 rpm while a jet of water, at
either 38C (100F) or 79C (175F), impinges on the bearing
housing for 1 h. The bearing is then dried, and the percent
grease loss by weight is determined.
This test method serves only as a relative measure of the resistance of a grease to water washout. It should not be considered the equivalent of a service evaluation unless such correlation has been established. Test results are affected by
grease texture and consistency. Test precision is poor, especially with soft greases. Although widely used, this test can
give misleading results. Even comparative results between
similar greases may not predict the relative performance of
the two greases in actual service.
Water Spray-Off
ASTM D 4049, Test Method for Resistance of Lubricating
Grease to Water Spray, is used to evaluate the ability of a
grease to adhere to a metal panel when subjected to direct
water spray. Test results correlate directly with operations involving direct water impingement, such as steel mill roll neck
bearing service and certain automotive body hardware applications.
In this test, a 0.79 mm (1/32 in.) film of test grease is uniformly coated onto a stainless steel panel; then water, at 38C
(100F), is sprayed directly on the panel for 5 min. The spray
is controlled by specified spray nozzle, pump, and plumbing.
After the spraying period, the panel is dried, weighed, and the
percentage of grease spray-off is determined.
Miscellaneous
Contamination
ASTM D 1404, Test Method for Estimation of Deleterious
Pcirticles in Lubricating Grease, defines a deleterious particle
as one which will scratch a polished plastic surface. The test
is applicable to all greases, even those containing fillers. In
fact, it can be used to test fillers, such as graphite, if they are
dispersed into a grease (or petrolatum) that is known to be
free of deleterious particles. It can be used also to test other
semi-solid or viscous-liquid substances.
With this method, the test material is placed between two
clean, highly polished acrylic plastic plates held rigidly and
parallel to each other in metal holders. The assembly is
pressed together by squeezing the grease into a thin layer between the plastic plates. Any solid particles in the grease
larger than the distance of separation of the plates and harder
than the plastic will become embedded in the opposing plastic surfaces. The apparatus is so constructed that one of the
plates can be rotated about 30 with respect to the other
while the whole assembly is under pressure. This will cause
the embedded particles to form characteristic arc-shaped
scratches in one or both plates.
The relative number of such solid particles is estimated by
counting the total number of arc-shaped scratches on the two
plates.
CHAPTER
The test has significcince because it is a rapid means for estimating the n u m b e r of deleterious particles in a lubricating
grease. However, a particle that is abrasive to acrylic plastic
m a y not be abrasive to steel or other bearing materials.
Therefore, the results of this test do not imply performance
in field service.
Elastomer
Compatibility
20: LUBRICATING
GREASES
569
Test
Chemical Analysis
D 128, Test Methods for Analysis of Lubricating Grease, is
the premier standard for grease analysis. This procedure
gives flow diagrams and details for the analysis of conventioneJ greases, i.e., those made of soap-thickened petroleum
oils. The constituents that can be determined are soap, unsaponifiable matter (petroleum oil, etc), water, free alkalinity, free fatty acid, fat, glycerin, a n d insolubles. A supplementary test method is provided for application to greases
that cannot be analyzed by conventional methods because of
the presence of nonpetroleum oils or nonsoap thickeners.
These test procedures can be used to identify and estimate
the a m o u n t of some of the constituents of lubricating
greases. The methods are applicable to many, but not all,
greases. Composition should not be considered as having a
direct bearing on service performance unless such correlation has been established.
D 128 references several useful, but nonstandard, methods
that can be used for grease analysis. Infrzired Spectroscopic
(IR) analysis is commonly used for research purposes, quality control, and specification purposes. But, a n IR method
has not been standardized because the technique frequently
must be adapted to the specific grease being analyzed.
Although D 128 is the general analytical method for
greases, t h e r e are other test m e t h o d s for specific constituents. These include the following:
D 95Test Method for Water in Petroleum Products and
Bituminous Materials by Distillation
D 129Test Method for Sulfur in Petroleum Products
(General B o m b Method)
D 808Test Method for Chlorine in New a n d Used
Petroleum Products (Bomb Method)
D 1317Test Method for Chlorine in New and Used Lubricants (Sodium Alcoholate Method)
D 3340^Test Method for Lithium and Sodium in Lubricating Greases by Flame Photometer.
570
HANDBOOK
DISCONTINUED STANDARDS
Severed standards have been discontinued since the 5th edition of the Manual on Significance of Tests for Petroleum
Products. Unless otherwise noted, the reason for discontinuance of the following test methods was lack of interest, i.e.,
the standcirds were no longer being used or supported by the
industry:
D 1262Test Method for Lead in New and Used Greases
(Discontinued 1991)
D 1402Test Method for Effect of Copper on Oxidation
Stability of Lubricating Greases by the Oxygen Bomb
Method (Discontinued 1985)
D 1741Test Method for Functional Life of Ball Bearing
Greases (Discontinued 1991)
D 3428Test Method for Torque Stability, Wear, and
Brine Sensitivity Evaluation of Ball Joint Greases (Discontinued 1990). (D 3428 was withdrawn because the ball joint
used as the test piece was no longer available and a suitable
substitute was not found.)
ISO STANDARDS
In 1987, ISO (International Standards Organization) published ISO 6743-9, which is an international classification
system for grease. About 75% of commercial greases can be
described by this standard. This standard classifies lubricating greases according to the operating conditions of the use
unlike most other ISO product standards, which are classified according to specific end-use. The nature of greases
allows a specific grease to be used in many applications. This
makes it impractical to classify greases by end-use, and a
properties description is a reasoned alternative. Consequently, users are advised to use ISO 6743-9 to define the requisite grease properties, but are they cautioned not to rely
solely on the standard for grease selection for a particular application. Rather, users are advised to consult with the grease
supplier, as well.
In this classification system, each grease will have one symbol only. This symbol should correspond to the most severe
conditions of temperature, water contamination, and load in
which the grease can be used. Grease products are designated
in a uniform manner, with each character having its own sig-
nificance. The line call-out code will have the following format:
ISO-L-XSiS2S3S4N
where:
ISO
L
X
Si
52
53
54
N
=
=
=
=
=
=
=
=
EP (load carrying
capacity)
ASTM STANDARDS*
No.
D 217
D 566
D 942
D 972
D 1092
Title
Test Methods for Cone Penetration of Lubricating
Grease
Test Method for Dropping Point of Lubricating
Grease
Test Method for Oxidation Stability of Lubricating
Greases by the Oxygen Bomb Method
Test Method for Evaporation Loss of Lubricating
Greases and Oils
Test Method for Apparent Viscosity of Lubricating
Greases
CHAPTER
D 1263
D 1264
D 1403
D 1404
D 1478
D 1742
D 1743
D 1831
D 2265
D 2266
D 2509
D 2595
D 2596
D 3232
D 3336
D 3337
D 3527
D 3704
D 4048
D 4049
D 4170
D 4289
D 4290
D 4425
D 4693
D 4950
D 5483
D 5706
D 5707
D 5969
D 6138
D 6184
D 6185
20: LUBRICATING
GREASES
OTHER STANDARDS^
Standard No.
ISO
DIN
2176
2137
51801
51804/1-2
132
50
51805
51802
51811
51803
220
112
5
51809/1-2
51813
37/137/139
134
51807/2
51807/1
51808
51817
215
2160
51814
51815
IP
FTM791b
COST
Characteristic/Property
102
132
1421
311
6793
5346
135
40001.2
5309.4
5757
NF-T 60
M 07-037
1461
6474
133/112
142
121
M 07-38
571
3005.3
6370
3453
321/2
5734
7142
1631
Absorption Spectroscopy
(continues)
DIN
IP
FTM 791 b
NF-T 60
COST
Characteristic/Property
9270
199
51831
3720/22
51832
59
183
74
3733
9566
1044
2077
113
51816/1
51816/2
139
51350-4/5
6503.2
239
326
331.2/333.1
51806
168
266
(51821/2)
(51821/1)
186
R868
1817
53505
53521
3104
3016
2592
2977
51562
51597
51376
51775/51787
51820 E
3603.3
71
15
36
2
Pumpability Properties
SheU-DeLimon Rheometer
Decompression Characteristics
Apparent Viscosity
Roll Stability
Extreme Pressure Properties
Shell-Four-Ball Test
Timken Test
Mechanical Dynamic Testing
SKF-R2F
Roller Bearing Performance
Churning
FAG-FE 8 (EP Greases)
FAG-FE 9
Wheel Bearing Leakage
Low Temperature Torque
Elastomer Compatibility
Hardness Change (Shore A)
Volume Change
Tests on Base Oil
Viscosity
Pour Point
Flash Point
Aniline Point
Infrared-Analysis
REFERENCES
[6]
[1] Polishuk, A. T., A Brief History of Lubricating Grease, Llewellyn
& McKane, Inc., Wilkes-Barre, PA, 1998.
[2] Boner, C. J., Manufacture and Application of Lubricating Grease,
Reinhold PubUshing Corp., NY, 1954.
[3] Boner, C. J., Modem Lubricating Greases, Scientific Publications
(G.B.) Ltd, Broseley, Shropshire, England, 1976.
[4] Lubricating Grease Guide, 4 * ed.. National Lubricating Grease
Institute, Kansas City, MO, 1996.
[5] Ward, C. E., "Polyurea Greases," National Lubricating Grease
[8]
[9]
[10]
MNL37-EB/Jun. 2003
DISCUSSION
Heat Transfer Coefficient
The Seider and Tate equation shows that higher heat transfer is favored by: increasing fluid density, increasing heat capacity, increasing conductivity, increasing fluid velocity and
turbulence, and decreasing fluid viscosity [2]. Rates of heat
transfer are also affected by system heat sources and heat
sinks, geometry, and temperature gradients [2].
Heat transfer properties of two fluids can be compared by
assuming they are flowing through the same pipe. Therefore,
2003 by A S I M International
(/x)-o-47
www.astm.org
574
MANUAL
HANDBOOK
Type of
Fluid
Fluid
Caloria
HT43
Dowtherm
A
Dowtherm
G
Therminol
66
Dowtherm
J
Dowtherm
Q
Mobiltherm
603
Paratherm
NF
Syltherm
800
Syltherm
XLT
Comparison
Inside Film Coefficients
(BTU/Hr) (ft^) (F) 2"
Sched 40 Pipe @ 87Sec
400^
500F
eoo-F
Max"
Bulk
Temp
F
Max"
Film
Temp
F
Flash
Point
(coc)
F
Fire
Point
(coc)
F
Auto
Ignition
Temp
F
Coefficient
of Thermal
Expansion
%rF
Pour
Point
"F
Vapor
Pressure
@600F
psia
Vise
100C
cSt
236
267
302
600
660
406
453
632
0.0483
10
15
5.0
492
547
590
750
800
236
245
1139
0.0642
53
45.34
0.13
350
404
449
685
750
266
275
1083
0.0525
-40
22
0.29
332
397
449
650
705
363
414
705
0.046
-25
449
428
384
600
650
136
140
788
0.105
-100
Diphenyl
417
451
465
625
675
249
255
773
0.0569
-30
Paraffinic
mineral oil
Napthenic
hydrocarbon
Polydimethylsiloxane
Polydimethylsiloxane
304
354
399
550
625
380
375
670
0.0531
25
317
388
464
600
650
345
385
690
0.0304
-45
239
265
279
750
800
320
380
725
0.0813
-76
87
0.46
329
298
242
500
550
116
N/A
662
0.1143
-168
163.4
0.09
Paraffinic
hydrocarbon
Diphenyl oxide/
biphenyl blend
Di- a n d triaryl
ether
Modified
terphenyl
Diethyl benzene
3.8
7.47
0.07
174
37.74
0.14
2.9
4.0
4.72
3.686
Pumping Limit
("F)"
Temperature for 10 cP
Viscosity'' (F)
Corrosion Inhibitor
Required"
Normal Boiling
Point (F)
5(FP)
6(FP)
141
-31
17
< 6 (FP)
51
20
Yes
Yes
Yes
Yes
212
212
223
224
<-120
<-120
- 1 0 0 (FP)
32 (FP)
-52
-85
-100
32
No
No
No
Yes
378
347
358
212
"Pumping (fluidity) limit is defined as the point where coolant is at the freezing point (FP) or 2000 cP viscosity [3].
^Possible limit to efficient heat exchange, below which turbulent flow is not effectively obtained in economic heat exchangers.
'When in contact with metal equipment.
''Data shown tor typical commercial grades in coolant service.
velocity and tube diameter are equal and the ratio of the two
heat transfer coefficients is dependent only on the ratio of the
fluid densities, specific heat capacities, thermal conductivities, and absolute viscosities raised to the appropriate power
[1].
From this equation and the above expressions for heat
transfer coefficient, it is evident that h is a good summary parameter that incorporates all of the important fluid properties as they relate to their effect on heat transfer.
Pressure Drop
An i m p o r t a n t p a r a m e t e r used by process designers in the
analysis of heat transfer systems is pressure drop (/IP). The
pressure drop of a system is related to the energy required to
move the heat transfer fluid through a stem at a given pressure and it is related to the physical properties of the fluid.
(62.3292)(p)(V)^
0.0001906 +
0.01171
(927.4777)(fi,)(p)(V)\o-381
where:
di = I.D. of pipe in inches
p = Fluid density in lb/gal
K = Thermal conductivity in BTU/hr-ft2 F/ft
fi = Viscosity in cPs
V = Fluid velocity in feet per second
Cp = Specific heat in BTU/lb F
NOTE: p, K, u, and Cp at average fluid temperature
(2)
CHAPTER
Many manufacturers supply computer programs that are
m o r e easily used to perform such calculations. These
programs are available upon request, or many fluid and hardware suppliers make such softweire available on the Internet.
Selected examples of such p r o g r a m s that are currently
available at a web site are provided in Table 4.
M i n e r a l Oil F l u i d C o m p o s i t i o n
Crude petroleum oil is a complex mixture of petroleum
hydrocarbons as well as nitrogen, oxygen, and s u l f u r containing compounds, which are separated into fractions
by refining. Solid components include petroleum coke, asphalt bitumen, and inorganics. Liquids of increasing viscosity vary from gasoline, kerosene (paraffin oil), diesel oil, engine crankcase oil, light a n d heavy m a c h i n e oil, a n d
cylinder oil. Also included are methane, ethane, propane
and butane, the major components of natural gas, which
are gases at room temperature [6]. Aromatic aspheilt com-
21: MINERAL
FLUIDS
575
pounds are classified as resins, asphaltines, or carbenes, depending on their solubility [6]:
Resinspentane or heptane soluble
Asphaltenespentane or heptane soluble
Carbenes^benzene insoluble, carbon disulfide soluble
Crude oils eire classified as paraffinic, naphthenic, intermediate (mixed), or asphaltic as shown in Table 5. Paraffinic
fractions are saturated linear or b r a n c h e d alkanes. Naphthenic fractions contain cyclic alkane fractions. Also included are aromatic (pol5ainsaturated cyclic) chemical structures derived from benzene. Aromatic components exhibit a
greater tendency to form sludge and varnish than paraffinic
or naphthenic derivatives [7]. Generic examples of typiceil
structures are illustrated in Fig. 1 [8,9]
In addition to paraffinic, n a p h t h e n i c , a n d aromatic
derivatives, petroleum oils also contain heterocyclic (cyclic
derivatives of nitrogen, sulfur and oxygen), and other polar
c o m p o u n d s such as carboxylic acids, usually saturated
aliphatic or cycloaliphatic (naphthenic) acids, and aldehy-
Code
Letter
General
Application
Particular
Application"
Heat
Transfer
Maximum
Measured
Temperature
<250C
Open circuit
Maximum
Measured
Temperature
<300C
Product Type
and Performance
Requirements
Symbol
ISO-L
Typical
Application
Refined mineral
oil or synthetic
fluid mechanical
or with stability
To oxidation
QA
Closed circuit
with/or
without
forced
circulation
Refined mineral
oil or synthetic
fluid with
thermal stability
OB
Maximum
Measured
Temperature
>300 C and
<320C
Closed circuit
with forced
circulation
QC
Maximum
Measured
Temperature
<320C
Maximum
Measured
Temperature
>-30Cand
<200C
Closed circuit
with forced
circulation
Synthetic fluid
with particularly
high thermal
stability
Refined mineral oil
or synthetic fluid
with low viscosity
at low temperatures
and with thermal
stability
QD
QE
Cooling
circuit
Remarks
"Temperatures indicated in the column are of the bulk of the oil, measured in the discharge line from the heater. They are not the temperatures of the film of
oil contact with the heater, which may reach higher values.
TABLE 4Sources and web site addresses for computer programs to calculate heat transfer coefficients.
Company
Program Name
FLUIDFILE
PARACALC
http://www.dow.com/heattrans/index.html
http;//www.paratherm.com
http://www.therminol.com
http://www.processassociates.com/process/tools.htm
http://www.tak2000.com
576
Crude Type
Solvent Neutral
Base Oil
Pciraffinic base
Naphthenic base
Mixed base
Asphaltic base
Yes
No
No
No
HANDBOOK
No
Yes
No
No
Yes
No
Yes
No
S&N
Content"
Asphalt
Low
Low
Low
High
No
No
Yes
Yes
API
Gravity''
>40
<33
33-40
NmmaiclatnTg
Viscosity
Index
n-Panffins
Very high
iso-Paraffins
m^
Low
Moderate
Low
Low
Low
Naphthenes
Anunatics
-^
T^Y^
^ I
Pour
Point
High
Dibenzothiophene
1,7-Phenandirone
Furan
Pynole
Thitqihene
FIG. 2Examples of heterocyclic
derivatives typically present in a
petroleum oil.
577
the viscosity-gravity constant (VGC) and refractivity to determine oil composition in terms of aromatic carbon (%CA),
naphthenic carbon (%CN), and paraffinic carbon (%CP). The
VGC parameter is derived from kinematic viscosity and density and is dependent on the saturated/aromatic hydrocarbon
ratio. The equation to calculate VGC from kinematic
viscosity at 100C (V') and density at 15C (G) is:
VGC-
n-Alltane
Napthene
Aromatic
Polar Compounds
Viscosity Index
Pour point (high/low)
Oxidative Stability
Very high
High
Good
High
Low
Good
iso-Alkane
Low
Low
Average
Low
Low
Average/Poor
Response to
Antioxidants
Volatillity
(high = poor)
(low = good)
Good
Good
Good
Some poor
Low
Low
S is antioxidant;
N and 0 are pro-oxidant
Poor
Good
Good/Average
Average
Poor
Poor
Paraffinic Carbon
Naphthenic Carbon
Aromatic Carbon
Density (kg/L)
Paraffinic
Naphthenic
Mixed
Aromatic
65-70
50-60
48-57
21-35
25-30
30-40
24-33
20-30
3-8
8-13
17-22
40-50
0.800-0.812
0.834-0.844
0.850-0.872
0.943-1.005
ASTM No.
D 1319
D2007
D2140
D2425
D2501
D2502
D2549
D2786
D3238
D3239
D3524
D3525
D4291
D4808
D5186
D5291
D5292
TABLE 8--ASTM test methods for determining petroleum oil composition used for heat transfer fluid formulation.
Standard Test Method for
Separation Type
Chromatography
Chromatography
Correlation
Spectrometry
Correlation
Correlation
Chromatography
Spectrometry
Chromatography
Spectrometry
Chromatography
Chromatography
Chromatography
Spectrometry
Chromatography
Spectrometry
Spectrometry
578
MANUAL
HANDBOOK
1.047
'
^^ - -^
mal/oxidative stability properties. This test method is not directly applicable to petroleum oils of greater than 0.1 mass %
pentane insolubles. The hydrocarbon types and structural
groups measured by this method include:
Asphaltenes, or n-pentane insolubles that are defined as insoluble matter that precipitates from a solution of oil in npentane under specified conditions.
Polar compounds that are material retained ion adsorbant
clay after percolation of the same in n-pentane eluent under specified conditions.
Polar aromatics, which is a synonym for polar compounds.
Aromatics that are materials that, o n percolation, pass
through a column of adsorbant clay in a pentane eluent but
adsorb on silica gel u n d e r the conditions specified.
Saturates which are materials that, on percolation in an npentane eluent, is not adsorbed on either clay or silica gel
under the conditions specified.
In addition to ASTM D 5186, which utilizes supercriticcJ
fluid chromatography (SFC), a n u m b e r of additional methods have been reported for use with petroleum oils including
thin layer chromatography (TLC) and high pressure liquid
chromatography (HPLC) [21,22-25].
There are various spectrometric methods for petroleum
compositional analysis, which are summarized in Table 8.
Non-ASTM methods for the use of infra-red (IR) spectroscopy for quantitative analysis of hydrocarbon t5^es have
been reported. Fourier trzmsform (FT) IR methods have also
been reported for the analysis of degradation by-products
present in used oils [21,26]. Nuclear magnetic resonance
(NMR) spectroscopy methods have been developed including
ASTM D 4808 and D 5292.
There are three spectrometric test methods for petroleum
analysis based on mass spectroscopy (MS): ASTM D 2549, D
2786, and D 3239. ASTM D 2786 yields information on the
relative amounts of paraffins, 1-through 6-ring naphthenes
and alkyl naphthenes. ASTM D 3239 determines eighteen
aromatic t3^es and three aromatic thiophene structures [21].
Both methods require the use of Test Method D 2549 for
prior separation of the paraffinic a n d aromatic fractions.
ASTM D 2425 may be applicable for petroleum oils in the
lower molecular weight range [21].
M i n e r a l Oil F l u i d P r o p e r t i e s
\
^ ~>-N
0.B2
It has been shown that heat transfer fluid performEuice is dependent on the physical properties of the fluid including:
thermal conductivity, density, specific heat capacity, and viscosity. It has also been shown that the physical and chemical
properties of a mineral oil are dependent on its composition
a n d degree of refining. However, Table 1 showed that the
physiced properties of heat transfer fluids of a given type, including mineral oil-derived fluids, varied with respect to each
other. This is illustrated in Table 9 where the physical properties of two commercially available mineral oil heat transfer
fluids are compared. One fluid is a hydrotreated pEiraffinic
base and the other is a napthenic base. It is essential that the
engineer obtain the actual data he requires for the fluid being
considered. This data is available from the fluid supplier.
0^
^^
.o\
IM
>
N
e
j
i-
'^
' ^
^
,\
^
y
"^
y
><
y
%
>
fP ^
\
\A
"'>,
ec
sMN
/'
iO<]
\
'
* rf)N
jPN
,^
1.033
0.64
/ >
, / -" /
/ ' ^'
/'
0.66
0.6B
0.70
OTZ
0.74
0cflsityaf2OC
0.76
07B
0.60
Density (lb/gallon)
300F
400F
500F
Specific Heat (BTU/lb-F)
300F
400F
500F
Thermal Conductivity (BTU/hr-ft^-F
300F
400F
500F
Vapor Pressure, psia @
300F
400''F
500F
Coefficient of Thermal Expansion
Viscosity
TABLE 10Summaiy of ASTM D 5372 recommended test
procedures for mineral oil heat transfer fluids.
Recommended Test
Mineral Oil Fluid Properties
Flash Point, Closed Cup
Pour Point
Viscosity
Specific Viscosity
Water Content
Safety
Autoignition Temperature
Flash Point, Open Cup
Flash Point, Closed Cup
Effect on Equipment
Rubber and Elastomeric Seals
Corrosion
Efficiency
Thermal Conductivity
Specific Heat
Service Life
Thermal Stability Laboratory Tests"
Precipitation Number
Insolubles
Flash Point, Open Cup
Flash Point, Closed Cup
Carbon Residue
"
"
Viscosity
Distillation
"
"
Neutralization Number
Water Content
D91
D893
D92
D93
D189
D524
D4530
D445
D86
D 1160
D2887
D664
D95
"At present no suitable method has been approved for heat transfer fluids.
Test method D 2160 is of limited value due to limitation in testing small noncirculatory samples in glass containers.
Fluid 2
Paraffinic
1.96
1.16
0.74
2.79
1.52
0.98
6.82
6.64
6.45
6.51
6.22
5.92
0.56
0.61
0.66
0.56
0.61
0.66
0.072
0.069
0.067
0.071
0.069
0.066
0.0003
0.1470
0.9670
0.000304/F
579
0.00039
0.00970
0.13500
0.000592/F
(ASTM D 445)
Pumpability
Pumpability refers to the ease of pumping a fluid in a heat
transfer system. According to ASTM D 5372, if the fluid viscosity is greater than 200 cS, it is difficult to p u m p . If a heat
transfer fluid is subjected to temperatures below its minim u m p u m p i n g t e m p e r a t u r e w h e n not in use, the system
should be heat traced to w a r m the fluid start-up. The p u m p
and system design will determine the viscosity limit required
for pumping, and therefore the minimum pumping temperature. The construction of a viscosity/temperature curve using
measured viscosities in the temperature range of interest can
be used to estimate m i n i m u m pumping temperature.
It should be noted that the "pumpability" concept of ASTM
D 5372 is not the same concept as "pumping limit" used by
Green and Morris [3] and cited in Table 2. The Green and
Morris concept refers to those conditions defined by freezing
point of the fluid or a viscosity of 2000 cP as conditions where
a fluid is n o longer p u m p a b l e . In the ASTM approach,
"pumpability" refers to that fluid viscosity (200 cS) above
which the fluid would be difficult to pumpwhich is a consensus value.
Thermal
Stability
580
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
temperatures as low as 250C while rapid changes in composition (thermal cracking or pjrolysis) begin around 350C.
These changes include evolution of solid carbon particles
(coke) and lower boiling point components (light ends). If
there are substantial a m o u n t s of asphaltenes and polar
residues in the fluid, the coke may adhere to the heater surfaces, causing fouling, which in t u r n reduces heat transfer
rates. The lower boiling point components will cause the
overall system pressure to increase and m a y result in vaporous cavitation at the p u m p section. These components
will also tend to depress the Flash Point of the fluid. Thermal
cracking is often accompanied by color change [19] however,
color change is more c o m m o n when oxidation is present.
While higher viscosity oils are generally more susceptible to
cracking than lower viscosity, the main cause is due to overheating. Overheating typically results from flame impingement and/or low velocity through the tubes of fired heaters.
In forced circulation electric immersion heating systems, satisfactory fluid life has been obtained with heat flux of 15-22
watts per square in., and in free convection systems (no circulating pumps), 5-12 watts per square in.
Thermal
Under
Test
Method
Although it is true that there are few tests that directly assess
the thermal stability of a heat transfer fluid, there is one test
currently being balloted within ASTM, Standard Test Method
for Thermal Stability of Organic Heat Transfer Fluids [ 1 ]. This
test is conducted by adding the heat transfer fluid to be analyzed into a test cell that is purged with nitrogen and tightly
sealed to remove and preclude the introduction of oxygen and
water from the atmosphere. The fluid is then heated in the test
cell for a prescribed time and temperature. The boiling range
of the fluid after themicJ stressing is then determined by gas
chromatography (using Test Method D 2887) and compared
to the unused fluid. This portion of the thermally stressed
fluid that has a boiling point outside of the boiling range of
new, unused fluid is defined as "degradation."
Guffey has introduced the concept of "overall degradation
rate" [1], where components exhibiting boiling points above
or below the original boiling point range are assumed to be
degradation products. To determine the overall degradation
rate, it is assumed that 99% of the fluid volume is equally distributed at the heater-outlet, heater-inlet, and the heater-inlet
temperature minus a selected amount such as 50F (which
accounts for the fluid in the system expansion tank). The remaining 1% is assumed to be at the fluid-film temperature.
Degradation rates are then taken from the test at various temperatures. This data is then used to calculate the "overall
degradation rate" [1].
Oxidative
increase in the amount of air contact (foaming air entrainment, fluid turbulence) will also affect the rate of oxidation.
Oxidative stability is a function of the base stock selected.
For example, paraffinic oils exhibit better oxidative stability
than naphthenic oils, but they exhibit poorer "solvency"
poorer ability to dissolve byproducts [17]. The presence of
alkylaromatic derivatives a n d some polar components further increases the susceptibility of a petroleum oil to oxidation, and other derivatives such as some sulfur-containing
compounds may exhibit a stabilizing effect [18].
Carbon Residue
4530)
"Carbon residue" is defined as the residue formed by evaporation and thermal degradation of a carbon containing material, which provides an indication of the fluid's tendency to
form carbonaceous deposits.
One test that is used to determine carbonaceous residues is
Test Method D 189 the Conradson Carbon Residue. In this
test, a sample is added to a crucible and subjected to destructive distillation. The residue formed undergoes cracking
and coking during the fixed period of severe heating. At the
conclusion of the test, the crucible is cooled and weighed.
The Conradson Carbon Residue is the % of residue remaining at the conclusion of the test. This test provides a rough
approximation of the tendency of the heat transfer fluid to
form deposits when heated and the formation of volatile byproducts is possible.
Another test that is used to determine the tendency for a
heat transfer fluid to form carbonaceous residues is Test
Method D 524, the Ramsbottom Carbon Residue test. In this
test, the sample is weighed into a special glass bulb and
placed in a metal furnace where it is heated quickly to 550C.
All volatile material is evaporated out of the bulb, with or
without decomposition, while the remaining residue undergoes cracking and coking reactions. After the test, the bulb is
cooled and weighed. The residue remaining is reported as %
of original sample and is called the R a m s b o t t o m Carbon
Residue.
Test Method D 4530 is a "Micro Method" for determination
of carbon residue. In this test, a weighed sample of the fluid
is heated in a 2 mL glass vial at 500C under an inert atmosphere (nitrogen) in a controlled manner for a specific time.
The sample undergoes coking reactions and the volatiles that
are formed are swept away by the nitrogen. The carbonaceous residue formed is reported as % of original sample as
"carbon residue (micro)." This test method is reported to be
equivalent to the Conradson Carbon Residue (ASTM D 189).
Specific
Gravity
(ASTM D
1298)
Stability
Oxidation occurs when the hot fluid comes into contact with
air (oxygen). Oxidation rates double every 10C (18F) increase temperature. The principal oxidation byproducts are
organic acids which can undergo further reaction to form extremely high molecular weight components that are soluble in
the fluid and increase the viscosity of the fluid [15]. Above
200C these components will precipitate out on hot surfaces
and become insoluble. Insoluble byproducts will lead to fouling of heater surfaces, filter plugging, and sticking valves. Any
Metal
Content
CHAPTER
These free radical processes, a n d others not shown, are
strongly affected by temperature. This is illustrated in Table
11 where it is shown that if both water and the metal are present, the oil degradation rate was 10-fold (iron) to 30 fold
(copper) that of the uncontaminated oil [16]. There are numerous test procedures that are discussed in detail in Chapter 26, Elemental Analysis, cind therefore will not be discussed
further here.
Thermal PropertiesThermal
Conductivity
2717) and Specific Heat (ASTM D 2766)
(ASTM
(ASTM E
659)
It is important to note that while heat transfer fluids are routinely used above their flash a n d fire points, they should
never b e used above their autoignition t e m p e r a t u r e . Autoignition is the temperature at which the fluid will ignite
spontaneously in contact with air. It is recommended that the
fluid supplier be consulted for standard recommended safe
practices. The autoignition temperature of a heat transfer
fluid is determined according to ASTM D 659.
Effect on Rubber
or Elastomeric
21: MINERAL
OIL HEAT
TRANSFER
FLUIDS
581
System
Inspection
Water
Hours
None
None
Iron
Iron
Copper
Copper
No
Yes
No
Yes
No
Yes
3500
3500
3500
400
3000
100
0.17
0.9
0.65
8.1
0.89
11.2
Unusual
Odors
Appearance
With the heater off, start the circulating pump(s) and wait ten
or fifteen minutes. Open a low-point valve, edlowing a small
amount of fluid to drain into a clear glass container. Put the
container on a bench and let it sit. Color may range from light
yellow to dark brown or black. Darker colors do not necessarily indicate that the fluid has become unusable. A hazy
fluid suggests water contamination or oxidation. If there are
particles on the b o t t o m (or floating in the liquid), fluid
"coking" may be indicated or mill scale or other hard contaminants may be present. Either condition should be investigated before problems escalate.
Fluid Sampling
Recommended locations from which to remove a fluid sample include a low-point drain near the p u m p or heater or the
blow-down valve mounted on the Y-strainer. The Y-strainer
is usually located in the return line just upstream of the p u m p
suction. Fluid samples should b e taken when the p u m p has
been running so that the sample is representative of the fluid
in the system. Ideally, the fluid should be removed from the
system between 180 and 280F and put directly into the sample container. If the fluid sampled is too hot, it will not only
smoke, but the acid n u m b e r may indicate artificially high
582
HANDBOOK
. . fion
o
(1)
550
High Boilers-
I-*
500
450
a)
CL
10)-
c 400
o
m
4-*
350
Laboratory analysis of the fluid should be performed at set intervals to ensure that abnormal degradation is not occurring.
Abnormal degradation can result from contamination that
catalyzes the breakdown, oxidation, or overheating. The condition of the fluid can be accurately established by three basic
tests, which determine the amount of thermal cracking and/or
oxidation that has occurred. Additional tests may be required
to identify specific contaminants such as water and solids.
Acid Number (ASTM D 664 and D 974)
Acid number (AN) measures the acidity produced when the
fluid is oxidized. Unless the expansion tank is maintained under inert gas blanket, some increases in AN are unavoidable
over time. The higher the operating temperature, the more
critical the AN becomes since the ensuing fluid degradation
is temperature dependant. In general an increase of 0.5
should be viewed as a warning sign, with immediate fluid replacement at an increase of 1.0. The increase in AN with increasing time is illustrated in Fig. 4 [19].
Test Method D 664 is conducted by dissolving a sample of
the HTF to be analyzed into a solution of toluene and isopropanol containing a small amount of water and titrated potentiometrically with alcoholic potassium hydroxide and a
saturated calomel reference electrode. The meter readings
are plotted manually or automatically against the respective
volumes of KOH titrant and endpoints are taken only at welldefined inflections of the resulting curve. This titration may
be performed colorimetrically according to Test Method D
974. Alternatively, infrared analyses may be used, which provides a more reliable method of detecting oxidation.
1.4
#n
5> 1.2
X
Oxidized Fluid
1.0
o>
e
3 0.6
D
B 0.4 -
|0 0.2 0
...U ....
1. n
o 300
a>
_ Low
Boilers
<
Fresh Fluid
JO 250
3
CO 200
10 20 30 40 50 60 70
80
_i_
90 100
ASTM Procedure
Fresh Fluid
D92
450
D445
D664
25.0
0.05
0.0
0.0
D2887
Used Fluid
392
94.5
2.12
7.6
700
4.7
N
(ppm)
S
(ppm)
Wt. %
aromatics
ASTM Color
After Heating
in Air
A
B
C
27
1
<0.2
6200
26"
4
1
>8
5.5
2.5
92
1
583
Safety
Mineral oil heat transfer fluids are hydrocarbons, and therefore are combustible with the associated safety risks. However, mineral oil based heat transfer systems have been in
safe operation for over 100 years.
System Leakage
Unlike hydraulic systems, mineral oil heat transfer systems
are not generally pressurized. The leaks that do occur are
found mostly in threaded fittings, joints, valves, and pumps
the fluid will slowly weep rather than gush or spray. Leaking
heat transfer fluid will tjrpically smoke rather than bumeven
at temperatures in excess of their flash and fire points. However, hot mineral oil fluid vapors can also be highly flammable
if allowed to accumulate in a poorly ventilated area.
Insulation Fires
All organic heat transfer fluids are capable of spontaneous
combustion when leaks occur into porous insulation (such as
fiberglass or calcium silicate). The exact mechanism of the
autoignition has not been established. One possibility is that
partial oxidative decomposition occurs in the insulation
(similar to the way heat is generated in a pile of oily rags or
wood chips). The heat produced adds to the system heat and
ultimately exceeds the autoignition temperature of the fluid.
An alternate mechanism is that the autoignition temperature
of the fluid decreases as it degrades in the insulation. In either case, if air enters the insulation at this point and contacts the degraded fluid, spontaneous combustion will occur.
Automatic Shutdown Controls
Although rare, fires have occurred in heaters when fluid circulation is interrupted (due to pump failure or blockage) and
the high temperature shutdown fails. In this situation, the
fluid temperature rapidly increases above the autoignition
temperature while the increasing thermal stress eventually
causes either the heater tube or housing to fail. All systems
should incorporate automatic shutdown controls for high
fluid outlet temperature and loss or reduction of fluid flow
through heater.
Design and Construction
Like any other industrial system, the proper design and installation of heat transfer fluid systems is critical to their
smooth functioning and extended operating life. In this section, an overview of recommended practices to minimize the
potential of system fires will be provided.
Component Selection
In designing and constructing a thermal oil system, attention
must be paid to the selection of appropriate components. If
care is not taken, poor operation, system failure, and fires
can result. In this section, an overview of various system design considerations for mineral oil heat transfer fluids will be
provided.
Piping
Schedule 40 seamless carbon steel piping is recommended.
Schedule 80 piping is recommended for threaded installations up to 1 in. Threaded fittings are not recommended for
584
MANUAL
HANDBOOK
Fittings
Gauges
Y-strainers
One-quarter to Ys in. opening is recommended. A 60 mesh element should be instcJled for start-up only.
Flow
Protection
Cleanliness
Care must be taken to assure that the system is clean and dry.
Both the "hard" and "soft" contamination must be removed
as the system is being assembled. Hard contamination such
as mill scale, weld spatter/slag, and dirt can cause premature
failure of p u m p and vzJve seals. A startup strainer should be
monitored continuously during initial system circulation.
Soft contamination such as quench oil, welding flux, and
protective lacquer coatings can potentially dissolve in the
fluid. Although this would be expected to exhibit only a minimal effect in most cases, such contaminants may be carried
through the heater where they may degrade at much lower
temperatures than the fluid itself, and can cause fouling of
heater surfaces.
Component
Orientation
Tightness
The system should be chcirged with an inert gas once construction is completed. Not only will corrosion be prevented,
but the system can be pressure-tested using simple soap-bubble detection methods at potential leak points.
ASTM STANDARDS
Expansion
No.
D 91
Joints
D 92
D 93
Title
Test Method for Precipitation Number of Lubricating Oils
Test Method for Flash and Fire Points by Cleveland
Open Cup
Test Method for Flash Point by Pensky-Martens
Closed Cup Tester
CHAPTER
D 97
D 130
D 189
D 445
D 471
D 524
D 611
D 664
D 877
D 893
D 1160
D 1169
D 1298
D 1319
D 1500
D 1744
D 1747
D 2007
D 2140
D 2425
D 2501
D 2502
D 2549
D 2717
D 2766
D 2786
D 2887
D 3238
D 3239
21: MINERAL
D 3524
D 3525
D 4291
D 4530
D 4808
D 5186
D 5291
D 5292
D 5372
D 6546
D 6743
E 659
G4
FLUIDS
585
OTHER STANDARDS
ISO 6743-12: 1989 (E) International Standard, "Lubricants;
Industrial Oils and Related Products (Class L)"-Classiication-Part 12: Family Q (Heat Transfer Fluids)
REFERENCES
[1] Guffey, G. E., "Sizing Up Heat Transfer Fluids and Heaters,"
Chemical Engineenng, Vol. 104, No. 10, 1997, pp. 126-131.
[2] Green, R. L., Larsen, A. H., and Pauls, A. C, "The Heat Transfer
Fluid Spectrum," Chemical Engineering, Vol. 96, No. 2, 1989, pp.
90-98.
[3] Green, R. L. and Morris, R. C, "Heat Transfer Fluids-Too Easy
to Overlook," Chemical Engineering, Vol. 102, No. 4, 1995, pp.
88-92.
[4] Seider, E. N. and Tate, G. E., "Heat Transfer and Pressure
Drop," Industrial Engineering and Chemistry, Vol. 28, 1936, pp.
1429-1436; b. Kern, D. Q., "Chapter 6-Counterflow: Double Pipe
Exchangers," Process Heat Transfer, McGraw Hill Inc., NY,
1950, p. 103.
[5] ASTM E 1, "Specification for ASTM Thermometers," Annual
Book of ASTM Standards, Vol. 14.03.
[6] Anon. "Product Review: Oil Refining and Lubricant Base
Stocks," Industrial Lubricatoin and Tribology, 1997, Vol. 49, No.
4, pp. 181-188.
[7] Singh, H., "Characterization of Lube Oil Base StockApproach
and Significance," Advances Production & Application of Lubricant Base Stocks, Proceedings, International Symposium, H.
Singh, P. Rao, and T. S. R. Tata, Eds., McGraw-Hill, New Delhi,
1994, pp. 303-310.
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
Base Oil," Symposium on Worldwide Prospectives on the Manufacture, Characterization, and Application of Lubricant Base Oils,
Division of Petroleum Chemistry, Inc., 213 National Meeting of
the American Chem. Society, 1997, pp. 227-228.
Fuchs, H. C. G., "Understand Thermal Ansdysis Techniques,"
Chemical Engineering Progress, Vol. 93, No. 12, 1997, pp. 39-44.
Kern, D. Q., Process Heat Transfer, McGraw-Hill Book Company, NY, 1950, pp. 99, 103.
"Chapter 3-Viscous Oils," Manual on Hydrocarbon Analysis, 6'*^
Edition, A. W. Drews, Ed., 1998, ASTM International, West Conshohocken, PA, p p . 25-30.
B a r m a n , B. N., "Hydrocarbon-Type Analysis of Base Oils
and Other Heavy Distillates by Thin Layer Chromatography
with Flame-Ionization Deection and by the Clay-Gel Method,"
Journal of Chromatograpic
Science, Vol. 34, No. 5, 1996,
pp. 219-225.
Sassiat, P., Machtalere, G., Hui, F., Kolodziejczyk, H., and Rosset, R., "Liquid Chromatographic Determination of Base Oil
Composition and Content in Lubricating Oils Containing Dispersants of the Polybuteneylsuccinimide Type," Analytical
Chimica Acta, Vol. 306, No. 1, 1995, pp. 73-79.
Kagdiyal, V., Joseph, M., Sastry, M. I. S., Satapathy, S., Basu,
B., Jain, S. K., et al., "Estimation of Polycyclic Aromatic Hydrocarbons of Base Oils by HPLC and by UV Spectroscopic
Technique: A Comparison," Proceedings of the Advances Production & Application of Lubricant Base Stocks, Proceedings
International Symposium, H. Singh and T. S. R. Prasada Rao,
Eds., Tata McGraw-Hill, New Delhi, India, 1994, pp. 295-302.
Jain, M. C , Bansal, V., Jain, S. K., Srivastava, S. P., and Bhatnagar, A. K., "The Role of Thermal and High Temperature Gas
Chromatographic Techniques in the Characterization of Base
Oils Blends," Proceedings Adv. Prod. Lube Base Stocks, H. Singh
and T. S. R. Prasada Rao, Eds., Tata McGraw-Hill, New Delhi,
India, 1994, pp. 272-279.
Powell, J. R. and Compton, D. A. C. "Automated FT-IR Spectrometry for Hydrocarbon-Based Engine Oils," Lube Engineering, Vol. 49, No. 3, 1993, pp. 233-239.
Anon., "Characterizing Base Oils," Lubrizol Newsline, Lubrizol
Corporation, Wickliffe, OH, December 1996, pp. 5.
MNL37-EB/Jun. 2003
HEAT TREATING APPLICATIONS. Quenching is the process of cooling metal parts to achieve the desired microstructure, hardness, strength or toughness. Quenching can produce both desirable and undesirable residual stresses and distortion in
addition to cracking. Steel, for example, is heated to the
austenitizing t e m p e r a t u r e , that t e m p e r a t u r e where the
austenite m i c r o s t r u c t u r e is formed. To obtain o p t i m u m
hardness, strength, and toughness, the maximum amount of
martensite transformation microstructure is desired. The
primary function of the quenching medium is to control the
rate of heat transfer from the surface to optimize the microstructure while minimizing undesirable features such as
cracking and distortion [1].
The selection of a quenching medium is dependent on the
composition of the alloy, the desired final microstructure and
the surface to volume ratio of the part. The most c o m m o n
quenchant media are usually liquids or gasses. Liquid quenchants include: mineral oils, water, water that may contain
salt or caustic additives, and aqueous polymer solutions. The
most c o m m o n gasses, which may or may not be pressurized,
include nitrogen, helium, and argon.
Various aspects of quenching technology will be discussed
in this chapter. This includes: hardenability, fundamentals of
quench processing, description of c o m m o n quench media,
cooling curve analysis, and quench bath maintenance. Included in this discussion is the current status of international
standards development for quenchant characterization. This
discussion will be limited to steel quenching technology.
Quenching of non-ferrous alloys are not discussed here
although the basic surface cooling principles involved are
the same.
DISCUSSION
Steel Transformation
Properties such as hardness, strength, ductility, and toughness are dependent on the microstructure and grain size. The
first step in the process is to heat the steel to its austenitizing
temperature. The steel is then cooled rapidly to avoid the formation of ferrite and maximize the formation of martensite,
which is a relatively hard transformation product, to achieve
the desired as-quenched hardness.
' University of Zagreb, Zagreb, Croatia.
^ Technical University of Munich, Munich, Germany.
^ G. E. Totten & Associates, Inc., LLC, Seattle, WA.
587
Copyright'
2003 by A S I M International
www.astm.org
i>6-
(a),(b)
^.>fl
'"-*-.^
:>..>'^
vs?i.
.v^>
-^y-.
/*
(d),(e)
- -
mA
f^-i-ii
(c)
i^-M'S
(g),(h)
FIG. 1Illustrations of microstructural transformation products:
a) Equiaxed austenite grains and annealing twins in an austenitic stainless steel. 250X; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002, Fig. 20, p. 26. b) Low-carbon ferritic sheet steel
etched to reveal ferrite grain boundaries-. 100X; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002, Fig. 25, p. 30. c) Pearlite structure in high-carbon steel (Fe-0.5C). The cementite lamellae
are white; the ferrite is dark: 500X; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH
44073-0002, Fig. 26, p. 30. d) White cast iron contains massive amounts of cementite (white) and pearlite (dark): 500X;
ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002, Fig. 64, p. 66. e) Upper
bainite in 4360 steel; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002,
Fig. 173, p.156. f) Lower bainite (dark plates) in 4150 steel; Reprinted from Ref. 3, p. 67 by courtesy of Marcel Dekker,
Inc. g) Microstructure of lath martensite; 500X; Reprinted from Ref. 3, p. 68 by courtesy of Marcel Dekker, Inc. h) Microstructure of plate martensite; light shading is retained austenite; 500X; Reprinted from Ref. 3, p. 69 by courtesy of
Marcel Dekker, Inc. i) Microstructure of tempered martensite; 500X; ASM Materials and Engineering Dictionary, ASM
international. Materials Park, OH 44073-0002, Fig. 365, p. 308.
(f)
CHAPTER
22: NON-LUBRICATING
PROCESS
Diagrams
TTT diagrams, which are also called isothermal transformation (IT) diagrams, are developed by heating small samples of
steel to the t e m p e r a t u r e where austenite transformation
structure is completely formed i.e., austenitizing temperature, and then rapidly cooling to a temperature intermediate
between the austenitizing and the Ms temperature, and then
holding for a fixed period of time until the transformation is
complete, at which point the trcinsformation products are determined. This is done repeatedly until a TTT diagram is constructed such as that shown for a n unalloyed steel (AISI
1045) in Fig. 2A. TTT diagrams can only be read along the
isotherms.
FLUIDS:
CCT
STEEL
QUENCHING
TECHNOLOGY
589
Diagrams
ill
m
800 A3
700 A l
T Fe rite
5 - BOO
2
III
500
Bajnite - >ta 1
2 m
Q.
Bainite
fc m ^ I v i d r i i
site^
1-
eoo
1 II
700
n
7
7(7'
Seconds
(a)
-Time-
B]pi0'
T l
End
1
1 II
10*
10^
h 15 30 ffb
Minutes
7 d t SB
Hours
7
1Sl*
-Time-
S f B 75 30
Minutes
T S ifB8 1BSt
l-lours
FIG. 2a) Time-Temperature-Transformation (TTT) diagram of an unalloyed steel containing 0.5% carbon; b) ContinuousCooling-Transformation diagram of an unalloyed steel containing 0.6% carbon.
(b)
590
MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
^600
S.400
E
\M,
o
ro 200
CO
I 0
0.5
1.0
Carbon Content (wt. %)
1.5
4
5
6
1
Round Dars-
in
<o
= 125
_o
E.
t 100
1
Plates
0)
c
o
*0)
-
I 75
<u
't
(0
TJ
3
T3
O
150
"^N^
<D
\-
50
*-^
u
25
D
O
0
25
50
75 100 125 150 175
Equivalent bar diarneter, mm
100
D)
C
w
^
>-
50
0.2
0.4
0.6
0.8
Carbon Content (wt. %)
I
30
25
20
Nickel Content (wt. %)
Where fx is a multiplicative factor for the particular substitutionally dissolved alloying element. The base Dj Base value and
one set of alloying factors are provided in Table 1 [6] (Note:
This is not an exhaustive listing of alloying factors but these
are commonly encountered and they permit calculations to
illustrate the effect of steel chemistry variation on hardenability.)
Grain size refers to the dimensions of grains or crystals in
a polycrystalline metal exclusive of twinned regions and subgrains when present. Grain size is usually estimated or measured on the cross section of an aggregate of grains. Common
units are: (1) average diameter, (2) average area, (3) number
of grains per linear unit, (4) number of grains per unit area,
and (5) number of grains per unit volume.
Grain size may be determined according to Test Method E
112. The test methods covered in Test Method E 112 describe
the measurement of average grain size and include the comparison procedure, the planimetric (or Jeffries) procedure,
and the intercept procedures. Standard comparison charts
are provided. These test methods apply chiefly to single phase
grain structures but they can be applied to determine the average size of a particular type of grain structure in a multiphase or multiconstituent specimen.
In addition, the test methods provided in E 112 are used to
determine the average grain size of specimens with a unimodal distribution of grain areas, diameters, or intercept
lengths. These distributions ire approximately log normal.
These test methods do not cover methods to characterize the
nature of these distributions. Characterization of grain size
in specimens with duplex grain size distributions is described
in Test Method E 1181. Measurement of individual, very
coarse grains in a fine-grained matrix is described in Test
Method E 930. These test methods deal only with determination of planar grain size, that is, characterization of the twodimensional grain sections revealed by the sectioning plane.
TECHNOLOGY
591
TABLE 1Hardenability factors for carbon content, grain size and selected alloying elements in steel.
Carbon
Content (%)
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
Alloying Element
Mn
Si
Ni
Cr
Mo
0.0814
0.1153
0.1413
0.1623
0.1820
0.1991
0.2154
0.2300
0.2440
0.2580
0.273
0.284
0.295
0.306
0.316
0.326
0.336
0.346
0.0750
0.1065
0.1315
0.1509
0.1678
0.1849
0.2000
0.2130
0.2259
0.2380
0.251
0.262
0.273
0.283
0.293
0.303
0.312
0.321
0.0697
0.0995
0.1212
0.1400
0.1560
0.1700
0.1842
0.1976
0.2090
0.2200
0.231
0.241
0.251
0.260
0.270
0.278
0.287
0.296
1.167
1.333
1.500
1.667
1.833
2.000
2.167
2.333
2.500
2.667
2.833
3.000
3.167
3.333
3.500
3.667
3.833
4.000
4.167
4.333
1.035
1.070
1.105
1.140
1.175
1.210
1.245
1.280
1.315
1.350
1.385
1.420
1.455
1.490
1.525
1.560
1.595
1.630
1.665
1.700
1.018
1.036
1.055
1.073
1.091
1.109
1.128
1.146
1.164
1.182
1.201
1.219
1.237
1.255
1.273
1.291
1.309
1.321
1.345
1.364
1.1080
1.2160
1.3240
1.4320
1.54
1.6480
1.7560
1.8640
1.9720
2.0800
2.1880
2.2960
2.4040
2.5120
2.62
2.7280
2.8360
2.9440
3.0520
3.1600
1.15
1.30
1.45
1.60
1.75
1.90
2.05
2.20
2.35
2.50
2.65
2.80
2.95
3.10
3.25
3.40
3.55
3.70
HANDBOOK
illustrated in Fig. 6 [3]. The austenitizing temperature is selected according to the specific steel alloy being studied, however, most steels are heated in the range of 870-900C
(1600-1650OF).
In the Jominy end-quench test, a cylindrical specimen is
heated to the desired austenitizing temperature and welldefined time, which is material composition dependent, and
then it is quenched on one end with water. The cooling velocity decreases with increasing distance from the quenched
end. After quenching, parallel flats are ground on opposite
sides of the bar and hardness measurements are made at 1/16
in. (1.6 mm) intervals along the bar, as illustrated in Fig. 7
[6]. The hardness as a function of distance from the
quenched end is measured and plotted and, together with
measurement of the relative areas of the martensite, bainite,
and pearlite that is formed, it is possible to compare the hardenability of different steels using Jominy curves. As the slope
of the Jominy curve increases, the abiUty to harden the steel
(hardenabihty) decreases. Conversely, decreasing slopes (or
increasing flatness) of the Jominy curve indicates increasing
hardenabihty (ease of hardening).
The Jominy end-quench is used to define the hardenabihty
of carbon steels with different alloying elements like
chromium (Cr), manganese (Mn), molybdenum (Mo) and
has different critical coohng velocities. Jominy curves for different alloy steels are provided in Fig. 8 [9]. These curves illustrate that the unalloyed, 0.4% carbon steel exhibits a relatively small distance for martensite (high hardness)
formation. The 1% Cr and 0.2% Mn steel, however, can be
hardened up to a distance of 40 mm. Figure 8 illustrates that
steel hardenabihty is dependent on the steel chemistry, that
unalloyed steels exhibit poor hardenabihty, and that Jominy
curves provide an excellent indicator of relative steel hardenabihty.
The Jominy test provides valid data for steels having an
ideal diameter from about 25-150 mm (1-6 in.). This test can
be used for Di values less than 25 mm (1 in.), but Vickers or
microhardness tests must be used to obtain readings that are
closer to the quenched end of the bar and closer together
than generally possible using the standard Rockwell "C"
hardness test method [4].
The austenitizing time and temperature, extent of special
carbide solution in the austenite and extent of oxidation or
surface decarburization during austenitizing, care and consistency of surface flat preparation, and bar positioning prior
I Cemenlite Lamella
Probi
WaterNozzlei
270 70 18 5-6
4B9-\Z4'-32.3"1<y
y.6 V,. y. 'V,,
-rr- 1
r,i}cooling rates
Distance from quenched end., in.
^
"a
\U
60
50
S 40
I
230
o
0
^ M
'
to
'
'
1.0
'
25
'
2.0
-^I
50
3.0 in.
I
I
75 mm
Hardenability
CHAPTER
22: NON-LUBRICATING
PROCESS
To identify a quenching medium and its condition, Grossm a n n introduced the Quenching Intensity (Severity) factor
"H". Table 2 provides a summary of Grossmann H-Factors
for different quench media and different quenching conditions [1]. Ahhough this data has been pubhshed in numerous
reference texts for many years, it is of relatively limited quantitative value. One of the most obvious reasons is that quenchant agitation is not adequately defined and is often unknown, yet it exhibits enormous effects on quench severity.
The Grossmann value "H" is based on the Biot (Bi) number, which interrelates the interfacial heat transfer coeffi-
FLUIDS:
STEEL
QUENCHING
TECHNOLOGY
593
Oil
Water
None
Mild
Moderate
Good
Strong
Violent
0.25-0.3
0.30-0.35
0.35-0.4
0.4-0.5
0.5-0.8
0.8-1.1
0.9-1.0
1.0-1.1
1.2-1.3
1.4-1.5
1.6-2.0
4
2
2-2.2
cient (a) thermal conductivity (A) and the radius (R) of the
round bar being hardened:
Bi = a/\-R
H = al{2-
0
10
20
30
40
50
Distance from the Quenched Front Side (mm)
FIG. 8Jominy curve comparison of the hardenability of one
unalloyed and a number of other different alloy steels. All alloy
concentrations are weight %.
i 40
r-i-
-HRC .,s50%M
i/i
a>
Cfll
"I 20
-?c^t^
o
I
'm
FIG. 9Determination of critical diameter Dcrit according to
Grossmann.
H-D
X)
Q u e n c h i n g F i m d a m e n t a l s a n d C o o l i n g Curve
Analysis
Steel Wetting
GO
Kinetics
Hardening of steels (so cedled Martensitic- or Bainitic- Hardening) requires preheating (austenitizing) of the steel to temperatures in the range of 750-1100C, from which the steel is
quenched (cooled) in a defined way to obtain the desired mechanical properties such as hardness a n d yield strength.
Most liquid vaporizable quenchants used for this process exhibit boiling temperatures between 100 and 300C at atmospheric pressure. When parts are quenched in these fluids,
the wetting of the surface is usually time dependant, which
influences the cooling process and the achievable hardness.
G. J. Leidenfrost described the wetting process about 250
years ago [10]. The Leidenfrost Temperature is defined as the
surface temperature where the vapor film collapses and the
surface is wetted by the liquid. Literature describes temperature-values for this event for water at atmospheric pressure
between 150 and 300C [11-14]. It is apparent that the Leidenfrost Temperature is influenced by a variety of factors,
part of which cannot be quantified precisely even today.
Immersion cooling
Wetting front
surface, which will depress the heat flux from the specimen
into the fluid.
Factors Influencing
Film
Boiling
Film boiling
Nucleate boiling
Convective beat
transfer
Heal transfer
coefficient at
Film cooling
Film of liquid
Convection boiling
Fluid drops
Wetting front ir
FIG. 10Wetting behavior and cliange of heat transfer coefficient a along the surface [13,16].
(a)
(b)
(c)
4.0 s
3.8 s
4.3 s
7.0 s
5.7 s
8.3 s
TECHNOLOGY
595
10 s
6.9 s
12,3
3^2 s
4,92 s
5,97 s
7,38 s
(d)
FIG. 11Process of transition between tlie three cooling phasesfilm boiling (FB), nucleate boiling (NB) and convective cooling (CONV) during immersion cooling of CrNi -steel specimens with a cylindrical geometry 25 mm dia x 100
mm), a. Wetting process of a cylindrical CrNi-steel specimen being quenched from 850C into water at 30C with an agitation rate of 0.3 m/s b. prismatic geometry (15 x 15 x 45 mm) in water of 60C without forced convection; Immersion
temperature of 860C, c. CrNi-steel probe (25 mm dia. x 100 mm) in oil at 60C without agitation, d. hollow cylinder (60
od X 30 id X 60 mm long) quenched into oil at 60 and no agitation. Note: there are two wetting fronts.
beginning the quenching process), having a "non-NEWTONIAN wetting" is shown in Fig. 16a. where there is a great
difference relative to that of the "NEWTONIAN wetting"
(Fig. 166). In the second case, the temperature gradient, T,
is radial whereas in the case 'a it is axial. Of course the
hardness distribution in the probes must be extremely different. In the case of "a," a strong axial hardness distribution (accompanied by a very low radial hardness distribution); in the case of "b," a very strong radial hardness
gradient is observed.
596
HANDBOOK
1000
O
o
!
*
750
(0
ki.
ID
Q.
; a
c_
JO
r",
(b)
(a)
500
2 \
"* \
1
/Water
AK
250 polymer ^
10
/3
X.
20
30
3
2
1
1-3
40 0
10
15
20
Time in s
Time in s
FIG. 14Comparison of cooling curves measured at different positions in a cylindrical CrNi-steel probe (25 dia. x 100
mm) during slow wetting (water) and sudden wetting (aqueous
polymer solution) at (a) center and (b) close to the probe surface at three indicated heights (1,2, and 3).
6.35 s
7.65 s
(t ==
FIG. 12Transition from film boiling (FB) to nucleate boiling (NB) during immersion of cylindrical silver
specimen (15 mm dia x 45 mm) quenched from 850C
into a 10% aqueous polymer quenchant solution at
25C without agitation [18] In comparison with the
tw-values of Fig. 13 a and b, the wetting time is extremely short [18].
iIk (a)
i^
0)
1
ts.tf
Atw
n
Ti
i
ti
Ti
i
ti
ti
".Parameters: ts'. time when wetting starts; tf. time when wetting is finished;
Atw- time interval of wetting [s]; a: heat transfer coefficient.
m
<o
o.
E
0)
Fluid Property
Type of quenchant
Addition of additives
Increasing agitation (v)
Increasing bath
Temperature (Tt)
Metal Property
Increasing thermal
Diffusivity (a)
Increasing cross
section Size
Increasing surface
Roughness
Increasing surface
Oxidation
^ ^
timet
ts = tf
timet
timet
FIG. 13a-d): Temperature decrease, Tc, and increasing electrical conductance, G, (proportional to
the wetted surface) during quenching in different
quenchants; a) slow wetting, b) rapid (explosive-like)
wetting; c) rapid wetting followed by isolation of bubbles adhering to the metal surface; d) rapid wetting
with repeated formation of film boiling after this process (see also Figs. 14 and 15) [13,18].
597
15
20
Quenching time
FIG. 15^Temperature drop on the surface of a cylindrical
steel probe (25 mm dia x 100 mm) at various distances zfrom
the lower end [16].
/=5s
-825'C
-775"C
t=5s
/=10s
/=11s
/=15s
60 Time (sec.)
40
20
80
60
100
120
140
_^^
^ 600 w
3
13
w 400
Q.
E
V
1-
200
n
0
-
*
11
10
2G
20
40
30
60
80
40
100
50
120
60 Time (sec.)
140
Daita collected at 5 HZ
60 Time (sec.)
0
20
40
60
80
100
120
140
TECHNOLOGY
599
168
-30mm
30mm-
M6mm
9.5mm
13mm (12.5mm after
- f
finish grinding)
1.5mm tight push
fit "nominar
Not to be
center drilled
Probe details
Probe body
Details Infig.3(a^
Finish
grind
Support tube
Material - Inconel alloy 600
Tl^t fit on probe end iwith
30 angle weld allowance
Dimensions as (a)
12.5 0 . 0 1 mm
End support
-tube
Material Stainless steel
Termination
Standard tttermocouple
typeV(NlCf/NlAI)
General assembly
FIG. 19^Wolfson Inconel 600 probe.
i I
60
50
DC
-o 40
(0
X
30
20
200
Measurements
Shock-film boiling
Full-film boiling
Nucleate boiling
9-20
0.05-1.5
0.5-4.0
1.S mm
9,IW
lot, 4r
i5o:
lOS
A136
100
sn
I A
2
jxi.m
iot,i
FIG. 23Comparison of quenching properties of aqueous PAG polymer quenchant (concentration 20% at 20(C). A5 and A136 correspond to 0.5 and 13.6 kc.
602
HANDBOOK
was required to observe the transition from shock- film boiling via full-film boiling to nucleate boiling.
Quench Oils
Quenching oils are analogous to other petroleum-derived
products including engine oils, spindle oils, and industrial lubricating oils such as gear lubricants [39]. Although
petroleum oils are usually refined for specific applications,
they remain complex mixtures with a variety of possible compositions, which may vary even when produced by a single
refinery. The compositional complexity of quench oils affects
their quenching performance. Segerberg [40] compared a series of mineral-oil-based quenchants, which were tested by
cooling curve analysis according to ISO 9950 (ASTM D 6200)
and obtained a wide variety of cooling rates, as shown in Fig.
24. Formulated oils can produce an even wider range of cooling rates.
Quenching oils that contain substantial quantities of naphthenic derivatives usually exhibit inferior cooling characteristics, greater deposit-forming tendency, and lower flash
points than paraffinic oils. Tensi [41] has shown that the
quench severity of a particular quench oil is directly related
to its ability to wet a metal surface. The wettability of a
quench oil is quantified by measuring "rewetting" times, as
shown in Fig. 25.
O
o
3
a
E
Cooling R a t e . ' C
FIG. 24Potential variation of the severity of different quench oils.
10
30
50
70
90
Code Letter
General
Application
Heat Treatment
Oil for
Oil for
Oil for
Oil for
Oil for
Oil for
normal hardening
quick hardening
normjd hardening
quick hardening
normal hardening
quick hardening
Vacuum hardening
Other cases
Aqueous Fluids
for Heat
treatment
Surface hardening
Mass hardening
Molten Salts
for Heat
Other cases
150C<e<500C
500X<6><700C
Other cases
603
Water
Aqueous fluid
Aqueous fluid
Water
Aqueous fluid
Aqueous fluid
Symbol
ISO-L
UHA
UHB
UHC
UHD
UHE
UHF
UHG
UHH
UHV
UHK
Remarks
Certain oils may be
easily eliminated by
washing with water.
This characteristic
is brought about by
the presence of
emulsifiers in the
oil formulation.
Such oils are then
known as
"washable." It is up
to the supplier at
the request of the
^^'^ user, to provide
this characteristic*
UAA
UAB
UAC
UAA
UAD
UAE
UAK
USA
USB
USK
UGA
UGB
UGC
UGD
UF
UK
Fluidized Bed
Other cases
"8 indicates the iluid temperature at the time of hardening;
''The washing solution used to remove the emulsified oil may be either detergent (soap) and water or water-borne alkaline cleaners. The cleaning conditions
shall be provided by the oil supplier.
604
MANUAL
HANDBOOK
Typical GM
Typical
Viscosity at 40C
(100F) SUS
340
355
570
105
94
700
16.0
10
30
Flash Point
Type of Oil
op
Conventional
Accelerated
Marquenching
<65
<120
<200
<150
<250
<400
C
170
180
300
Time (s)
1600
1400
1200
G?
N ^^Conventional
V
quench oil
\
150F
\
\
\
Martempering oil
500 F
Fused salt
500 F
2 1000
2
800
600
400
0.7
1.0
1.5
10
"^.^ ^ > ^
'^Molten
"^.^ N.
metal
'^O'^
500 F
15
20
30
40
60
Time (sec)
FIG. 26Comparison of cooling curves for various quench media.
facilitates surface wetting, which destabilizes the film boiling
process. Examples of additives that may be used to accomplish this include: calcium naphthenate [47], alkenyl succinate [47], and sodium sulfonate [48]. Viscosities of these oils
may vary from 50-100 SUS at 40 (100F).
For some steels, quenching at an elevated temperature is
necessary to reduce thermal and transformational stresses
that may lead to cracking and increased distortion. One process that may be used to accomplish this is martempering (or
marquenching). In meirtempering, metal is usually quenched
from the austenitization temperature to a temperature just
above (see Fig. 27B) the stcirt of martensite transformation
(Ms) just long enough for the temperature to equalize between the surface and the center of the steel. The metal is
then removed from the quench bath and air-cooled. The thermal cycle for both conventional quenching Eind martempering is illustrated in Fig. 27 [1].
Martempering or hot quenching oils are used at temperatures between 95-230C (200 a n d 450F). They are usually formulated from solvent-refined mineral oils with a very high
parafBnic fraction to optimize oxidative and thermal stability.
Stability is enhanced by the addition of antioxidants. Nonaccelerated and accelerated martempering oils are available
Typical t e m p e r a t u r e ranges for m a r t e m p e r i n g oils are
shown in Table 7 [46]. Because martempering oils are used at
relatively high temperatures, a protective, nonoxidizing
atmosphere over the oil is typically used, which allows operation closer to the flash point of the oil t h a n if open-air conditions are used [49]. A protective atmosphere is any atmo-
by GM Quenchometer
Cooling
Times
Surface
TECHNOLOGY
Surface
Center
Center
Time
(b)
I
o
o.
E
FIG. 27Types of quenching cycles: (a) conventional quenching and tempering, (b) martempering,
(c) isothermal quenching and tempering, and (d) austempering.
TABLE 7 --Typical use temperatures for martempering oils.
Use Temperature
Minimum
Flash Point
605
Viscosity at
40C (100F)
SUS
"C
250-550
700-1500
2000-2800
220
250
290
430
480
550
95-150
120-175
150-205
200-300
250-350
300-400
Open Air
Protective Atmosphere
F
C
95-175
120-205
150-230
200-350
250-400
300^50
Curie point
Separation
temperature
"C
80
90
F
(175)
(195)
70
46
Heat
100 0(212?)
Water with
contaminants
Separated
polymer
quenchant
Homogeneous
auenchant solution
FIG. 29Thermal separation of an aqueous solution
of a polyalkylene glycol quenchant.
Standards
CHAPTER
22: NON-LUBRICATING
PROCESS
FLUIDS:
STEEL
QUENCHING
TECHNOLOGY
Insulating lube
607
il
S i l v e r wire
Pipe made of
silver
Heat resistanl
insulator
M6 X pitch 1
Alumel wire
M> X pitch 0 . 5
Dead
M5 X pitch 0 . 5
> <
Insulating tube
FIG. 30Japanese JIS K 2242 silver probe (All dimensions are in mm).
eral oil whose physical properties are summarized in Table
10 [65].
The ASTM Test Method D 6200 is based on the Wolfson
standeird [65] and ISO 9950, except the specification limits
are controlled more tightly and were based on various statistically designed experimentation as required by ASTM
[68-70].
Development
of Cooling
with
Agitation
Curve Analyses
Methods
Many quenchants, a n d nearly all aqueous polymer quenchants, cannot be evaluated reproducibly without the use of
agitation. Such quenchants always require the use of agitation w h e n used industrially in various heat-treating processes. All of the cooling curve methods discussed d o not employ agitation and are essentially limited to analysis of
minercd oil derived quenchants.
There are two ASTM stcindards for cooling curve analysis
with agitation. One method is ASTM D 6482 and the other is
ASTM D 6549. Both test methods utilize the Wolfson probe
illustrated in Fig. 19. Test Method D 6482 uses an agitation
device, which is shown in Figs 33. [65,71] and 34A. This device is constructed from a transparent material such as Plexiglas or glass and holds approximately 1.5 L of quenchant.
Agitation is provided by a plastic impeller of 50 m m dia. and
pitch of 42 m m [72]. One of the advantages of this agitation
system is the uniformity of turbulence and flow throughout
the quench zone as shown in Fig. 35 [71]. This means that the
sensitivity to error with respect to precise placement of the
probe in the quench zone will be minimal.
Test Method ASTM D 6549 is significantly different from D
6482 in that p u m p agitation is used. This is illustrated in Fig.
34B. This p u m p agitation system is based on earlier work
performed by N.A. Hilder at Aston University [73]. Probe
placement in the fluid reservoir during quenching is illustrated in Fig. 36.
Quench Bath Mamtenance
Sampling
Flow is never uniform in agitated quench tanks. There is always variation of flow rate and turbulence from top to bot-
608
HANDBOOK
torn and across the tank. This means that there may be
significant variations of particulate contaminants including
sludge from oil oxidation and metal scale. For uniform
sampling, a number of sampling recommendations have
been developed:
1. Minimum Sampling TimeThe circulation pump shall be
in operation for at least 1 h prior to taking a sample from
a quench system.
pef^etofv Ofobecamg.
Thermocoupfe0l
m*
' < l i
iJ
1B.m.4>Wi
' " "^ 'J!^ " ^ ""^ p* 4 . *fc w w * . nMk mmt mm* mmtmmm^m
s\\\\
30ia.26
mm mm i .
mmm
MiO.fi
I a
FIG. 32Chinese silver probe (All dimensions are in mm).
Variable
ISO 9950
Probe Alloy
Inconel 600
Probe
Dimensions
Standard
Reference Oil
Vessel
Dimensions
Oil Volume
Oil Temperature
12.5 m m Dia. X
60 m m
See Table 10
Silver
99.999% pure
16 m m Dia X
48 m m
See Table 10
115 5 m m
diameter
2000 mL
40C 2C
height 138 m m X
diameter 99 m m
800 mL
50C 2C
850C 5C
800C 5 X
Probe
Temperature
GB
(ZB E 45003)
Silver
99.99% pure
10 m m Dia X
30 m m
Dioctyl
phthalate
300 mL beaker
Silver
99.96% pure
10 m m Dia X
30 m m
Dioctyl
phthalate
300 mL beaker
250 mL
80''C,120C,
160C
810C 5C
250 mL
80C 2C
See Table 10
115 5 m m
diameter
2000 mL
40C 2C
810C 5C
850''C 5C
ASTM D 6200
Inconel 600
12.5 m m Dia X
60 m m
TABLE 10Physical properties of the so-called "Wolfson Oil" used as a reference for ASTM D 6200, ISO 9950,
and AFNOR NRT 60778 standards.
Institute of Petroleum Test
Minimum
Maximum
Method/ASTM Method
Value
Physical Characteristics
Value
Kinematic Viscosity at 40C, cS"
23.0
19.0
IP 71/D 445
Kinematic Viscosity at 100C, cS"
4.4
3.9
IP 71/D 445
Viscosity Index
105
IP 226/D 2270
95
Density at 15C, kg/L
IP 160/D 1298
0.855
0.870
Flash Point PMCC, "C
IP 34/D 93
210
190
5% Distillation, C
IP 123
360
330
50% Distillation, C
IP 123
420
400
' 1 cS = lO"** m^/s.
Although the viscosity of a martempering oil may not fluctuate substantially at elevated t e m p e r a t u r e s , the oil may
become almost solid u p o n cooling. Thus, the viscositytemperature relationship of a quench oil may be critically
important from the dual standpoint of quench severity and
flow velocity.
Typically kinematic viscosity determination by Test
Method D 445 is used. Viscosity measurements are made at
40C (100F) for conventional or accelerated oils and also at
100C (212F) for martempering oils.
Flash Point and Fire Point (Test Methods D92, D93, D13I0)
Use of a quench oil at a temperature near its flash point in an
unprotected environment, or near its fire point, may result in
an oil fire. General guidelines have been developed for usetemperatures of a quench oil relative to its flash point.
N o t e 2: There are various manufacturer-dependent guidelines for relating the suitability for use of a used quenching oil with respect to its flash point and they shall be
followed. In the absence of such guidelines, it is recommended that the use temperature of a quenching oil in an
open system with n o protective a t m o s p h e r e shall be
60-65C (108-117F) lower than the actual open-cup flash
point. In closed systems where a protective atmosphere is
used, the use temperature of the used quenching oil shall
be at least 35C (60F) lower than its actual open-cup
flash point.
Specific Gravity (Test Method D287)Specific
gravity depends on the chemical composition of the base stock used to
formulate a quenching oil. The oxidative stability of the
quenching oil is dependent on the chemical composition,
such as naphthenic/paraffinic ratio. Therefore, the specific
Oils
610
MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
absence of such a value, it is recommended that the AN not
exceed 2.00 mg/g for a used quenching oil.
Infra-Red Spectroscopy^An alternative method that is being
used increasingly to identify and quantify oil oxidation, even
in the presence of additives, is infra-red (IR) spectroscopy.
Figure 37 provides an illustration of the use of IR spectral
cmcJysis to identify oil oxidation [77]. Mang zmd Jiinemann
monitored the IR stretching vibrations o f C B O a t l 7 1 0
c m ~ \ for carboxylic acids contained in oxidized oil. IR analysis has been used to detect and qucintify other carbonyl-containing compounds [78]:
Metal carboxylate salts-1600 and 1400 c m " '
Carboxylic Acids-1710 c m " '
Metal sulfates-1100 and 1600 cm '
Esters-1270 and 1735 cm '
Saponification Number (Test Method D 94)Oil degradation
may produce both acids and ester by-products. The acid number quantifies the amount of acidic degradation by-products in
the oil, whereas the saponification number is a measure of the
presence of esters or fatty esters in the oil. The saponification
number of an oil is determined (Test Method D 94) by heating
a sample of the oil with a known amount of basic reagent and
measuring the amount of reagent consumed. Because some
quench oils are formulated with components that also have
saponification numbers, it is necessciry to monitor trends over
time than to rely on an absolute value [81]. An increase in the
saponification number indicates an increased propensity to
sludge formation. It has been suggested that if the results of
other tests are satisfactory, that saponification numbers below
3 mg KOH/g oil may be acceptable [75,82].
Contamination-Oil
dard base (Test Methods D 664 or D 974). The test is performed by dissolving the oil in a mixture of toluene and isopropanol, then titrating it with a standard solution of potassium hydroxide (KOH). The end-point may be determined
colorimetrically with a pH-sensitive indicator. The acid n u m ber (AN) is reported in units of milligrams of KOH per g r a m
of sample (mg/g).
Note 4: The quenching oil supplier will provide a maxim u m TAN value for the quenching oil being used. In the
Quenchants
CHAPTER
22: NON-LUBRICATING
PROCESS
FLUIDS:
STEEL
QUENCHING
TECHNOLOGY
611
(b)
FIG. 34Illustration of commercially available quenchant agitation systems: (A) Tensi agitation system, (B) Drayton agitation
system.
A quantitative test for water contamination involves titration of the oil with Karl Fisher chemical reagent to an electrometric endpoint (Test Method D 1744). This test is recommended for water levels of 50-1000 p p m (less than 0.1%).
Higher levels of water contamination may be quantified by
distillation (Test Method D 95) or centrifugation of the sample and measurement of the volume of separated water according to Test Method D 4007.
Note 6: A c o m m o n qualitative field test for water contamination is the so-called "crackle test," which is conducted
by heating a sample of the quenching oil and listening for
an audible crackling sound [77]. If the oil is contaminated
with water, a crackling sound will be heard before the
quenching oil has reached its smoke-point.
Carbon Residue (Test Method D189)One of the greatest problems encountered when using a quenching oil is the formation
and accumulation of sludge. Although the various analyses
procedures including viscosity, neutralization number, and
saponification number may indicate that a quench oil is adequate for continued use, the amount of sludge build-up in the
tank may demand that the system be drained and cleEtned.
Clccining and sludge disposal cire growing problems for the
612
HANDBOOK
heat treating industry. Therefore, determination of the sludgeforming potential of a quench oil prior to use is important.
One method of quantifying sludge-forming potential involves determination of the Conradson carbon residue (Test
Method D 189) measures the polymeric material remaining
in the oil after heating to elevated temperatures in the absence of sufficient oxygen to bum off all of the organic com-
pounds present. The Conradson carbon residue is determined by placing a weighed sample in an iron crucible. The
crucible is heated with a Meeker-type gas burner to a sufficiently high temperature to evaporate and bum the oil. The
sample is forther heated until the bottom and sides of the
crucible are cherry red and is held at this temperature for 30
min. The crucible is then cooled and weighed. The amount of
PLAN VIEW
FIG. 36Recommended probe placement in the Drayton centrifugal
pump apparatus shown in Fig. 34b (all dimensions are in mm).
TECHNOLOGY
613
ou
c
<D
jQ
<
1600
1700
1800
Wave number, cm - ^
FIG. 37Infra-red spectral identification of oxidation of a used quenching oil.
waterquantity
FIG. 38Illustration of the volumetric expansion of
1 mL of liquid water to 1700 mL of water vapor.
614
MANUAL
HANDBOOK
Properties
of Oil
Magnetic Quenchometer Method (Test Method D 3520)Cooling rates produced by quenching oils are often classified on
the basis of Test Method D 3520, the magnetic quenchometer
test illustrated in Fig. 28 [46]. Table 8 provides a summary for
quench oil classification by magnetic quenchometer times
[46]. Although this is a widely used test, the quenchometer
times do not relate to metallurgical properties. This is because only a single cooling time is determined; therefore,
there is insufficient information to indicate the actual temperature-time cooling pathway that is required to determine
if a specific steel may be successfully hardened. This is illustrated in Fig. 39 [46] Therefore, this test is of limited value,
with the possible exception as a quench oil classification test.
Guisbert and Moore conducted an extensive study in an at-
Time (Sec.)
FIG. 39Illustration of the Inability of a single cooling time value to successfully predict the outcome of a steel hardening process where a cooling
temperature-time curve is required.
4months'
oxidation
Smonttu'
oxidation '
L..I...I
i
ANawel
BAftarSnwntha
CMarSmonttia
PAttarOmortha
I i
SSSSSS
^^5tsp--B
amonths'
oxidation
_...4....f...f..
1 momh's
oxidation
^^.^f^^Z^^^^^
^"-""'''''^
No ox'tdatton*
Rr^
1 i i
\
Oiddation Of I ,
quendiing oii[ j
40
.
80
60
j
100
L.
4-1
120
20
.J
40
eo
80
100
CoollnoiataCcya)
(b)
140
Coolingrate(C/s)
(a)
FIG. 40Illustration of tlie effect of oil oxidation on tfie cooling rate curve for (A) a conventional quenching oil and (B) an
accelerated quencliing oil.
Accelerated-speed oil
' 1 " -
...|...j....
No contamination \
0.01%
water {
2%
No water
0.5% water
1 % water
water
0.05% water
0.10% water
i 0.20% water -;
J
40
(a)
60
80
^ I
100
i
120
i
140
FIG. 41Illustration of the effect of water contamination on the cooling rate curve for (A) a conventional quenching oil and
(B) an accelerated quenching oil.
(b)
616
HANDBOOK
1.341
10.0
15.0
QUENCHANT CONCENTRATION (%)
FIG. 42Illustration of the linear relationship between refractive index and concentration of an aqueous solution of a
polymer quenchant.
Refractive Index, (Test Method 1747)One of the most common methods of monitoring the concentration of aqueous
polymer quenchants formulated using poly(alkylene glycol)
copolymers is refractive index. As Fig. 42 [86] shows, there is
a linear relationship between quenchant concentration and
refractive index. The refractive index of the quenchant solution is determined using an Abb6 refractometer (Test Method
1747) equipped with a constant temperature bath. Although
the refractive index could potentially be used at any temperature with the control limits of the constant temperature
bath, typically either 40C or 100F is selected.
Although refractive index is a relatively simple and rapid
method for determination of polymer quenchant concentration, it is not sensitive to low levels of polymer degradation and it is often significantly affected by solution
contamination.
Note 10: Refractive index is typically unsuitable for aqueous polymer quenchants formulated with polymers with
molecular weights greater than 50000-60 000 because: 1)
The total amount of water-soluble polymer in solution is
not sufficiently different from the water diluent to provide
adequate sensitivity and 2) because the total concentration
is relatively low, small changes in polymer concentration
may result even from normal use, which imparts significant process effects. However, the corresponding variation
in refractive index may not be detectable.
Note 11: Although it is most desirable to use an Abbe refractometer because of its sensitivity, this is only practical
in a laboratory environment. In the heat treating industry,
for tankside monitoring and control, a temperature-compensated handheld refractometer similar to the one illustrated in Fig. 43a and b should be used. The hand-held refractometer is self-compensated for temperatures of 60
and 100F. Although there are various models available,
the most common models provide refractive index readings in Brix degrees over a 0-30 range. Typically, the
smallest scale that can be read directly is in divisions of
0.2 as shown in Fig. 44. A concentration-refractive index
curve obtained by a hand-held refractometer is shown in
Fig. 45 [86].
FIG. 43Typical hand-held refractometer; (A) application of quenchant solution to refractometer, (B) observation
of refractive index.
CHAPTER
22: NON-LUBRICATING
PROCESS
DEGREES
BRIX
T/C
FIG. 44Illustration of the Brix refractive index scale used
for a hand-held refractometer.
3MU
FLUIDS:
STEEL
QUENCHING
TECHNOLOGY
Comparison of Concentration by Refractive Index and Viscosity^A useful procedure for monitoring variations in aqueous
polymer quenchants, particularly poly(alkylene glycol) quenchants, is to compare the difference (delta) in the quenchant
concentration values obtained by refractive index (C) and
viscosity {Cv) [87].
^ =
CR-CV
MU
'^.."
'S
^%m-
<J
om
109 zw
,, ^ ,^ .
i-'.
3.to
im
617
, - { . > :
Sio
evoo jm
-i
s.m Mm mm
, ,^ ,:fihifltaettelnfelt'|''Bpix):
HANDBOOK
250
-
<0
a
z
o
o
u
200
(75 F, 23.9C)yC^
fsS'F,
29.4 C)
(0 150
s;ff
(6 }F, 18.3
oyy
UJ
(100 F,37.8C)
>
100
3 90
80
>:
^
70
60
50
-.
-
>
40
30
10
15
20
25
30
35
40
45
Polymer degradation is t5^ically accompanied by the formation of acidic by-products, which will decrease pH. Some
polymer quenchants, particularly when containing sodium
nitrite as a corrosion inhibitor, cannot be used below pH 7.0
without increasing the polymer degradation rate.
Some aqueous polymer quenchants contain amine or
amine/fatty acid mixtures as corrosion inhibitors. If substantial decrease in the concentration of these inhibitors occurs,
a decrease in pH will result. Thus, pH determination may be
a useful indicator of corrosion protection of some quenchants.
In some cases, the quench bath may be contaminated by
ammonia, which is used in some heat treatment processes.
Clearly, pH is an excellent indicator of potential ammonia
contamination. Quench baths may be contaminated by various hydraulic and metalworking fluids, which may significantly affect the resulting pH of the aqueous polymer quenchant.
Conductance, Test Method D 2624One of the most common
and most deleterious contaminants of an aqueous polymer
quenchant is hard metal ions (Ca"^^, Mg"^^, Mn"^^, and Fe"^^).
The presence of hard metal ions will lead to corresponding
increases in cooling rates. To extend the lifetime of the quenchant, it is often recommended that either distilled or deionized water be used for initial polymer quenchant dilution or
TECHNOLOGY
619
SOtOTION IMMEDIATELY
AFTER SEPARATION
(WITH AGITATION)
REDISSOLUTION OF
SOLUTION AFTER
LAYER FORMATION
FIG. 49Illustration of the reversible thermal separation process of an aqueous solution of a polyalkylene glycol quenchant.
620
MANUAL
HANDBOOK
determined according to Test Method D 3867, a cadmium reduction method that may be performed manually or by an
a u t o m a t e d procedure. Alternatively, nitrite anion m a y be
quantitatively determined by ion chromatography according
to Test Method D 4327.
Note 14: The concentration of nitrite in a quenchant may
also be determined by a relatively simple color test using a
commercially available test kit. A tablet, furnished with the
test kit, is dissolved in a specific volume of the solution,
and the resulting color of the quenchant solution is compared to a standard color chart of known concentrations of
sodium nitrite, as shown in Fig. 50.
Although sodium nitrite is a commonly used corrosion inhibitor used in the formulation of aqueous polymer quenchants, there is an increasing trend in the marketplace for socalled non-nitrite quenchants. Many of non-nitrite inhibitor
systems are based on various amines or amine-fatty acid
combinations. Due to the specificity of the required analytical procedures for determination of each non-nitrite inhibitor package that may be used, it is most common to submit samples periodically to the quenchant manufacturer for
analysis.
Foam Testing, Test Methods D 892, D 3519, and D 3601A
commonly encountered problem in production quench tanks
is excessive foaming. Excessive foaming is bad because it
may potentially lead to cracking and/or increased distortion.
Relative foaming propensity for one fresh quenchant compEired to another or a used quencheint compared to a fresh
quenchant or two used quenchant samples may be readily determined by various tests including Test Methods D 892 (using a gas diffusion tube), D 3519 (blender test), or D 3601
(bottle test).
Polymer Molecular Weight Analysis, Test Method D 5296^As a
test for pol5rmer degradation, gel permeation chromatogra-
200
150;
z
LxJ
I
Z 100
SEC trace for a polymer
from an unused aqueous
polymer quenchant solution
y
50H
CO
40
50
55
60
65
70
Stability
Fluid Biodeterioration ProcessesFluid biodeterioration involves the reaction of water with a substrate, such as the water-soluble polymer used to formulate a n aqueous polymer
quenchant, in the presence of b a c t e r i a or fungi to yield
biomass [89]. If this degradation process is not inhibited,
enormous queintities of biomass may be present in the system
in the form of sludge or microbial scum, which are composed
of dead cells, gelatinous slimes, and fungal threads. It has
been reported that a bacterial cell may double in size cind divide into two new cells every 15 min until a limiting condition
is encountered [89,90].
CHAPTER
22: NON-LUBRICATING
PROCESS
.':
*/
l'wf\.
STEEL
QUENCHING
TECHNOLOGY
M%
io>
800
U
~
600
8
3
? 400
a.
"V.
V\
,
\
5%
--
\ \
:\\
p
v. V
1 ''
3
2 400
2(
. ' ^ ,^
^<.
0)
a.
E
\ ^ -.^
^^.i
^^Zy^
,15%
10%
15%]
'^'
''
' - '
, -
5%
<-'
10%
15
Time(s)
621
FLUIDS:
SO
100
150
200
Cooling Rate(C/s)
"^
~YN
o
o
- ^ 600
a>
a.
E
fl 200
800
\\ \ \ 1
, \ \ V40C
50C
', \
30OcX\ N \
1 /
\^^^^.
*"*-<^
jy
-
^'
---'
1-
i:
0
10
15
.^^^
50C
40C\ / ^;.--
0
S
--.
'^^ . ..=--^.
*-st,-
'
/
/
_^
100
20
150
200
Cooling Rate(C/s)
Time (s)
FIG. 54Illustration of tlie effect of bath temperature on cooling curve and cooling rate curve performance of a 15% aqueous solution of a polyalkylene glycol quenchant.
-
800 i
800 > v
\^
o
a>
O
S_
.0 m/s
( .6 m/ .}\Lo.2ni/5
3
"2 400
a>
a
E
"-1
"
0.4 m/
1 m/i;'i"
0.6
600
^^^
a2m/s
. ^
>Yr
[j I
400
(1.4 m/ "'^
a.
E
%^;-
|2
k=
'. '^
200
10
15
50
20
100
150
200
Time (s)
FIG. 55liiustration of the effect of agitation on cooling curve and cooling rate
curve performance for a polymer quenchant.
^600-
UJ
K
.3
1400
s
tu
200
-WATER
20
40
60
TIME (Sec)
r - r I I I IT-T
80
> I I I I I I I
100
FIG. 56liiustration of cooling curve performance of a severely degraded aqueous polymer quenchant
compared to water and a fresh solution at the same concentration, bath temperature, and agitation.
CHAPTER
22: NON-LUBRICATING
PROCESS
Gradient
Quenchant
Analysis
BackgroundLiscic
designed a system for practical measurement, recording, and evaluation of quenching (cooling)
intensity u n d e r w o r k s h o p conditions, which expresses
quenching intensity by a continuous change in relevant therm o d j n a m i c functions during the entire quenching process.
This approach should be contrasted with the Grossmann Hfactor concept, which expresses quenching intensity with a
single value and which was shown earlier to be of limited
value in quantitatively represented quench severity when agitation is used.
All of the different cooling curve analysis methods discussed thus far utilize relatively small, usually 12.5 m m or 0.5
in diameter, round bar probes with a single thermocouple
placed at the geometric center. Such probes, while excellent
for quality control purposes, are of limited value for use under workshop conditions. The reasons include:
Because of its relatively small mass and low heat capacity,
these small probes will cool in about 10-30 s whereas an
actual workpiece of 50 m m (2.0 in) diameter will require
500-600 s to cool below 200C (392F) in the center of the
workpiece when quenched into an unagitated quench oil.
Therefore, to adequately model actual quench processes
under production conditions, a probe of similar mass and
dimensions is necessary.
The actual heat transfer coefficient during quenching of actual production parts may be simulated using a small cylindrical probe. However, the heat transfer coefficient during
nucleate boiling is heavily dependent on bar diameter [92].
The magnitude of this dependence increases with decreasing bar diameter below 50 m m (2.0 in). The dependence is
less pronounced for bar diameters greater than 50 m m (2.0
in). Therefore, for the same quenching conditions, the heat
transfer coefficient on the surface of a small diameter cylinder is quite different than that expected on the surface of
most production parts with diameters > 5 0 m m (2.0 in).
Important criteria for a cooling curve analysis system to be
utilized to model quench processes under workshop conditions should be applicable to: 1) a wide variety of quenchant
media including: water, brine, aqueous polymer solutions,
salt baths, quench oils, fluidized beds, and gas quenchants; 2)
a wide variety of quenching conditions including: different
bath temperatures, agitation rates, and fluid pressures; and
3) all quenching techniques including: direct i m m e r s i o n
quenching, interrupted quenching, martempering, austempering, and spray quenching.
The method to be reported here provides for recording of
thermodynamic functions during each test to enable the user
to ancdyze the peirticular quenching process of interest and
quenching conditions, to evaluate quenching intensity, and to
compare it with previously performed tests in other facilities
under different conditions. To do this, the user will establish
a database of quenching intensities of different systems
within the production facility. This database will provide the
user with input data for subsequent computer simulation of
FLUIDS:
STEEL
QUENCHING
TECHNOLOGY
623
dT
dx
624
HANDBOOK
(10-5 s)
Handle(optional
i
|.060"(1.5mm)
Adaptor
NANMAC Surface T
(990.6 mm)
(100.3 mm)
. 7.90"
(200.6 mm)
Thermocouple body
Mica insulation
Thermocouple w i r e
fiberglass
insulated leads
# 20 gage X 36."
Standard connector
attached.
(3-required-one
shown for c l a r i t y ) .
CHAPTER
22: NON-LUBRICATING
PROCESS
FLUIDS:
STEEL
QUENCHING
TECHNOLOGY
625
TCST2*-ncc
TCXTJi .CC
...4.--i-i-;-4
..i.j..j..j..i.4
-f-t"i"i-r-
IDO
2CX1
300
Time t
LOOO
20
Isl
(a)
SO
lOO
^^
i i u r f o c e l e m p e r o t u r e ; Ti t m p e r o l u r e l . S m m b e l o w l h s u r f o c c ;
t e m p e r o i u r e in t h e c e n t e r ot t b e probe
ZOO
Time
300
tsl
lOOO
T = s u r f a c e
f e m p e r o t u r e ; T; t m p e r o t u r e 1.5 mm b e l o w t h e s u r f a c e :
t e m p e r a t u r e in t h e c e n t e r of t h e p r o b e .
TESTzft . n c c
TCXTX-ncc
*.-.4...ii..i.^^
^^..-l-i-M.^^
^---<-t-t1
(b)
300
^oa
Time t IsJ
rc-
tc-n
Zi-r*
TCSTXC.nEC
Tttft.HCC
acoo
"e , ,
1 xooa
1 1 1 1 / 1.
..., I.. 1 ,.. .\
1 ,,,./.,
>*
^
T3
K laoo
_3
1 K.
i- l\
1
1 1 1i \
i
5.
: \
_
"o
(c)
XAJT{
1 ..l^^^^'i
too
aoa
>oo
400
9 6O
00
Tn
lac
1*01
>oo
xooo xxoo
T r o p r a t u r Tn
jiioo
I'Cl.
FIG. 58Graphical Display from Module 1 (TEMP-GRAD) when quenching the LISCIC/NANIVIAC probe into a 20C mineral oil bath
without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40C bath temperature and 0.8
m/s agitation rate (right row, vertically), (a) Measured and recorded temperature versus time, T = f{t); (b) Calculated heat flux density versus time q = f{t),; and (c) Calculated heat flux density versus surface temperature, q = f(T).
rcxTi.nee
(d)
l-^
>c-l
TE&TZtc .nee
rcsTi.ncc
oo
1 i....|.. .1.1.14-11...
0
i...-.i.-i..U.
70
"e**"
1 ::
-:
4-tiliy
-|
I--" -4"lili4i
4- ....... i..i.4.i.ii
-I-j-t'
. I
f-i-t
.^^^^.^^..Ji
*"-]-t-i
, A*o
i il
?,o
5
or-to
: : ;:
rlOO
1 j 1 iiji
i i l l ' Hi
-"J*
A
J
"j jtt'4-t-^i
to . . , . . . _ . t^Ifno
yJTi
= = * 1
i 1
.io
90
so
lOO
>t-'f!
. XOQ
Time I
(e) - .
Ul
>0
II-"
20
Jc-i
rcir.Ec
TcsTt.ncc
>3
ste>o
*
414f-
1 "1
.J
^^..
J..
...|...
\ \ J j . ....;1.....4..._..4
"!
~"r
:"V"-r
i-
...;... - I - -\
"l "
'T'"
. . .
"'"t
-T
>o
|v-f
to
too
\ \
4- -|
(f)
aoo
X:
-i--v
r^j^
r-Lj
sod
oo
i. i
1.00
too
>00
400
900
coo
700
FIG. 59Graphical display from Module 1 (Temp-Grad) when quenching the LISCIC/NANMAC probe into a 20C mineral oil bath
without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40C bath temperature and 0.8
m/s agitation rate (right row, vertically), (d) Calculated temperature difference versus time, AT= i(t); (e) Calculated integral of the
heat flux (heat extracted) versus time, Iqdt = f(t), and 1. Calculated cooling rates versus temperature, dT/df = 1{J,^.
2000
a ^ . ^ i Z B w;mK
o, . 595 W/m'K
gi800
1800
"6
J 1600
? 1600
"UOO
", I t O O
/A
;;i200
o
-^
o 1200
olOOO
o
o
* 1000
o
I BOO
~ too
200
V,
0,1
0.01
II nil
1 1 illill
10
600
>00
.
2000
Siaoo
Sl600
S: 1600
5
_.1t00
c
, f^
ni
0 1200
glOOO
o
800
0:
(b)
800
I 600
\
\
300
too
SOO
600
Tempcrature/C
700
600
ly
Uf
/
/
N
\
"t
200
\
200
JV
-, 1 0 0 0
o
*/
100
\ -^
I 1200
o
s\
too
a:
200
K^A
1800
d itOO
1 600
lb
0:
900
900
\
100
200
300
400
500
600
Temperature/*<;
700
^..
900
^*=^K
700
o
-~ 600
at
CI
500
\\
\\
\\
e too
0/
o 500
'
Q.
V
300
200
. simulated
' m<aasured
200
\
\ ,
100
800
900
800
100
10
Time /s
2000
0.1
0.01
( 1 mm 1 1 ( i i i i i ,
1 f I I m i^ - 1 i I I t i l l
1 f ((((If
1000
Time/ s
i1
1
200'
1 1 nun
100
1 1 / I f ^ / i
/ 1 llliii
(a)
800
(A
^800
0.01
0.1
10
Timc/s
100
1 1 IIIIII
1000
,1 1 IIIUJ ...1 i i i i i i i
0.01
0,1
I I 11 U.ll
10
1 1 IIIIII
100
1 1 IIIIII
1000
Time/s
FIG. 60Graphical display from Module 2 (HEAT-TRANSF), when quenching the LISCIC/NANMAC probe into a 20C mineral oil
bath without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40C bath temperature and
0.8 m/s agitation rate (right row, vertically), (a) Heat transfer coefficient versus time, a = f(t); (b) Heat transfer coefficient versus
surface temperature, a = f(r); and (c) Comparison of measured and simulated cooling curves for the center of the quench probe
(50 mm diameter).
CHAPTER
22: NON-LUBRICATING
C
Chemicot
Composition 0.38
Si
0.23
PROCESS
FLUIDS:
STEEL
Mn
P
Cr
S
0.64 0.019 0.013 0.99
Cu
0,17
QUENCHING
Mo
0.16
TECHNOLOGY
629
V
Ni
0,08 0.01
1000
Times
FIG. 61CCT diagram of AISI4140 steel with superimposed calculated cooling curves for surface (S), three-quarter radius (3/4 R), and center (C) of a round bar of 50 mm diameter.
HANDBOOK
500
1
log t tsl
1000
10|
""
(a)
500
388
^333
J 277
o
^ 222
.^^
166
/
/
55
i - i 1 mili-f-rnm
1.01
0.1
i i i iim
10
11
iiVu
J-t-W-lIU
100
1000
(b)
log t Is)
500
_388
"e 333
I 277
o
-222
166
55
0.01
1 1 llllll
1 1 1 IIITI
0.1
1 1 llllll
10
1 1 iii!i}~t_J-llllll
,100
1000
log t Isl
Title
Standard Method for Determination of Hardenability of Steel
Test Method for Precipitation Number of Lubricating Oils
Standard Test Method for Flash and Fire Points by
Cleveland Open Cup
Standard Test Method for Flash-Point by PenskeMartens Closed Cup Tester
(c)
CHAPTER
D 94
22: NON-LUBRICATING
PROCESS
FLUIDS:
D 6482
D 6549
D 6666
D 6710
E 112
E 131
E 349
E 686
E 930
E 979
E 1181
E 1382
STEEL
QUENCHING
TECHNOLOGY
631
OTHER STANDARDS
SAE J406
DIN 50191
IP 34
IP 71
IP 123
IP 160
IP 226
ISO 642
ISO 6743
ISO 9950
JIS K2242
Standard Liquor
H e a t T r e a t i n g O i l s - D e t e r m i n a t i o n of
C o o l i n g Ability
Industrial Quenching Oils-Determinat i o n of C o o l i n g C h e i r a c t e r i s t i c s - S i l v e r
Probe Test Method
REFERENCES
[1] Bates, C. E., Totten, G. E., and Brennan, R. L., "Quenching of
Steel," ASM Handbook-Volume
4 Heat Treating, ASM International, Materials Park, OH, 1991, pp. 67-120.
[2] Davis, J. R., ASM Materials Engineering Dictionary, ASM International, Materials Park, OH, 1992,
[3] Sverdlin, A. V. and Ness, A. R., "The Effects of Alloying Elements
on the Heat Treatment of Steel: Chapter 2," Steel Heat Treatment
Handbook, G. E. Totten a n d M. A. H. Howes, Eds., Marcel
Dekker, Inc., NY, 1997, pp. 45-91.
[4] Liscic, B., "Chapter 3-Hardenability," Heat Treatment of Steel
Handbook, G. E. Totten a n d M. A. H. Howes, Eds., Marcel
Dekker, NY, 1997, pp. 93-156.
[5] Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter 3-Cooling Curve Analysis," Quenchants and Quenching
Technology,
ASM International, Materials Park, OH, 1993, pp. 69-128.
[6] Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter 2-Measuring Hardenability and Ouench Severity," Quenchants and
Quenching Technology, ASM International, Materials Park, OH,
1993, pp. 35-68.
[7] Winchell, P. G. and Cohen, M., "Strength of Martensite," ASM
Transactions, Vol. 55, No. 2, June 1962, pp. 347-361.
[8] Houdremont, E., "Strength of Martensite," ASM
Transactions,
Vol. 55, No. 2, June 1962, pp. 347-361.
[9] Hornbogen, E., "Strength of Martensite," ASM
Transactions,
Vol. 55, No. 2, June 1962, pp. 347-361.
[10] Leidenfrost, G. J., "De Aqua Communis Nonnullis Tractus,"
Original from 1756, in C. Waves, Inemational Journal of Mass
Transfer, Vol. 9, 1966, pp. 1153-1166 (trans.).
[11] Yamanouchi, A., "Effect of Core Spray Cooling in Transient
State after Loss of Cooling Accident," Journal of Nuclear Science
and Technology, No. 5, 1968, pp. 547-558.
[12] Duffly, R. B. and Porthouse, D. T. C , "The Physics of Rewetting
in Water Reactor Engineering Core Cooling," Nuclear Engineering and Design, Vol. 3 1 , 1973, pp. 234-245.
[13] Kunzel, T., "Einfluss der Wiederbenetzung auf die allotrope
Modifikationsanderung tauchgekiihlter Metallkorper," Dissertation, Faculty for Mechanical Engineering of the Technical
University of Munich, 1986, 138 pp.
[14] Hein, D., "Modellvorstellung zur Wiederbenetzung d u r c h
Fluten," Doctoral Thesis, Technical University of Hannover,
1980, 182 pp.
[15] Ladish, R., "Untersuchung der minimalen Filmsiedetemperaturen auf keramischen u n d metallischen Leitem," Report of
"Kemforschungsstelle Karlsruhe," KfK-2970, 1980, 96 pp.
[16] Stitzelberger-Jakob, P., "Hartevorherbestimmung mit Hilfe des
Benetzungsablaufes beim Tauchkiihlen von Stahlen," Dissertation, Faculty for Mechanical Engineering of the Technical University Munich, 1991, 160 p p .
[17] Tensi, H. M. and Lainer, K., "Wiederbenetzung und Warmeilbergang beim Tauchkiihlen in Hochleistungsolen," HTM, 1997, 52,
pp. 298-303.
[18] Tensi, H. M., "Wetting Kinematics," Theory and Technology of
Quenching, B. Liscic, H. M. Tensi, and W. Luty, Eds., SpringerVerlag, Berlin, 1991.
[19] Tensi, H. M., Stich, A., and Totten, G. E., "Fundamentals of
Quenching," Metal Heat Treating, Mar/Apr 1995, pp. 20-28.
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[68]
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[83]
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[86]
[87]
[88]
[89]
Centre Engineering Group Specification, Wolfson Heat Treatment Centre, Birmingham, UK, 1982.
Tensi, H. M., "Methods and Standards for Laboratory Tests,"
Theory and Technology of Quenching: A Handbook, B. Liscic, H.
M. Tensi, and W. Luty, Eds, Springer-Verlag, Berlin, Germany,
1992, p p . 208-219.
Guisbert, D. A., "Precision and Accuracy of the Cooling Curve
Analysis Test Method," Proceedings of the 16th ASM Heat Treating Society Conference and Exposition, Cincinnati, OH, 19-21
M a r c h 1996, ASM International, Materials Park, OH, p p .
435^42.
Guisbert, D. A., "Correlation with Magnetic Quenchometer to
Cooling Curve Analysis Technique," Proceedings of the 16th ASM
Heat Treating Society Conference and Exposition, Cincinnati,
OH, 19-21 March 1996, pp. 4 5 1 ^ 6 0 .
Guisbert, D. A. and Moore, D. L., "Influence of Test Conditions
on Cooling Curve Test Results," The 1st International
Automotive Heat Treating Conference, R. Colas, K. Funatani, and C. A.
Stickels, Eds., ASM International, Materials Park, OH, 1998, pp.
449-455.
Tensi, H. M. and Stich, A., "Characterization of Polymer Quenchants," Heat Treating, May 1993, pp. 25-29.
One source of the "dynamic boat propeller" Part #1472, is Fa.
Robbe. D-36355, Grebenhain, Germany.
Hilder, N. A., "The Behavior of Polymer Quenchant," PhD Thesis, University of Birmingham, UK, 1988.
Tagaya, M. and Tamura, I., Technol. Rep., Osaka University, Vol.
7, 1957, pp. 4 0 3 ^ 2 4 .
Boyer, H. E. and Cary, P. R., Quenching and Control of Distortion, ASM International, Materials Park, OH, 1988, p. 169.
Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter
6-Quench Bath Maintenance," Handbook of Quenchants and
Quenching Technology, ASM International, Materials Park, OH,
1993, pp. 191-238.
Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter
6-Quench Bath Maintenance," Handbook of Quenchants and
Quenching Technology, ASM International, Materials Park, OH,
1993, pp. 191-238.
Horton, B. R. and Weetman, R., "Quench Oil Recovery," Heat
Treatment of Metals, Vol. 2, 1984, pp. 49-51.
Watanabe, H. and Kobayashi, C , Lubrication Engineering, Vol.
38, No. 8, 1978, pp. 421-428.
Hasson, J. A., "Preventative Maintenance for Quenching Oils,"
Industrial Heating, Sept. 1981, pp. 21-23.
Boyer, H. E. and Cary, P. R., Quenching and Control of Distortion, ASM International, Materials Park, OH, 1988, pp. 4 4 ^ 5 .
von Bergen, R. T., "The Control and Monitoring of Polymer
Quenchant Systems," Heat Treatment of Metals Vol. 2, 1991,
pp.37^2.
Srimongkolkul, V., "Is There a Need for Really Clean Oil in
Quenching Operations?," Heat Treating, December 1990, p p .
27-28.
Bates, C. E. and Totten, G. E., "Quantifying Quench-Oil Cooling
Characteristics," Advanced Materials & Processes, 1991, No. 3,
pp. 25-28.
Totten, G. E. and Webster, G. M., "Quenching Fundamentals:
Maintaining Polymer Quenchants," Advanced Materials and Processes, Vol. 149, No. 6, 1996, pp. 64AA-64DD.
Mueller, E. R., "Polyglycol Quenchant Cleanliness: Are There
Benefits," Heat Treating, October 1993, pp. 24-27.
Jarvis, L. M., Blackwood, R. R., and Totten, G. E., "Thermal Separation of Polymer Quenchants for More Efficient Heat Treatments,"/nrfwiina/Heafrng, November, 1989, pp. 23-24.
HiU, E. C. and Hill, G. C , "Biodegradable After Use But Not In
Use," Industrial Lubrication & Tribology, Vol. 46, No. 3, 1994,
pp. 7-9.
Hill, E. C , "The Significance and Control of Microorganisms in
MNL37-EB/Jun. 2003
the
procedures and methods used to determine the quantity of liquid in a storage tank, marine vessel, road transport vehicle, or
a rail tank car. In determining the quantity of the liquid in the
container, there may be other things in the container that detract from determining the quantity of useable petroleum or
petroleum products. They do take u p space in the container
and therefore must be desilt with as peirt of any measurement
procedure. These can include water, sediment, sludge, rust
scale, and sand to n a m e just a few. As used here, petroleum
refers to crude oil, therefore the continuous reference to
petroleum and petroleum products. Petroleum products as
used here are the liquid stocks (e.g., naphtha, kerosene, fuel
oils) derived from the refinery processes from crude oil. It is
important to know the total of the liquids and solids in a tank
to prevent a tank from overflowing during a receipt. However,
the more exacting science of static petroleum measurement is
concerned with determining a n accurate measure of the
quantity of petroleum Eind petroleum products used in the
purchase, sale, or inventory control of the commodity. This
section on static petroleum measurement will deal primary
with manual gauging techniques and the related sampling
and quality tests needed to obtain accurate petroleum and
petroleum product quantity measurements. Automatic tank
gauging, not discussed in this chapter, relies on the manued
gauging methods for calibration purposes. Newer techniques
for leak detection combine a form of static petroleum measureraent with inventory control to assure that tanks and lines
storing and moving the products are tight. Leak detection
procedures primarily combine automatic gauging methods
with computer programming. This chapter is designed to explain h o w to accurately m e a s u r e the petroleum and
petroleum products, why certain procedures are necessary,
sampling and testing processes, and the basics of converting
these measures into quantity m e a s u r e m e n t s used in the
industry.
635
Copyright'
2003 by A S I M International
www.astm.org
636
HANDBOOK
REFERENCE
POINT
READING
GAGING TAPE
GAGING HATCH
REFERENCE
POINT
READING
GAGING TAPE
/ GAGING HATCH
OUTAGE
TAPE
CUT
TANK
SHELL
LIQUID
LEVEL
BOB
CUT
TANK
SHELL
LIQUID
LEVEL
INNAQE
INNAGE
OUTAGE
637
A
r-B
II
r-ll
IS
'OUTAGE TAPE-
-H
0
U
r-ll
in
\f
\ /
10"
r-J
INNAGEtOa
SCALE
ZERO
EXTCNSION
OUTACe
SOB
PIAIM
OUTASE
SOB
DEEP
GROOVED
OUTAGE
BOS
bC^
the top of the outage bob where the tape latches onto the
bob. The bob will then be graduated from the top of the bob
downwards. An extension outage bob is designed to be attached to an innage tape. Below where the zero point would
be if an innage bob was attached is a metal extension. Readings begin at the zero point and increase below the zero
point. When using an outage tape, readings on the bob below the zero point are added to the reading tciken at the reference gauge point. Treat the tape properly as the linear
measure is a critical step in getting the quantity accurate.
Kinks in the tape are to be avoided. Tapes that have been
spliced together shall not be used when gauging for custody
transfer purposes as it may change the measurement above
the splice point. A bob showing wear at the tip may affect
gauging accuracy.
Where primarily water and small amounts of soft sediment
may be the contaminant, a water gauging bar may be used to
measure the water that has settled to the bottom of the tank.
One drawback is if the bar is not attached to a corresponding
tape, it is not possible to obtain a reading of the reference
height gauge. Therefore if the bar did not hit the datum plate
or floor of the tank, the gauger will not know if the bar actually reached the datum plate or the floor.
A new tape and bob should be checked before use. Inspect
638
MANUAL
HANDBOOK
the entire length to assure that the n u m b e r s are clcEirly indicated in the correct order and the graduation meirks between
the numbers are present. Tapes should be made of steel or
corrosion resistant material. Meike sure the snaps and eyes
between the tape and the bob afford for proper fit and accuracy for measurement purposes. Tapes and bobs should be
checked daily w h e n in use. Check the tape for kinks and
splices, which would make the apparatus unsuitable for accurate gauging. The tape and bob fittings should provide for
an accurate measure. Also ensure that the bob tip has not
been worn down or damaged, which would create another
measurement error. Lastly, make sure the tape and bob Eire
fit for the purpose to be used. A tape and bob shall not be introduced into another product where the residue on the tape
and bob would contaminate the product to be measured. A
s t a n d a r d operating procedure to r e m e m b e r is t h a t crude
oil/residual fuel oil tapes should not be used to measure distillate products. Many specialty petrochemical products are
very sensitive to extremely small levels of contamination. Either separate tape and bobs may be necessary or the tape and
bob may require special cleaning before use.
There are still several items needed before a linear measurement is m a d e at the tank. Remember several other factors m u s t be accounted for to obtain accurate petroleum
measures. The first to be discussed is what is needed in determining the temperature of the product to be measured. A
thermometer or temperature measuring device is required.
The industry standard for reference is API MPMS Chapter 7,
Method of Measuring the Temperature of Petroleum and
Petroleum Products. The temperature of the product is critical to correct the measured quantity to the standcird temperature.
The temperature in a tank may vary greatly, especially for
crude oil and residual fuel oils that are heated to higher temperatures to maintain fluidity and preventing gelling of the
product. The heating coils are near the floor and heat convection helps swirl the product in the tank. It may not, however, provide for a uniform t e m p e r a t u r e within the tank.
Even distillate products in tanks have t e m p e r a t u r e variations. After distillation and condensation of the product, it
enters a storage tank. If measurements are made soon after
that, there may be a temperature gradient within the tank.
The equilibration of the product has not occurred. Another
factor affecting the temperature within a tank is the external
environmental conditions. If gauging is performed on a side
of the tank were the sun is shining, it may indicate a higher
temperature than if the gauge was taken on the shady side of
the tank. Rapid ambient temperature cheinges may also increase the t e m p e r a t u r e variation within a tank. Product
within the tank may not have h a d a chance to equilibrate. Increased temperature readings are advisable where temperature stratification is found within a tank.
The temperature within the tank is measured using a thermometer or an electronic temperature probe (thermoprobe).
Thermometers must meet ASTM E l , ASTM
Thermometers
specifications for the range of temperatures cinticipated in the
product to be measured. Thermometers shall be calibrated at
least yearly against a thermometer traceable to a certified national standard thermometer. In the U.S., the Standard body
is the National Institute of Standards and Technology (NIST).
Thermoprobes rely on electronic instrumentation to provide
639
CLAMP.
ASTMTHERMOMETER
CORROStONRCSBTANT
METAL
CD
CUP CASE
FIG. 3Cup case Thermometer.
MAX.p
FIG. 5Armored cup
case.
ASTM
THERMOMETER
FLUSHING CASE
640
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
representative sample of the product to be sampled. Distillate products and finished lubricating oils from a single
batch are normally considered to be homogenous. That is, a
sample from anywhere in the product should be uniform
and, in theory, represent the product. In reality, slight
changes in the refining or manufacturing process may cause
some variation in the product. A permitted testing variation
on specified parameters determined by prior agreement
would provide for agreement that the batch tank is deemed
homogeneous for quality and quantity procedures. Not discussed in this chapter is the automatic in-line sampling procedures covered by API MPMS Chapter 8.2 (ASTM D 4177),
Automatic Sampling of Petroleum and Petroleum Products.
While previously used to determine the quality of crude oil
and residual fuel oils in the past, they are increasingly being
used for automotive gasolines, aviation fuels and diesels
both for quality control purposes and environmental regulation compliance.
The tools needed for manual sampling include a sample
bottle(s) and sampling cage or a weighted beaker (Figs. 6 and
7). A sample receiver or receptacle is a container in which all
sample bites are collected during the sampling operation. The
n u m b e r of bottles and sample receivers needed must be determined before going out to sample. Bottles and weighted
beakers must be properly cleaned so as not to contaminate the
sample before taking the samples. Sample bottles and containers may be clear or brown glass. Ccins used must have their
seams soldered on the exterior surfaces to preclude contamination with flux used in their manufacture. Polyethylene unpigmented linear plastic bottles can be used for gas oil, diesel
oil, fuel oil, and lubricating oils. These plastic bottles should
not be used for gasoline, aviation jet fuel, kerosene, crude oil,
white spirit, medicinal white oil, and special boiling-point
products unless testing indicates there is no problem with solubility, contamination, or loss of light ends. The container closure must be clean and ensure a good tight seal. Loss of light
ends have an effect on the density of petroleum and petroleum
products, which is an important element for petroleum mea-
1-Lllre (1 qt.)
Sample Weighted Cage
(can be (abricated
to HI any size bottle)
CHAPTER
Copper
handle
hitah
Copper
wire
lugs
Sheet
lead
Cork arrangements
Beaker
23: STATIC
PETROLEUM
MEASUREMENT
641
When any sample is taken where the loss of volatile components would affect the sample result, the procedures in API
MPMS Chapter 8.4, ASTM D 5842, Standard Practice for
Manual Sampling and Handling of Fuels for Volatility Measurement, should be used. The object is to take and handle a
sample without losing the light hydrocarbons. For instance,
when a density is to be run, the loss of the light ends will increase the density (lower the API Gravity) of the tested sample. This is t u r n m a y affect the volume correction factor
(VCF) used in determining the net quantity of fuel at the standard temperature. Basic technique requires the sample container to be filled to the 80% fill level, capped quickly, kept
cool, and delivered to the laboratory for testing promptly.
Volatile samples taken from taps should use an extension
that can reach close to the bottle of the sample container.
This will preclude splashing and the generation of vapors
leading to light end loss. Brown or a m b e r bottles or sample
cans must be used when taking samples of petroleum products that are light sensitive. Failure to use the appropriate
container could cause changes to the quality of the product
before testing of the product is accomplished. This could lead
to inappropriate results that may affect the quantity determination also.
When taking spot samples to be composited for a representative sample, a standard way to take samples is as follows: For tanks over 1000 barrels that contain more than 15
ft. of oil, an upper, middle and lower sample are taken and
combined in equal volume to make a composite sample. For
tanks over 1000 barrels which contain between 10 and 15 ft
of oil, a middle sample from the top half and a middle sample from the bottom half are taken and composited. A single
sample is taken normally when the level of the oil is less than
ten feet. For tanks smaller than 1000 barrels, either a single
sample or multiple spots can be used. Again make sure the
parties involved agree on the t3rpes of samples in advance of
the sampling process. Other spot samples can be designated
or taken upon mutucd agreement for custody transfer purposes. A bottom sample is one that obtains material from the
bottom surface of the tank or container at its lowest point. A
Hatch
r
rj
TH
Tank
contents
Outlet
15 cm (6")
Top sample
Upper sample
Upper third
- Middle sample
Middle third
Lower sample
Outlet sample
Lower third
Bottom sample
NOTE 1TTie location shown tor the outlet sample appfes only to tanks with
side Qutltta. It doea not apply whaa ttn outiat comas from the tkxx of the tani( or
turns down into a sump. Bottom sample location must tie specified.
NOTE 2Samples shoiid t otitained from within solid stand pipes as the
materials normaiiy not representative of the material in the tanit at that point.
FiG. 8Sampiing terms.
642
HANDBOOK
bottom water sample is a spot sample of free water taken beneath the petroleum contained in a tank or marine vessel
tank. These last two samples are used as indicators of the
contamination accumulating on the bottom of a tank, to determine where water came from (process water or sea water),
or to detect bacteriological or fungal growth.
Combining agreed upon spot samples is one acceptable
method as is testing individual spot samples and averaging
the results. A composite spot sample is a blend of spot samples
mixed volumetrically proportionally for testing. For instance
a multiple-tank composite tciken from marine vessel compartment tanks is a mixture of individual samples from several
compartments, each of which contains the same grade of
petroleum material. The mixture is blended in proportion to
the volume of material in each compartment (weighted average method). API MPMS Chapter 8.3, ASTM D 5854, Standard Practice for Mixing and Handling of Liquid Samples of
Petroleum and Petroleum Products, should be used for this
process. This blending should be performed in a laboratory.
Some tests may be made on the spot samples before blending
and the results averaged.
Two types of samples can be taken that represent the column of petroleum or petroleum product in the tank. Each
has drawbacks as to its being a representative sample. They
are used primarily for homogeneous product. First is an alllevel sample. An all-level sample is taken by submerging a
stoppered bottle or beaker as near as possible to the draw-off
level, and then opening the sampler, and raising the sampler
at a uniform rate such that it is about three-fourths full as it
emerges from the liquid. A running sample is one obtained by
lowering an unstoppered beaker or bottle from the top of the
oil level to the level of the bottom of the outlet connection and
returning it to the top of the oil at a uniform rate of speed so
that the beaker or bottle is about three-fourths full when it
breaks the surface of the oil. Both a running sample and an
all-level sample may not be a true representative sample, because the tank volume may not be proportional to the depth
or because the operator may not be able to maintain the variable rate required for proportional filling. The rate of filling
is proportional to the square root of the depth of immersion
also affecting sample representativeness. The lower the
beciker or bottle, the faster liquid flows into the beeiker or bottle.
Pipeline samples can be of several t3rpes. Automatic samplers are covered by API MPMS Chapter 8.2 (ASTM D 4177),
Automatic Sampling of Petroleum and Petroleum Products.
Automatic samplers are designed to take a representative
sample from liquid flowing through a pipeline. It consists
generally of a probe, an extracting mechanism, a controller
that determines when to extract the sample bites, and a sample receiver. Flow proportioning samplers adjust to product
volume changes resulting from changes in the flow rate. This
is the best way to get a representative sample from a pipeline.
Another tj^e is a time controlled automatic sampler. It takes
a sample bite at preset time intervals. Manual samples from
pipelines, sometimes called drip samples, can be taken. A
valve is cracked leading to a sample receiver so that over the
duration of the movement, product slowly fills the sample receiver so that it fills the container over the determined period. This does not provide for a truly representative sample.
Pipeline spot samples are another tj^e of manual samples.
They represent the product at a particular moment of sampling. Several pipeline spot samples can be combined to
make a pipeline composite sample to represent the product
in question. The number of samples required should be
agreed between buyer and seller when used for custody transfer purposes. Changes in flow rates have little effect on the
amount of sample being taken. Care must be taken to preclude overfilling samples taken from a pipeline. To get a truly
representative sample from a pipeline, the product must be
flowing at a turbulent flow rate. Turbulent flow promotes
product and contaminants distributed equally throughout
the pipeline cross section. When product has a laminar flow,
there is a faster section moving above a slower section. Contaminants such as sediment and water can settle to the lower
section of the pipeline or at the low points. Samples taken at
laminar flow tend not to be representative.
Before climbing the tanks, determine if control of the volumes in the pipeline are required. For custody transfer purposes, the condition of fill of the pipelines to be used must be
known, both before and after the movement. If the pipelines
are stated as full, validate by pressure or other means that the
line is full. One reference for this operation can be found in
API MPMS Chapter 17.6, Guidelines for Determining the Fullness of Pipelines Between Vessels and Shore Tanks. If empty,
confirm as best as possible. If there is a difference in the condition of the pipeline fill before and after a movement, the differences must be accounted for in the product calculations.
It's time to climb that tank or go to the marine vessel to
take samples and to gauge the tanks. What is the proper order to perform the water cut, product gauge, temperature,
and sampling? If water cut is done first, the oil column above
the water layer may become contaminated. This would lead
to erroneous results coming from the contaminated samples.
Therefore the order should be to take the samples first.
Which samples should be taken? For the same reason, taking
the bottom water cut measurement, samples are taken starting from the highest in the tank. If a top sample is needed,
take that first. Then the upper, middle, lower, outlet, and bottom samples. If after these samples an all-level or running
sample is required, take these after the spot samples. The order of taking the samples is the same from compartments on
a marine vessel. When homogeneous product is on board a
vessel, a single middle spot sample may only be required. At
other times the individual compartment may only require an
all-level sample. However, when crude and heavy fuel oils
that contain water and sediment in a non-homogeneous
manner are sampled, several spot samples may be required
and/or a running or all-level sample. Samples are taken and
properly labeled with a marker that will not be affected
should the oil splash or be introduced onto the label. The label must be affixed to the sample bottle or containers immediately after the sample is taken. This is extremely important
when several different samples are taken from one tank. Always check that any labels, especicilly preprinted ones, are
put on the correct sample. Ensure that all relevant details are
on the sample label. No one wants to climb a tank a second
time because the results from the testing indicate a problem.
Side tap samples along the staircase can be taken either going up or going down. However, if samples are taken on the
way up, it will make the carrier weigh more as you ascend the
staircase. Recommend tEiking the samples on the way down
643
644
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
surement. First, gauge the free water, first getting the reference height estabhshed once. This is only done once. Then
proceed on with gauging for the total height of the liquid in
the tank. SecondPerform b o t h the free water and total
height of the liquid simultaneously. Assure that an agreement
has been reached on this point between the buyer and seller
or as a company policy and then advise the ganger and/or independent surveyor of the agreed procedure.
Continuing on with the innage method using the second
school of thought, raise the tape until the product cut can be
seen. Read the location of the product, referred to as a cut, to
the nearest millimeter (or 1/8 in). Record the product cut.
Raise the tape and bring the bob to be viewed. Be careful
when bringing the bob u p and out so as not to disturb the water finding paste. Read the water cut and record it also. For
tanks with crude oil and heavy fuel oils, it may be necessary
to rinse the oil off the bob to view the water cut. Use an appropriate solvent to clean the bob. Take care in rinsing with
a solvent so as not to push the water line u p or down. Be environmentally friendly when performing these actions. Additionally, do not blow or wipe the petroleum or petroleum
products off the bob as this too may distort the water cut and
thereby give incorrect readings.
Perform the gauging actions again. They should be identical. If not try once more. If all three are within 3 m m (1/8 in)
of each other and two are identical, then the two identical
readings are reported as the official gauge. If not within 3
m m (1/8 in), continue gauging until three consecutive gauges
are within 3 m m (1/8 in) of each other. If none are identical,
averaging of the gauges m a y be permitted. Averages are to
the nearest millimeter or 1/8 in, depending on the unit being
used. Other a r r a n g e m e n t s are permitted by agreement.
Smcdler tanks or tanks gauged in windy conditions may preclude the level of accuracy desired as the product level in the
tank is unstable. Small waves are created by the wind and the
differences in the wave heights between each measurement
create the inaccuracy in measuring the product height. Once
completed it is time to return to the office to perform the calculations. However, before coming down off the tanks, if several people are gauging or witnessing the gauging, agree on
the gauges before coming down. This precludes disagreements after the fact.
Most marine measurements are not used for custody transfer purposes, but primarily for inventory control purposes.
Let us look at performing a n outage or ullage gauge. This is
used for most heavy dark oils and is the preferred method for
marine vessel gauging. The basic difference is that the bob
does not reach the bottom of the tank. When using an outage
tape and bob, ground the tape and bob to the tank. Lower the
tape and bob into the product. Lower the bob into the product only slightly. Remember, the object of a n outage tape and
bob is that the product reading is on the bob between the zero
cmd the plus side (lower end of the bob). At the reference point,
have the tape come to a whole increment, either centimeter or
inch. Note the distance the tape has been lowered into the
tank. Bring the tape back to the surface emd read the bob. If
within the correct reading zone, the bob reading is added to
the distance the tape was measured as being lowered into the
tank. Unfortunately, there are occasions when the gauger for
any n u m b e r of reasons lowers the tape too far. When you
bring the tape and bob back up, you can read a measurement
645
646
MANUAL
HANDBOOK
layered on the bottom of a marine vessel, trim and list corrections are not applied. Rather for this layer, it can be considered as layering the bottom of the vessel as a solid sheet.
Use the strapping chart to obtain this quantity as if the vessel
were on even keel.
Nov*? for the really easy pEirt, the calculations back in the
shore office or the ship's office. The calculation procedures
are governed by API MPMS Chapter 12.1, Calculation of
Static Petroleum Quantities. We will be taking the linear measurements and converting them to volumes now. In doing so,
we need to define some terms.
Total Observed Volume (TOV) is the volume found from the
measured total liquid height. It includes all petroleum liquids, water, and sediment in the product, free water, and
bottom sediment.
Free Water (FW) means all free water and bottom sediment.
This is the water cut measurement converted to a liquid
volume. It includes the bottom sediment a n d sludge, if present, as the measurement includes it. Additionally, the free
water and the sediment and sludge have different volume
correction factors from petroleum products.
Gross Observed Volume (GOV). This is the total volume of
petroleum liquids and sediment and water in the product
less the free water volume. (GOV = TOV FW).
The Volume Correction Factor (VCF) is correction for temperature of the liquid to a standard temperature. It may
also be referred to as the Correction for Temperature of the
Liquid or CTL.
Gross Standard Volume (GSV) is the GOV times the VCF
(GOV X VCF).
Net Standard Volume (NSV) is the total volume of all
petroleum liquids, excluding S & W and free water, corrected by the appropriate VCF. (G.S.V. - S & W = N.S.V.)
For sales, this is the value required. However for inventory
purposes and storage, shipping, and handling, we need to
know and understand the other definitions.
A tank may be able to contain the NSV, but not the TOV.
Remember that petroleum products expand when the temperature of the product increases. Leave enough room in the
tank for said expansion. Volumes in pipelines also expand
and contract. Static lines may not be full if several expansion/contraction cycles caused by day/night t e m p e r a t u r e
variations have occurred. Some product may have moved to
another tank through the pressure relief system.
From the laboratory tests we receive the density at 15C (API
Gravity at 60F) and the tested S & W contained in the product
as a percent reading. Performing a density or API Gravity test,
follow the procedures in API MPMS Chapter 9 Density Determination. Several ASTM test methods are D 5002 (Crude Oil
by Digital Density AnjJyzer), D 4052 (Liquids by Digital Density Meter), and D 1298 (Hydrometer Method). The basic principle for the manual method is to take the sample and place it
in a hydrometer cylinder. Make sure all air bubbles Eire eliminated from the top of the liquid. Use a hydrometer with an appropriate scale reading. Some hydrometers have a thermometer as p a r t of the hydrometer. Otherwise, a separate
thermometer is required. It is best to have the product being
measured equilibrate with the ambient temperature as it precludes temperature drift during the measurement. Especially
in the field, this may not also be possible. Lower the hydrometer into the liquid to a position close to where the hydrometer
would float. Getting liquid above this position on the hydrometer stem can result in slightly inaccurate readings as the liquid may be retained above the level of the product depressing
the hydrometer slightly. Spin the hydrometer to disperse air
bubbles on the bottom of the hydrometer. Allow the hydrometer to come to rest. Read the hydrometer to get the observed
density. As quickly as possible read the thermometer to obtain
the temperature that the observed density was taken. When using separate hydrometer and thermometer, remember to allow
the thermometer time to equilibrate in the liquid before reading it. To convert density at observed temperature to density
(API Gravity) at standard temperature, follow the procedures
in API MPMS Chapter 11.1 (ASTM D1250 or IP 200) and the
appropriate table designations. There are tables for specific
range of products. Table A is used for crude oil and naphtha
based aviation turbine fuels. Table B is used for most other
petroleum fuels. Table D is used for lubricating oils. For those
that wish to perform the coefficient of expansion tests each
time a VCF is needed for a specified product, use table C. Tests
for S & W include centrifuge method, water by distillation, water by Karl Fischer and Sediment by extraction. Round values
to the precision required as stated in API MPMS Chapter
12.1.1, paragraph 6.2 and Table 1. You can do the calculations
or a computer may be able to do them if programmed appropriately Eind the correct numbers are entered into it.
For shore tanks, take the total liquids gauged measurement
and go to the strapping chart. The volume obtained is the
TOV. For marine vessels, the trim and list factors must be applied to t h e total liquids gauged. This will b e contained
within the strapping chart. Based on the trim and list, the
strapping chart will advise you to add or subtract some linear
measurement to the observed reading. From this correct linear measurement, obtain the TOV from the strapping chart.
Whether a shore or marine tank, free water is normally obtained as an innage value. Look u p the total volume of free
water (remember this includes the b o t t o m sediment) and
record this volume as FW. There may be occasions when the
level or type of free water and sediment necessitated an outage gauge. If the chart is in innage measurements, convert
the outage gauge to a n innage gauge and look u p the FW volume. If the volume of free water and b o t t o m sediment is
great, using the outage gauge table may be appropriate. On
marine vessels, remember trim and list corrections when the
bottom layer is fluid.
For true corrections, the correction for temperature of the
shell (CTsh) is needed. This compensates for the expansion
and contraction of the tank shell caused by the temperatures
of the product and the ambient air. Tanks are strapped assuming a specified temperature range. The CTsh is used to
bring the liquid volume back into calibration. In accordance
with API MPMS Chapter 12.1.1, Section 9.1.3 the adjustment
used is CTsh = 1 - 1 - 2aA T + a^\^. The symbol a equals a linear coefficient of expansion of the tank shell, with Appendix
B-2 containing several coefficients for various metals. The AT
equals the Tank Shell Temperature Base Temperature. The
base temperature is the temperature that the strapping chart
was calibrated at. The tank shell temperature for an insulated
tank is assumed to be the temperature of the product. For
noninsulated tanks, use the formula in Appendix B of API
MPMS Chapter 12.1.1.
Calculations for a floating roof tank include a floating roof
CHAPTER
adjustment (FRA). Remember that a floating roof displaces
product due to its weight. Some strapping charts contain the
formula for this adjustment. Others just provide the weight of
the roof and the FRA must be calculated. Check this carefully
w h e n performing the CcJculations. The basic principle is that
the roof correction = weight of the roof / (density X VCF).
The displacement a m o u n t was also determined at a specified
density and part of the correction includes an adjustment for
the difference between the observed density and the density
used in the calibration, most likely 15C or 60F. Now we can
determine the GOV.
For shore tanks, the GOV is the [(TOV - FW) X CTsh]
FRA. The FW is deducted before the FRA because water and
s e d i m e n t compress differently t h a n petroleum a n d
petroleum products. For most purposes, it is assumed not to
have a compression factor and therefore is ignored in the calculations. For marine vessels the GOV = (TOV Trim/List
Corrections) FW. This now gives the total liquid volume to
be sold or moved. The next step is to convert this volume at
an observed temperature to a volume at the standcird temperature, referred to as the Gross Standard Volume (GSV).
The GSV = GOV X VCF. For distillate fuels and lubricating
oils, the trace amounts of entrained water and sediment are
accepted without adjustments to the quantity. Therefore for
distillates and lubricating oils, we also have the Net Standard
Volume (NSV). In fact for these products, we normally do not
refer to a GSV, only the NSV in the CcJculations.
However, in the case of crude oil and some heavy heating
oils, a deduction is made for the amount of S & W contained
in the product. From the laboratory, the water and sediment
value is provided as a percentage. The NSV is therefore the
GSV times a correction for the sediment and water (CSW).
To obtain the CSW, convert the sediment and water percentage into a decimal and then subtract that value from one
(1.0000). For example, if the sediment and water contained in
a crude oil is 4.25%, converting to a decimal gives 0.0425.
Then (1.0000 - 0.0425) = 0.9575 as the CSW. Then the
NSV = GSV X CSW. Conversely, use the converted sediment
and water decimal and multiply it times the GSV. This will
give a volume of sediment and water contained in the GSV.
Then the NSV = GSV minus the volume of sediment and water CcJculated. This concludes volume calculation.
Lastly, many users of this information also require the apparent mass or weight in air of the product. For this we use a
Weight Conversion Factor (WCF), which is a relationship between the density of the product and its weight in air. There
are m a n y tables contained in Volume XI a n d XII of API
MPMS Chapter 11.1 that give these relationships. There are
also numerous methods to convert from volume to weight. It
is preferable to approach the ceJculation process from the
simplest, most direct direction. Using different approaches
results in slightly different weights. It is best to obtain agreement on the conversion process as part of the agreement between buyer and seller or as a company policy for internal
use. This will preclude problems by those performing the calculations or inventory control reviews.
The order of calculation is TOV to GOV to GSV to NSV to
Weight in Air. The exception is when the tank measurement
is by a direct mass method, for example a hydrostatic tank
gauge. The reading is already in mass units and the calculations are performed within the little black box. All that is
23: STATIC
PETROLEUM
MEASUREMENT
647
GOV
CTsh
10,250,581 USG
VCF table 6A x 0.9969
GSV
10,218,804 USG
Note: (S = Standard temperature, in this example it is 60F)
CSW (1-0.0225)
0.9775
times
equals
NSV
9,988,881 USG
Divided by 42 USG/barrel equals
237,830.50 barrels
times
WCF (table 11)
0.13 808 long
tons/barrel
Long Tons
648
HANDBOOK
ASTM STANDARDS
No.
D 1250
D 1298
D 4052
D 4057
D 4177
D 5002
D 5842
Title
Petroleum Measurement Tables
Hydrometer Method
Liquids by Digital Density Meter
Manual Sampling of Petroleum and Petroleum
Products
Automatic Sampling of Petroleum and Petroleum
Products
Crude Oil by Digital Density Analyzer
Sampling and Handling of Fuels for Volatility
Measurement
D5854
El
OTHER STANDARDS
American Petroleum Institute (API) Manual of Petroleum
Measurement Standards (MPMS), Chapter 3.1
API MPMS Chapter 7, Method of Measuring the Temperature of Petroleum and Petroleum Products
API MPMS Chapter 8.1, Manual Sampling of Petroleum and
Petroleum Products
API MPMS Chapter 8.2, Automatic Sampling of Petroleum
and Petroleum Products
API MPMS Chapter 8.3, Standard Practice for Mixing and
Handling of Liquid Samples of Petroleum and Petroleum
Products
API MPMS Chapter 8.4, Standard Practice for Manual Sampling and Handling of Fuels for Volatility Measurements
API MPMS Chapter 10, Density Determinations
API MPMS Chapter 11.1, Physical Properties Data
API MPMS Chapter 12.1, Calculation of Static Petroleum
Quantities
API MPMS Chapter 17.4, Method of Quantification of Small
Volumes on Marine Vessels (OBQ/RBOB)
API MPMS Chapter 17.6, Guidelines for Determining the
Fullness of Pipelines Between Vessels and Shore Tanks International Petroleum (IP) 200, Petroleum Measurement
Tables
MNL37-EB/Jun. 2003
Hydrocarbon Analysis
James C. Fitch^ and Mark Barnes^'^
Absorption spectrometry works because applied electromagnetic radiation of an appropriate frequency induces a transition from one (lower) energy level to another (higher) energy
level within the molecule, causing the radiation to be absorbed by the sample. In IR and UV spectrometry, these energy levels are the vibrational and electronic energy levels of
the molecule, whereas in NMR the energy levels are associated with the nuclear spin of the nuclei that make up the
molecule. For the purpose of detailing how NMR works, we
will focus on the most commonly studied nucleus, the hydrogen nucleus 'H, which has a nuclear spin of li.
A nucleus such as 'H with a spin of 'A possesses two nuclear
spin states, +'A and 'A. Under normal circumstances, these
spin states have the same energy and are said to be degenerate. However, in the presence of a strong magnetic field (typically 2.33 tesla (T) for the ^H nucleus), the two nuclear spin
states split into two energy levels, their separation being proNUCLEAR MAGNETIC RESONANCE (NMR)
portional to the applied magnetic field as shown in Fig. 1 [1].
SPECTROSCOPY
Applying a source of electromagnetic radiation and slowly
Introduction
scanning the frequency can induce absorption when the radiation frequency matches or is in resonance with the energy
Nuclear magnetic resonance (NMR) spectroscopy is one of
separation of the two nuclear spin states under the applied
the most widely used analytical tools in chemical analysis.
magnetic field. The frequency of radiation that must be apJust like infrared (IR) and ultraviolet (UV) spectroscopy,
plied to induce such a transition is typically in the radio freNMR is a form of absorption spectrometry, whereby the
quency (rf) range. For a ^H nucleus under an applied magamount of absorbed electromagnetic radiation at a given frenetic field of 2.33 T, the resonance frequency is around 100
quency can be related to the concentration of certain chemiMHz [2]. For practical reasons, NMR spectrometers usually
cal species that absorb at that frequency. However, unlike IR
work in the opposite sense, with a fixed electromagnetic raspectroscopy, which looks at functional groups within a
diation frequency (commonly 100 MHz for ^H NMR) and a
molecule, or UV spectroscopy, which looks at the molecule as
scanning magnetic field [3]. However, the same principle apa whole, NMR is used to determine the concentration of speplies: the magnetic field is scanned until the energy separacific atoms within a sample.
tion of nuclear spin states induced by the field comes into resonance with the applied electromagnetic radiation.
It is not the mandate of this chapter to provide a detailed
quantum physical explanation of NMR or any other analytiIn reality, the magnetic field that must be applied to bring
cal method described herein. However, the basic theory bea nuclear spin transition into resonance with the applied
hind NMR spectroscopy will be outlined in this section, so
electromagnetic radiation varies slightly with the chemical
that the reader can obtain an understanding of NMR and
environment of the nuclei in question. This phenomenon is
how it can be applied to the analysis of large hydrocarbon
known as shielding and can be attributed to the effects of the
molecules typically found in fuels and lubricants.
electrons surrounding a particular nucleus, shielding the nucleus from the effects of the magnetic field [2]. Because the
electron density surrounding a particular nucleus is directly
related to the chemical structure of the molecule, the electron
distribution within the molecule gives rise to shielding ef1 Noria Corporation, 1328 E. 43''' Court, Tulsa, OK 74105.
^ Technical Editor, Practicing Oil Analysis Magazine, Tulsa, OK fects, which are typically called the chemical shift, which can
be used to differentiate between the same nuclei (for example
74105.
649
Copyright'
2003 by A S I M International
www.astm.org
C _ H
H
Magnetic
Field of
Strength
Relative
Energy
Absorbed
Energy
Increasing Frequency
FIG. 1The separation of proton nuclear spin states under
an applied magnetic field.
aromatic hydrogen
resonance
methyl hydrogen
resonance
X 10*
Chemical Shift/ppm
10.0-60.0
14.1
29.2
110-160
perimental resolution, the NMR spectrum of samples containing ''C nuclei in natural abundance can be recorded and
analyzed, in much the same way as 'H NMR spectra can be
analyzed to determine key structural properties of the
molecules that comprise the bulk sample.
Just like ' H NMR, the resonant frequency of the ^'C nuclei
are influenced by the chemical environment in which they
are surrounded and again, chemical shifts can be calculated
in ppm relative to a calibration standard such as TMS using
the same formula used to calculate 'H chemical shifts. Chemical shifts for '^C nuclei tend to be somewhat larger than 'H
shifts in hydrocarbon molecules. Some typical chemical
shifts for '^C nuclei in hydrocarbon molecules are shown in
Table 2 [5].
Because the natural abundance of ^^C is so low, the experimental measurement of '^C NMR spectra is slightly more
difficult than 'H NMR spectra because the spectra tend to be
much weaker. To overcome this difficulty, the spectra are
recorded not by scanning the frequency as for *H NMR (a
technique often called continuous wave or CW) but by pulsing a series of short pulses of broad band radiation (of the order of 0.5-50 fjis) and monitoring the free induction decay of
the signal from the '^C nuclei. This time domain single is
then converted into the frequency domain using Fourier
Transformation [2]. This, coupled with other techniques too
advanced to discuss here, have made the recording and interpretation of '^C NMR spectra commonplace [5].
The Use of ^H and " C NMR in the Analysis of
Hydrocarbons
Because 'H and '^C are the two nuclei most commonly analyzed by NMR spectrometry, it stands to reason that NMR
has proven useful in hydrocarbon analysis. There are two
main areas where NMR has been used for hydrocarbon fuel
and lubricant aneJysis, specifically the identification of hydrogen content in aviation fuels (ASTM D 3701) and
petroleum distillates (ASTM D 4808), and in determining the
aromatic hydrogen and aromatic carbon content using 'H
and " C NMR spectrometry (ASTM D 5292).
The determination of hydrogen content is an important
property of a fuel or lubricant because it is closely related to
key performance characteristics and can be used as a measure of quality control both during and after production.
Both test methods (ASTM D 3701 and ASTM 4808) work by
taking the ratio of the total integrated hydrogen signal from
the sample NMR spectrum to a known n-dodecane standard
run on the same NMR instrument. In each case, the total hydrogen content by mass (H%) is then calculated using the
formula,
H(%)
= S/R X (WR/WS)
15.39
ANALYSIS
651
where S is the total integrated hydrogen signal from the sample, R is the integrated signal from the n-dodecane reference,
Wn is the weight of n-dodecane used, Ws is the weight of sample used, and 15.39 simply reflects the percentage by mass of
hydrogen in the n-dodecane reference standard. The accuracy of this test method is around 0.2-0.4% for a typical hydrogen content of 14% [5]. Other variations on this method
have also been used, which involve pulsed FT NMR, which
are capable of errors as low as 0.05% [6, 7].
Hydrocarbon oils made by the refining of crude petroleum
are generally classified parafHnic or naphthenic depending
on the predominant class of hydrocarbon compounds found
in the oil [8]. Despite this, most oils of this type contain a significant proportion of aromatic hydrocarbons. The aromatic
content of an oil can affect a number of physical and chemical properties such as boiling range, viscosity, stability, and
compatibility. For this reason, it is important to be able to determine to amount of aromatic hydrocarbon content in a hydrocarbon oil [9].
One way of characterizing the aromatic content is to count
the number of aromatic carbon and hydrogen atoms in a
bulk sample. Because NMR is capable of separating signals
from different atoms within molecules based on their chemical structure and environment using the concept of chemical
shifts, NMR is a natural for this type of determination: this is
the basis behind ASTM D 5292. In this case, the test method
is even simpler than measuring total hydrogen content. The
sample is analyzed using pulsed FT NMR and the total aromatic ' H and "C content determined by taking the ratio of
the aromatic carbon or hydrogen nuclei integrated signal to
the corresponding aliphatic signal. For the purpose of assigning ' H nuclear environments, peaks in the chemical shift
range 0.5 to 5.0 ppm are considered aliphatic hydrogen,
while those in the 5.0-10.0 ppm range are considered aromatic. A t5^ical NMR spectrum of this kind is shown in Fig.
3. For " C NMR, peaks in the 10 to 70 ppm range are considered aliphatic, while those in the 100-170 ppm range are
considered aromatic carbons [9].
The biggest drawback with NMR is the expense of purchasing and running an NMR instrument. However, in circumstances where the determination of the relative proportions of various constituents of a bulk sample in different
chemical environments at high precision are required, NMR
offers a quick simple means of obtaining quick, accurate
data. For this reason, the use of NMR as a tool for hydrocarbon analysis will continue to grow.
ASTM Petroleum Products and Lubricants NMR
Test Standards Under Subcommittee D 02.04
Aromatics in Hydrocarbon Oils by High Resolution
Nuclear Magnetic Resonance
(HR-NMR)
(ASTM D 5292)
This method is applicable to a wide range of hydrocarbon oils
that are completely soluble in chloroform and Cctrbon tetrachloride at ambient temperature. The data obtained by this
method can be used to evaluate changes in aromatic contents
of hydrocarbon oils due to process changes. Hydrogen ('H)
NMR spectra are obtained on sample solutions in chloroform-d using a continuous wave or pulsed FT high resolution
NMR spectrometer. Carbon ('^C) NMR spectra are obtained
652
MANUAL
HANDBOOK
1HFTNMR
PPM
FIG. 3^H NMR spectrum of gas oil showing thie aliphatic
(-0.5 to 5.0 ppm) and aromatic (5.0 to 10.0 ppm) hydrogen
peaks. Reprinted from ASTM D 5292-93.
Gas Chromatography
Gas Chromatography can be subdivided into two categories,
gas-liquid chromatography a n d gas-solid chromatography
[10]. In each case, the technique involves the separation of
components of a gaseous sample using a stationary phase, either a liquid in the case of gas-liquid chromatography, or a
solid in the case of gas-solid chromatography. Because the
overwhelming majority of test standards used for hydrocar-
bon analysis rely on gas-liquid chromatography, we will focus exclusively on this method, although the same basic principals apply to both methods.
In gas-liquid chromatography, it is the interaction between
the gaseous sample being carried t h r o u g h the column by
means of an inert gas (the mobile phase) and a standard liquid (the stationary phase), which causes the separation of different molecular constituents. The stationary phase is either
a polar or nonpolar liquid, which either coats the inside of
the column, in the case of a capillary column, or is impregnated onto an inert solid, which is then packed into the GC
column [ 11 ]. A schematic layout of a GC instrument is shown
in Fig. 4. The basic components are a n inert carrier gas, most
commonly helium, nitrogen or hydrogen, a GC column,
which will be described below, held inside an oven that allows for precise temperature control, and some type of detector capable of detecting the sample as it elutes from the
column.
Gas-liquid GC works because the molecules in the samples
are carried along the column in the carrier gas and partition
between the gas phase a n d the liquid phase. Because this partitioning is critically dependent on the solubility of the sample in the liquid phase, different molecular species travel
along the column a n d exit or elute at different times. Those
molecules that have a greater solubility in the liquid phase
take a longer time to elute and thus are measured at a longer
time interval. Because solubility is dependent on the physical
and chemical properties of the solute, separation between
different components of the sample occurs based on molecular properties such as relative polarity (for example, oxygenated molecules, aromatics and nonaromatics) and boiling
point. A tjTDical gas chromatogram is shown in Fig. 5.
In order to create this separation, a n u m b e r of different
liquid phase materials are used that can be broadly classified
as either polar or nonpolar. For hydrocarbon analysis the two
most commonly used liquid phase materials are TCEP (1,2,3tris(2-cyanoyethoxy)propane) for polar columns, and methyl
silicone for nonpolar columns, although a multitude of different polar and nonpolar columns suitable for hydrocarbon
analysis are commercially available. I n general, polar
columns are used to separate aromatics from nonaromatics,
while nonpolar columns are used to sepeirate hydrocarbon
components by their boiling point.
There are two basic ways in which GCs are used for hydrocarbon analysis, either to separate different components of
the sample based on their differing chemical characteristics
(for example, aromatics versus nonaromatics), or to separate
different chemically similar fractions based on their boiling
point. To separate molecules based on their chemical properties, a GC is run in the method described above, with a polar column used to provide longer retention times for compounds such as aromatics relative to paraffins and olefins.
For accuracy, it is vital that the oven temperature in which
the GC column is housed is precisely controlled. This method
is called isothermal GC analysis [10].
GCs can also be used in another mode called temperature
programming. In temperature programming, the oven temperature is slowly swept from an initially low temperature
( s e e ) to a much higher temperature (typically 350-400C) at
a CcirefuUy controlled rate [12]. The effect is to cause an increased separation of chemically similar species based on
CHAPTER
24: HYDROCARBON
ANALYSIS
653
VENT
OVEN
CARRIER
GAS
^ RECORDER
INJECTION
PORT
COLUMN
R s REFERENCE
S s SENSING
u_
TIME. MINUTES
1 | ^
e ^ 1
-Collector electrode
Flame ignition
coil
+300V
Polarising voltage
Hydrogen
Column
FIG. 6Flame ionization detector.
using temperature programming, and the detection of certain contaminants such as diesel fuel or ethylene glycol in engine oil or oxygenated additives such as MTBE.
The determination of the aromatic content of hydrocarbon
fuels is a n important application of GC because benzene,
toluene, and other aromatics pose a serious heedth threat and
654
MANUAL
HANDBOOK
is carefully regulated in gasolines and other petroleum products. There are a n u m b e r of test methods that use GC for this
purpose, all of which follow the same basic principle (see
ASTM D 3606, D 4420, and D 5580). In each case, a sample
containing an internal calibration standard is injected into a
GC instrument equipped with two columns, one containing a
nonpolar liquid phase such as methyl silicone, the second using a polar liquid phase such as TCEP. The polar liquid phase
separates aromatics and nonaromatics because aromatics
take longer to elute from a polar column, while the nonpolar
column separates the aromatic components by their boiling
point, allowing the concentrations of benzene, toluene, and
heavier aromatics to be determined. In each case, the measurements are carried out isothermally (that is at a fixed colu m n temperature). A tjrpical gas chromatogram of the aromatic components of gasoline using this method is shown in
Fig. 7.
Another i m p o r t a n t application of GC to h y d r o c a r b o n
analysis is the simulated distillation of crude petroleum [13].
Determining the boiling point range of petroleum fractions
has a variety of uses, from determining the composition of
feed stocks to evaluating the presence of volatile components,
which may have implications on the performance or safety
cheiracteristics of finished hydrocarbon fuels and lubricants.
Historically, the boiling point range of petroleum fractions
has been determined by trial distillations in the laboratory.
While this method still has some validity, and in some circumstances may be advantageous, the use of gas chromatography offers a quick, simple alternative for controlling refining processes and product evaluations.
Boiling point range determination of petroleum products
using GC involves injecting a sample into a nonpolar column,
which is housed in a temperature programmable oven. The
GC is first calibrated using a calibration solution containing
known concentrations of normal paraffins. The temperature
of the column is increased at a known rate and the retention
time of the n-paraffins is plotted against their known boiling
points, as shown in Fig. 8. The crude sample is then analyzed
in the same way, and the retention times of the eluting sam-
Toluene
0}
c
m
N
<-8
aromatics
Non-aromatics
aromatics
t^r^
10
15
Time, minutes
25
1100
600
10
15
20
25
30
Retention Time, Minutes
35
40
FIG. 8^Typical boiling point ranges of n-paraffins as a function of column retention time. Reprinted from ASTM D 5307.
ANALYSIS
655
23500-
21500
19500
17500V)
Z 15500
O
0.
tU 13500
OC
538C (1000F)
11500
BASELINE
9500
7500
JIMMAAAAMA^
AIS
5500
3500
TIME
00
CO
CM
P4
A. CRUDE + INTERNALSTANDARD
B = TOTAL ELUTED AREA
UPTO538*C(1000F)
B' = AREA CORRESPONDING TO
NON-ELUTED SAMPLE
BIS " AREA OF SEGMENT WHERE
INTERNAL STANDARD ELUTES IN
FIGURE 9A
19500
538''C(1000''F)
BASELINE
yUwiiUAAAz/AAx^
I BIS
TIME
B. CRUDE ONLY
FIG. 9Gas chromatogram of calibration mixture and crude oil sample used to determine boiling point range. Reprinted with permission from ASTM D 5307.
with complex mixtures such as fuels and lubricants. However, one way of addressing this issue is to couple GC with
some other applicable method that is capable of not only detecting eluting fractions, but can also identify their chemical
composition. For this reason, the dual combination of GC
with mass spectrometry (GC-MS), infra-red spectrometry
(GC-FTIR), and atomic emission (GC-AES) will continue to
grow in importance in the quantitative analysis of hydrocarbon fuels and lubricants [16,17]. The application of GC to MS
and FTIR is covered in the appropriate spectrometric analysis sections of this review.
656
MANUAL
HANDBOOK
time axis from a calibration curve, obtained under the same
conditions by running a known mixture of hydrocarbons covering the boiling range expected in the sample.
A S T M P e t r o l e u m P r o d u c t s a n d L u b r i c a n t s GC
Test Standards
Aromatics in Finished Gasoline by Gas
Chromatography
(ASTM D 4420)
This test method determines benzene, toluene, Cs, C9, and
heavier aromatics, and total aromatics in finished m o t o r
gasoline and gasoline blending components. A two column
chromatographic system connected to a dual filament thermal conductivity detector (or two single filament detectors)
is used.
Aromatics
in Finished
Gasoline
by GC (ASTM D
5580)
Aromatics in the following concentration reinge can be determined by this test method; benzene 0.1-5; toluene 1-15; individual Cg aromatics 0.5-10; total C9 and heavier aromatics
5-30; and total aromatics 10-80 liquid volume percent. The
aromatic hydrocarbons are separated without interference
from other hydrocarbons in the finished gasoline. A two colu m n c h r o m a t o g r a p h i c system equipped with a columnswitching valve and a flame ionization detector is used.
Benzene/Toluene
in Gasoline
(ASTM D 3606)
by Gas
Chromatography
by Gas
by
Distillates
by
Fractions
by
Oils by Gas
by Capillary
Gas
The determination of engine oil volatility at 371C is a requirement in some lubricant specifications. A sample aliquot
diluted with a viscosity reducing solvent is introduced into
the gas chromatographic system, which uses a nonpolar open
tubular capillary gas chromatographic column for eluting the
hydrocarbon components of the sample in the order of increasing boiling point.
Ethanol Content In Denatured
(ASTM D 5501)
Fuel Ethanol
by GC
Oil (ASTM D
4291)
Oil Volatility
by GC ASTM
(D
5480)
Ether in Gasoline
by GC
CHAPTER
control in the production of gasoline and the determination
of deliberate or extraneous oxygenate additions or contamination. A gasoline sample is doped with an internal standard
such as 1,2-dimethoxyethane, and is injected into a gas chromatograph equipped with two columns and a column switching valve. The eluted components are detected by a flame ionization or a thermal conductivity detector.
Olefins In Engine
Fuels by GC (ASTM D
6296)
by Gas
Chromatography
in Fuels by
by GC-Sulfur
Detector
24: HYDROCARBON
ANALYSIS
657
LIQUID C H R O M A T O G R A P H Y (LC)
TIME
Introduction
The technique of liquid chromatography (LC) is closely allied
with gas chromatography (GC) and other chromatographic
methods. Just like GC, liquid chromatography separates different molecules or molecular groups based on their physical
and chemical properties. However, unlike gas chromatography, LC as the name implies the use of a liquid mobile phase
to analyze samples. The field of liquid chromatography is
very broad ranging and is used in many different areas of analj^ical chemistry. In this section, we will cover just those areas of liquid chromatography that Eire used in the analysis of
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X X
xoxo
oxox
0 0
0 0
X X
X X
X X
oxox
0 0
|0 O
0 0
X X
XX
X X
X X
0 0
0 0
0 0
O 0
U 1/ W U \J
FIG. 10The chromatographic process.
X X
X X
X X
X X
O 0
O 0
0 0
0 0
658
HANDBOOK
SOLVENT RESERVOIR
5=
INJECTION POINT
DETECTOR
RECORDER
COLUMN-
\J
THERMOSTAT
240
ANALYSIS
659
1
1
210
180
>
E ISO
!&
c
o
^ 1
sQ \
j!l20
c
90
o
o
^
X
o
13
E
8
_
"
60
30
> 11
"
to
>
o I
i\^i
X- 1
I
<=
-
3i-Aromatic Hydrocarbons
c1
CO
^
6 1
"
1
I
I
M
'
Time (minutes)
FIG. 12^The use of liquid chromatographic separation to differentiate mono and di-aromatics in aviation fuel. Reprinted with permission from ASTM D 6379.
HANDBOOK
Introduction
ULTRAVIOLET S P E C T R O S C O P Y
Ultraviolet (UV) spectroscopy, also known as UV spectrometry, was one of the first spectroscopic techniques used to
quantify chemical composition [27]. Like other spectroscopic techniques, it is used to identify characteristic moleculEir fingerprints enabling the quantitative detection of specific molecules or molecular species in complex mixtures. UV
spectroscopy is most commonly used in hydrocarbon analysis as a detection tool after high performance liquid chromatography (HPLC).
i k
^
i k
i L
i k
>
increasing
energy
J
ground electronic state
ANALYSIS
661
lamp
entrance
slit
diffraction
grating
photo cell
detector
max
Beer's Law
In order to use UV spectrometry as a quantitative tool, we
need to understand the relationship between the concentration of specific molecules and the amount of light they absorb. This fundamental property is determined by Beer's
Law:
A = d)c
where A is the absorbance, e is the molar absorptivity, b is the
cell path length containing the sample, through which the UV
light passes, and c is the concentration in mol/L [27]. Because
the molar absorptivities of most molecules of interest have
been measured, and i> is a known quantity based solely on instrument design, measuring the amount of light absorbed by
the sample (A in the above equation) allows the concentration c to be determined simply by rearranging the Beer's law
equation.
UV Spectrometers
A schematic illustration of a UV spectrometer is shown in Fig.
14. The main components are a white light source, which is focused onto the entrance slits of a spectrometer, a cuvette or cell
containing the sample to be analyzed, and a photocell detector
to measure light intensity. The spectrometer is equipped with
a diffraction grating, which acts much like a prism to split the
white light into discrete wavelengths. Because the angle of
diffraction is defined by the wavelength of light, slowly changing the angle of the grating relative to the incoming light allows
the wavelength of light that exits the spectrometer through the
exit slits to be slowly scanned, allowing an absorption spectrum to be recorded, as shown in Fig. 15. The amount of light
absorbed at the maximum excitation wavelength (Amax). will
be dependent on the concentration c, path length b, and molar
absorptivity Smax as per Beer's Law.
'max
FIG. 15Typical UV absorption spectrum.
HANDBOOK
Molar Absorption
1
100,000
1 Mono
|Di
[ Tricycli
1
/ / N j /^(~" \
10,000
^-^
1
1
11
1
1
1 I
1
1
1
)1
1
\.
Dicyclics
^ ^
^
1
1
Monocyclics
1,,^
/
yf
1 \
/
1 \
/
1
\ ^ /
1
1
1
1
1
1 t
180
190
'
200
210 220
230 240
\ ^
1
1
11
100
10
VMono
1,000
-/^
'iTriX/
^ '
\'
|Di
1
1
1
1
1
1
1
1
1
250
'
k.
260 A(nm)
trofiuorometry [29]. The principle behind spectrofluorometry is illustrated in Fig. 17, which shows theoretical absorption spectra for two different polyaromatic molecules
(molecules A and B), together with the corresponding fluorescence spectra. Because both molecules are polyaromatic,
the absorption spectrum for each will show a meiximum
around 260 nm. Recording the absorption spectrum for a
mixture of molecule A and molecule B will not allow the relative concentrations of each to be determined because both
absorb simultaneously at 260 nm. However, after excitation
at 260 nm, both molecules are in an excited electronic state
etnd will emit radiation to return to a lower lying electronic
state, typically in the form of light. Because molecule A and
molecule B possess different electronic structures, the energy of the lower lying electronic states will not necessarily
be the same. Because the emitted radiation is quantized,
measuring the emission (fluorescence) spectrum as opposed
to the absorption spectrum allows the concentration of two
molecules to be determined independently of each other.
Used in conjunction with LC, spectrofluorometry is an extremely sensitive technique capable of detecting concentrations of polycyclic aromatics and other species as low as
picograms [32].
ASTM Petroleum Products and Lubricants UV
Test Standards
Naphthalene Hydrocarbons in Aviation Turbine Fuels
by Ultraviolet (UV) Spectrophotometry (ASTM D 1840)
This test method covers the determination of the total concentration of naphthalene, acenapthene, and alkylated
derivatives of these hydrocarbons in straight-run jet fuels
containing no more than 5% of such components and having
end points below 600F. The total concentration of naphthalenes in jet fuels is measured by absorbance at 285 nm of
a solution of the fuel at known concentration.
MASS SPECTROMETERY
Introduction
Mass spectrometry is used to detect the presence of different
molecules in bulk samples. The technique involves the gas
phase cinalysis of samples that are either already gases, or are
liquids or solids that can be vaporized prior to mass spectrometric analysis. In conventional mass spectrometry, the gas
phase sample is ionized to form various primary and fragmentation ions, which are then analyzed according to their
mass-to-charge ratio. The mass spectrum thus generated can
then be used as a cheiracteristic fingerprint to detect the presence of certain molecules with the relative intensity of the
mass spectra allowing an estimate of the concentration of the
molecule or molecular species within a bulk sample. The application of Mass Spectrometry (MS) to the analysis of hydrocarbon fuels emd lubricants is outlined in this section.
MS Theory
As previously mentioned, MS works on the principal of separating primary and fragmentation ions according to their
CHAPTER
mass-to-charge (m/z) ratios. Take for example the w a t e r
molecule H2O. Bombarding water vapor with a high-energy
electron source will create both primary ions and fragmentation ions as follows:
HOH
>HOH+
+ OH+
I
primary ion
m/z = 18
+ 0+
m/z = 17
H+-F3e~
.
secondary ions
m/z = 16
m/z = 1
24: HYDROCARBON
ANALYSIS
663
of hydrocarbons typicedly found in petroleum fuels and lubricants. With many thousands of different components including paraffins, branched paraffins, naphthenic molecules,
and aromatics, the m a s s spectrum of a typical petroleum
fraction is extremely complex. Nevertheless, mass spectrometry can and has been successfully applied to the analysis of
complex petroleum mixtures as will be discussed later.
MS Instrumentation
Recording the mass spectrum of a bulk sample and measuring the relative intensities of the m/z = 1, 16, 17, and 18
peaks will allow the presence of water to be determined, and
by inference its concentration, provided a suitable calibration standard has been determined.
The biggest drawback with MS is that the complexity of the
m a s s s p e c t r u m increases exponentially with increasing
molecular size (molecular mass). Take for example benzene,
a relatively simple hydrocarbon. The electron ionization
mass spectrum of benzene (Fig. 18) has 17 different peaks
corresponding to m/z values ranging from 27-79, which include primary and fragmentation ion mass peaks, as well as
peaks associated with the naturally occurring isotope '^C
[35]. Now consider applying mass spectrometry to a mixture
-* energy
UV absorption (A&B)
Amaxs260nm
absorption
molecule A
emission
absorption
molecule B
emission
664
HANDBOOK
<n
1) 60-
U 40
a:
20
10
15
20
25
30
35
40
45
50
"i""|i il'i""i"'lMl'h
55
60
65
70
75
80
m/z
FIG. 18Mass spectrum of benzene.
Sample
Inlet
Ionization
Source
Mass Analyzer
Ion
Detector
Once in the gas phase, the sample is drawn into the ionization section of the instrument where it is intersected at right
angles by a high-energy electron beam created by a hot filament. This is called an electron ionization mass spectrometer. The electron beam ionizes the sample into primary and
fragmentation ions, which are accelerated into the mass analyzer section using an electrostatic field formed by a series
of electrodes, which serve to focus and accelerate the ions
into the mass analyzer.
There are many different types of commercial mass spectrometers available. They all differ slightly in their design,
but all use one of three basic methods to mass analyze the
ionized sample, namely magnetic field deflection,
quadrupole mass spectrometry, or time-of-flight [35]. A detailed explanation of these different types of mass analyzers
is beyond the scope of this chapter, but an excellent description of these different methods can be found in Ref. 35. No
matter what type of mass analyzer is used, they all separate
ions according to their m/z ratio, with the ion signal being detected, amplified, and recorded as a function of their massto-charge (m/z) ratio.
Gas Chromatography-Mass Spectrometry (GC-MS)
One adaptation, which has served to simplify the interpretation of MS data, is to use a standard Gas Chromatograph (GC)
as the sample inlet source for the mass spectrometer. As explained earlier in this chapter, a gas chromatograph is an instrument that separates complex mixtures of chemicals into
single molecular components, or groups of components with
similar physical properties. By combining MS with GC, the
analysis of complex mixtures of chemicals such as hydrocarbon fuels and lubricants has become greatly simplified.
CHAPTER
TABLE 3ASTM test procedures that use mass spectrometry for
determining the composition of different fractions.
ASTM Test Procedure
D 2425
D 2786
D 2789
D 3239
Significance
Saturates and aromatics in middle distillates
Saturates in gas oil fractions
Hydrocarbon types in low olefinic gasoline
Aromatics in gas oil fractions
2786 that is based on the Hood and O'Neal method, the mass
grouping E71 is defined as the sum of peaks at m/z = 71,85,
99, and 113 and is used to determine alkane content [37,38].
The difference in masses between each peak in the summation is simply the extension of the aJkane chain by one CH2
unit, with a corresponding increase in molecular mass of 14
atomic mass units. The biggest drawback with this method,
and indeed MS in general, for the analysis of hydrocarbons is
that the n u m b e r of mass peaks that must be considered increases significantly with molecular size. To illustrate this
complexity, consider the complete list of mass groupings,
which must be considered under ASTM D 2786, and the corresponding molecular types they represent;
S71 = 71 + 85 + 99 -F 113
alkanes
1 6 9 = 69 -I- 83 + 97 + 111 -F 125 + 139 1 ring naphthenes
E109 = 109 -I- 123 + 137 -I- 151 + 165
-I- 179 -I- 193
2 ring naphthenes
X149 = 149 + 163 + 177 + 191 -I- 205
+ 219-I-233-(-249
S189 = 189 + 203 + 217 + 231 + 245
+ 259 + 273 + 287 + 301
X229 = 229 + 243 + 257 + 271 -I- 285
+ 299 + 313 + 111 + 341 + 355
1269 = 269 + 283 4- 297 -F 311 + 325
-I- 339 + 353 -1-367-1-381
-F 395 + 409
S91 = 91 -F- 105 + 117 -I- 119 + 129
+ 131 4- 133 -I- 143 + 145 -I- 147
+ 159-1- 171
3 ring naphthenes
4 ring naphthenes
5 ring naphthenes
6 ring naphthenes
Mono-aromatics
24: HYDROCARBON
ANALYSIS
665
by Mass
Spectrometry
This test method covers the determination by mass spect r o m e t r y of total paraffins, monocycloparaffins, dicycloparaffins, alkylbenzenes, indans, or tetralins or both, and
n a p h t h a l e n e s in gasoline. Samples are analyzed by m a s s
spectrometry, based o n the s u m m a t i o n of characteristic
mass fragments, to determine the concentration of the hydrocarbon types.
Aromatics
in Gasoline by Gas
Spectrometry
(GC-MS) (ASTM D
Chromatography-Mass
5769)
This test method can be used for gasolines that contain oxygenates such as alcohols and ethers as additives. They do not
interfere with the analysis of benzene and other aromatics by
this test method. The sample is injected either through the
capillary splitter port or a cool-on-column injector into a gas
c h r o m a t o g r a p h equipped with a dimethylpolysiloxane
WCOT column interfaced to a fast scanning mass spectrometer. The mass analyzer processes the signal at specific m/z
values corresponding to the principal ion masses for various
components allowing benzene, toluene, and total aromatic
content to be measured in gasolines.
INFRARED SPECTROSCOPY
Infrared spectroscopy is a widely applied, nondestructive test
method for assessing a variety of molecular physical qualities
of a lubricant or fuel sample. The spectrum analyzed by the
method is considered a distinct physical property of the sample and, as such, is unique from other physical and chemical
properties, such as viscosity, specific gravity, flash point, etc.
From the spectrum, in most cases, a positive identification of
the sample and its greater molecular constituents can be obtained [40].
666
MANUAL
HANDBOOK
Most p e t r o l e u m products, a n d more specifically, lubriCcints, fuels, additives, and contaminants are mixtures, which
results in the spectrum being a composite of m a n y different
spectral components that are additive. Nevertheless, for most
fluids, the spectrum is sufficiently characteristic to enable
the identification of the unique spectred features of individual
components. Still, in certain cases, a physical or chemical
separation of the tcirget components from the rest of the sample, such as gas chromatography, m a y be desirable to improve detection limits and resolving power of the technique.
The infreired spectrum of a substance is produced when a
portion of a beam of infrared energy passing through a fixed
path length of the sample is absorbed by a specific functional
group within a specific molecule present in the sample. This
absorption has unique wavelength dependencies relating to
the sample's molecules. Most molecules are in constant
modes of rotation, stretching, and bending at unique and often multiple frequencies. In addition, these vibrational frequencies will vary as the bonded atoms, functional groups,
a n d bond strengths are changed. These differences in absorption at certain wavelengths in the mid-infrired spectrum
collectively describe the quality and quantity of molecular
makeup of the sample [41].
Infrared spectroscopy is especially well suited for the analysis of organic c o m p o u n d s comprised of characteristic
molecular structures. The various groups, called functional
Abundance.,
ION 128
80000:
70000.
60000.
SCOOO.
NAPHTHALENE
40000:
30000'
2000010000
0
Time 18 00
^
18.50
Abundance
50000
19.00
19.50
20.00
20.50
21.00
21.50
22.00
ION 142
4S000
2-METHYmAPHTHALENE
40000
39000:
1-METHYL-NAPHTHALENE,
30000
""-*
2SOO0'
20000
15000100005000;
0^
Time - 18 00
,
18.50
19.00
19.50
20.00
20.50
21.00
21.50
22.00
MINUTES
FIG. 20^Typical mass selected gas chromatogram showing the ability of GC-MS to separate molecular species by their elution time and
characteristic ion mass peak. Reprinted with permission from ASTIVI D
5769-98.
Wavelength
4000- - 2 . 5 - 1
3500-
-3
3000;
2500- ^ 4
Functional
group
region
2000- ^ 5
1800^
: L-e /Am
(micrometei)
1600 L
f-7
1400|-8
1200^9
1 0 0 0 - |-10
8 0 0 - |-12
tl5
elength goo
P-20
conversion scale
for
efor
infrared data.
1.
400 - F 3 0
2 0 0 - ^50
Frequency Wavele ngth
-1
cm
Fingerprint
region
ANALYSIS
667
The reference and sample beams are then passed ahematively by a rotating half mirror to a dispersive device, which
separates the radiation into specific frequencies (wavelengths). A prism is one type of dispersive device that separates radiation in different wavelengths based on differences
in refractive indexes at different wavelengths. Since glass will
absorb infrared radiation sodium chloride, other materials
cire required. Alternatively, a grating can be used as a dispersive device using a series of closely spaced parallel grooves
etched into a flat surface. The grating simply reflects the
diffracted light from its surface and absorbs very little radiation. Many infrared spectrometers require special temperature cind/or desiccants to prevent moisture damage to the optics in the monochromator [42].
The monochromator directs the radiation reflecting
from the grating through a series of narrow slits, which luminate onto a detector, for example, a thermocouple. This
quantifies the intensity of the energy at only the desired
band of frequencies. Many dispersive-type infrared spectrometers are of the double-beam optical null type. In such
cases, the radiation passing through the reference beam is
reduced or attenuated to match the intensity of the sample
beam [42].
Beer-Lambert Law
A good place to begin the discussion of using infrared spectroscopy for quantitative analysis of fuels and lubricants is
the Beer-Lambert Law. It relates the amount of infrared light
absorbed by a given sample to the concentration of the target
compound and path length. More to the point, the law states
that concentration is directly proportional to absorbance at a
given wavelength and path length at a specified temperature
and pressure.
Compared to the dispersive spectrometer, the Fourier transform spectrometer provides improved speed and range of
spectral sensitivity in making infrared measurements. The
Michelson interferometer is a basic component of the
Fourier transform instrument. Unlike the dispersive spectrometer, the interferometer has no slits or grating. Instead,
it consists of two mirrors and a beam splitter. The beam
splitter transmits half of all the incident radiation from a
source to a moving mirror and reflects half to a stationary
mirror. Each component reflected by the two mirrors returns to the beam splitter where the amplitudes of the
waves eire combined to form an inteferogram, which is
Fourier-trEinsformed into the frequency spectrum. The interferometer scans the infrared spectrum in just fractions of
a second at moderate resolution. The resolution is uniform
across the optical range. Multiple scans can be co-added to
reduce background noise [42].
(1)
A = absorbance
/ = IR power-reaching detector with sample in beam
7 IR power-reaching detector with no sample in beam
a = absorption coefficient of pure component of interest at
anal54ical wavelength; the units depend on those chosen
for b and c
b = sample path length
c = concentration of sample component
This linearity permits simple calibration plots of known
samples between absorbance (A) and concentration (C) for
analyzing the concentration in unknown samples. In addition, the Law is helpful in choosing the optimum sample path
length for accurate eincJysis, as will be further discussed [43].
Dispersive-Type Infrared Spectrometers
In this design, zin infrared source of energy is usually provided by a Nemst glower, which is composed of rare earth oxides (zirconium, cerium, etc.) formed into a cylinder. On
electrically heating to approximately 1500C, this filament
material produces the needed infrared radiation. The beam
of radiation is split into a reference and sample beam by mirrors. The reference beam is passed through air or a beam attenuator and the sample beam is passed through the sample
where selective radiation absorption occurs [42].
668
HANDBOOK
rected for baselines as further discussed. The procedure is repeated for a range of concentrations covering the expected
concentrations. From this, absorbance is plotted against concentration. Analytical curves can also be constructed for each
of the wavenumbers or bands where the target component is
represented. So too, the procedure is repeated for each of the
components to be analyzed in the solution [44].
Analysis of Gases
For gases, all calibration measurements for a given analysis
must be made at a fixed total pressure. This pressure must be
equal to the total pressure employed in the analysis. Low
molecular weight gases frequently produce very strong, sharp
absorption features. Addition of a diluent gas and use of pressure below atmospheric may be necessary. Absorbances cire
measured for each of the standard wavenumbers selected for
analysis. Where possible, integrated absorbances are preferred to offset the effect of small pressure vetriations. The absorbances Eire plotted against the partial pressures (or mole
fractions) to produce analytical curves [44].
Achieving Reproducible Baselines
Any quantitative method depends on the choice of a reproducible baseline. The correction of raw data for baseline absorbance is important in some methods. The guiding factor
in baseline selection is the reproducibility of the results.
Methods used for drawing baselines with computerized instruments are similar in most ways to those for data recorded
on chart paper [44].
A technique known as the cell-in-cell-out method is often
used in single-beam infrared work. In this method, a blank
(that is, solvent in cell, potassium bromide (KBr) pellet, or
other substrate) is measured at a fixed wavenumber and then
the analyte readings are recorded. One variation involves the
subtraction of the absorbance minimum from the absorbance
maximum at the chosen baseline point. The point of minimum absorbance is adjacent to or at least near the band under evaluation. Alternatively, two points may be needed if the
band of interest is superimposed on a sloping background. In
such case, a line is drawn from one side to the other and absorbance is calculated as the value at the peak maximum minus the baseline absorbance minimum. An inappropriate
choice of baseline in this situation may have deleterious effects on the accuracy of the final calculation [44].
The baseline correction described above should be performed only if the spectrum is plotted in absorbance units.
When the spectrum is plotted in transmittance, the two-baseline transmittances and the transmittance at the analytical
wavenumber Eire converted to absorbance. Conversion to absorbance is required because a sloping linear baseline in
transmittance becomes curved in absorbance [44].
Employing the Difference Method
Spectral subtraction using a computer is a common practice
in qualitative infrared analysis. This technique is also used to
perform quantitative infrared analyses. The advantage of
spectral subtraction (the difference method) is that small
concentration differences can be measured with greater ac-
Hydrocarbon Analysis
Hydrocarbon analysis using infrared spectroscopy must begin at the parent backbone structure. The simple aliphatic hydrocarbon is the root of most Ediphatic compounds and consists of simple linear chains, branched chains, and cyclic
structures. Aliphatic compounds can consist of one or more
of these structures. The infrared spectrum is useful in providing specific information on the existence of most of these
structures, by inference or directly. The spectrEd contributions
are characterized by CH and CC stretching and bending
vibrations, which are generally unique for each molecule. For
aromatic compounds, ring C=C-C stretching and bending
vibrations are distinctly characteristic as are carbon-carbon
multiple bonding in alkene and alkjrne structures [45].
In terms of recognizing a compound as having an organic
structure with aliphatic constituents, the CH stretch vibrations for methyl and methylene are the most characteristic.
In Fig. 22, methylene/methyl bands can be seen at 1470 and
720 cm"^ An important methylene rocking vibration occurs
at 725-720 cm~'. As CH stretching absorptions all occur
below 3000 cm"', bands between 3150 and 3000 cm~' and
are almost always associated with unsaturation, for example,
C=CH and/or aromatic rings. Figure 23 shows examples of
either single or pair absorbancies of unsaturated hydrocarbons featuring C=C with attached hydrocarbons. The number of bands and their associated positions point to the double bond location Emd spacing around the double bond [45].
One or more aromatic rings can tj^ically be recognized by
the C=CC and C-H ring-related vibrations/bending. Typically, the CH stretching occurs about 3000 cm~\ revealing
a number of weak-moderate bands compared with the
aliphatic CH stretch. The number and locations of the CH
CHAPTER
Functional group/assignment
Methyl (-CHj>
Methyl C-H asym./sym. stretch
Methyl C-H asym./sym. bend
gem-Dimethyl or "iso" - (doublet)
Trimethyl or "tert-butyl" (mlltiplet)
Methylene (>CH2)
Methylene C-H asym./gym. stretch
Methylene C-H bend
Methylene - (CH2)-rocklng
(n>3)
Cyclohexane ring vibrations
Methyne (>CH-)
Methyne C-H stretch
Methyne C-H bend
Skeletal C-C vibrations
Special methyl (-CHj) frequencies
Methoxy methyl ether O-CH3
C-H stretch
Methylamino, N-CH3, C-H stretch
C-H
Group frequency
wavenumber (cm')
1680-1620
1625
1600
3095-3075
+3040-3010
3095-3075
3040-3010
0-H
1420-1410
1310-1290
C-H
995-985+915-890
895-885
C-H
970-960
700 (broad)
Assignment
Alkenyl 0 = 0 stretch
Aryl-substituted C=C
Conjugated 0 = 0
Tenninal (vinyl) C-H stretch
Pendant (vinylldene) C-H
stretch
Medial, cis- or frans-C-H
stretch
Vinyl C-H in-plane bend
Vinylidene C-H in plane
bend
Vinyl C-H out-of-plane bend
Vinylidene 0-H out-of-plane
bend
trans 0-H out-of-plane bend
cis C-H out-of-plane bend
ANALYSIS
669
tinctive spectral contribution. T5T3ically, a unique group frequency associated with halogen-carbon stretching is assigned to the C^X bond (Fig. 24). If more than one halogen
is present, the identification of the group frequency is somewhat more complex. It is largely influenced by whether the
halogens are on the same or different CcU"bon atoms, and if
different, their relative proximity is important.
Relating to alcohols and hydroxy c o m p o u n d s , the 0H
stretch is probably one of the most pronounced and characteristic of all the infrared group frequencies. There is typiCcdly a high degree of association coming from hydrogen
bonding with other hydroxy groups. And, in cases, these may
come from hydroxy groups from within the same molecule
(intramolecular bonding). Alternatively, they may associate
with nearby molecules (intermolecular bonding). Collectively, the effects of hydrogen bonding result in the production of a well-defined but broad band cuid the lowering of
mean absorption frequency. This is exhibited in compounds
such as carboxylic acids, which produce strong hydrogen
bonding. See Fig. 25 for alcohol a n d hydroxy c o m p o u n d
group frequencies [45].
Because alcohols exist as three distinct classes, primary,
secondcury, and tertiary, they are identified by the extent of
carbon substitution on the central hydroxy-substituted carbon. The infrared characterization of these alcohols is reflected in the position of the OH stretch absorption but also
by other absorptions including the CO stretching frequency. These can be observed in the primary and secondary
alcohols shown in the spectra shown in Fig. 26. Ethers are
somewhat related to edcohol and hydroxy compounds where
the hydrogen of the hydroxy group is substituted by an aromatic (aryl) or aliphatic (alkyl) molecular fragment. Otherwise, the overall appearance of an ether spectrum is sharply
different from any associated alcohol due to the impact of the
hydrogen bonding on the hydroxy group [45].
In amines, the terms primary, secondary, and tertisiry are
used to describe the substituted nitrogen as opposed to carbon as with alcohols. As with alcohols, these structural differences are significant and distinctly influence the infrared
24: HYDROCARBON
Group frequency
wavenumber (cm"')
C-F
1150-1000
C-CI
800-700
C-Br
700-600
0-1
600-500
Assignment
670
HANDBOOK
0-H
0-H
C-0
3570-3200 (broad)
3400-3200
3550-3450
3570-3600
3645-3630
3635-3620
3620-3540
3640-3530'
1350-1260
1410-1310
720-590
-1050'
-1100
-1150'
-1200'
FIG. 25Alcohol and hydroxy compound group frequencies. Courtesy Coates Consulting.
I I I I I I I I I I I I I
o
o
o o
o o
o
Wavenumber (cm')
100
o
<o
<o
e
M
n
o
eo
CM
.
M
Wavenumber (cm'')
ATR spectra of (a) primary (1-octanol) and (b) secondary
(2-octanol) alcohols. Courtesy poates Consulting.
FIG. 26ATR spectra of (a) primary (1-octanol) and (b) secondary (2-octanol) alcohols. Courtesy Coates Consulting.
Origin
N-H
Group frequency
wavenumber (cm"^)
N-H
C-N
3400-3380
+3345-3325
3510-3460
+3415-3380
1650-1590
1090-1020
>N-H
3360-3310
>N-H
-3450
>N-H
3490-3430
=N-H
3350-3320
>N-H
C-N
1650-1550
1190-1130
C-N
1210-1150
C-N
1340-1250
C-N
1350-1280
C-N
1360-1310
N-H
Assignment
Primary amino
Aliphatic primary amine,
NH stretch
Aromatic primary amine,
NH stretch
Primary amine, NH bend
Primary amine, CN stretch
Secondary amino
Aliphatic secondary amine,
NH stretch
Aromatic secondary amine,
NH stretch
Heterocyclic amine,
NH stretch
Imino compounds,
NH stretch
Secondary amino, NH bend
Secondary amine,
CN stretch
Tertiary amino
Tertiary amine, CN stretch
Aromatic amino
Aromatic primary amine,
CN stretch
Aromatic secondary amine,
CN stretch
Aromatic tertiary amine,
CN stretch
Functional group
Carboxylate (carboxyllc acid salt)
Amide
Quinone or conjugated ketone
Carboxyllc add
Ketone
Aldehydle
Ester
SIx-membered ring lactone
Alkyl carbonate
Add (acyl) hallde
Aryl carbonate
Open-chain add anhydride
Five-membered ring anhydride
Transition metal carbonyls
ANALYSIS
671
OTHER STANDARDS
IP 156
REFERENCES
[1] Oehler, U., NMR-A Short Course, University of Guelph, Ontario,
Canada, http://www.chembio.uogueIph.ca/driguana/NMR/TOC.
HTM, Jan. 2001.
[2] Silverstein, R., Bassler, G., and Morrill, T., Spectrometric Identification of Organic Compounds, Fifth Edition, John WUey and
Sons, Inc., NY, 1991, pp. 166-201.
[3] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition, McGraw-Hill, Inc., NY, 1996,
pp. 802-808.
[4] NMR Spectral Archive, National Institute of Advanced Industrial Science and Technology. Tsukuba, Ibaraki, Japsin. SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/.
[5] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing, Editions Technlp, Paris, 2000, p. 21.
[6] Bouquet, M., "Determination of Hydrogen Content of Petroleum
Products Using Low Resolution Pulsed NMR Spectrometry,"
Fuel, Vol. 64, 1985, pp. 226-228.
[7] Gauthier, S. and Quignard, A., "Accurate Determination of Hydrogen Content in Petroleum Products by Low Resolution," '//
NMR Revue IFF. Vol. 50, No. 2, 1995, pp. 249-282.
[8] Willis, J., Lubrication Fundamentals, Marcel-Dekker, Inc., NY,
1980, pp. 1-25.
[9] ASTM D 5292-93: Aromatic Carbon Contents of Hydrocarbon
Oils by High Resolution Nuclear Magnetic Resonance Spectroscopy, Annual Book of ASTM Standards, ASTM International,
West Conshohocken, PA, 1993.
[10] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition. McGraw-Hill, Inc., NY, 1996,
pp. 831-864.
[11] Norris, T. A., "Chromatography II," Lubrication, Vol. 65, No. 2,
1979, pp. 13-24.
[12] ASTM D 5307: Determination of Boiling Range Distribution of
Crude Petroleum by Gas Chromatography, Annual Book of
ASTM Standards, ASTM International, West Conshohocken, PA.
[13] Altgelt, K. and Gouw, T., Chromatography in Petroleum Analysis,
Marcel-Dekker, Inc., NY, 1979, pp. 41-73.
[14] Troyer, D. and Fitch, J., Oil Analysis Basics, Nona Corporation,
Tulsa, OK, 1999.
[15] Fitch, J., "Oil and Water Don't Mix," Practicing Oil Analysis Magazine, July/August 2001, p. 20.
[16] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing Editions Technip, Paris, p. 53.
[17] "Gas Chromatography with Atomic Emission Detector for Turbine Engine Lubricant Analysis," JOAP Conference Proceedings,
University of Dayton Research Institute, Dayton, OH, 1994, pp.
485^96.
[18] Norris, T. A., "Chromatography II," Lubrication, Vol. 65, No. 2,
1979, pp. 13-24.
[19] Li, Z., "Separation Techniques with Liquid Chromatography,"
The FRH Journal, 1984, pp. 69-76.
[20] Stevenson, R., "Rapid Separation of Petroleum Fuels by Hydrocarbon Type," Journal of Chromatographic Science, Vol. 9, 1971,
pp. 257-262.
[21] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing, Editions Technip, Paris, 2000, pp. 31.
[22] "La Chromatographic d'Exclusion sur Gel," Journal of Dubois
Analysis 16, Vol. 3, No. LWVI-LXXIII, 1988.
[23] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition, McGraw-HUl, Inc., NY, 1996,
pp. 865-896.
[24] API 1509, Engine Oil Licensing and Certification System, American Petroleum Institute, Washington, DC, 1996.
[25] ASTM Test Standard D 2007: Characteristic Groups in Rubber
Extender and Processing Oils and Other Petroleum-Derived Oils
by the Clay-Gel Absorption Chromatographic Method, Annual
Book of ASTM Standards, ASTM International, West Conshohocken, PA.
[26] RR: D02-1388, ASTM International, West Conshohocken, PA,
1996.
[27] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Reference Handbook, Fourth Edition, McGraw-Hill, Inc., NY, 1996,
pp. 753-759.
[28] Silverstein, R., Bassler, G., and MorriU, T., Spectrometric Identification of Organic Compounds, Fifth Edition, John Wiley and
Sons, Inc., NY, 1991, pp. 289-314.
[29] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analysis and Testing, Editions Technip, Paris, 2000, pp. 41-58.
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
673
MNL37-EB/Jun. 2003
Volatility
Rey G. Montemayor^
DISCUSSION
' Imperial Oil Ltd., Products and Chemicals Division, Sarnia, Ontario Canada
Distillation
Distillation parameters are importcuit volatility characteristics of motor and other automotive spark-ignition fuels, aviation gasoline, aviation turbine fuels, diesel and other nonaviation gas turbine fuels, solvents, and other petroleum
products. Gasolines and gasoline blends are used in a variety
of engines operating u n d e r various atmospheric and mechanical conditions. In order to provide satisfactory performance, gasoline must have the optimum distillation characteristics. Gasoline that vaporizes too readily in pumps, fuel
lines, and carburetors will cause decreased fuel flow to the
engine resulting in rough engine operation or stoppage. If the
gasoline does not vaporize easily, difficulty in start-up, poor
warm-up and acceleration, as well as unequal distribution of
fuel to the combustion cylinders may result. The distillation
temperatures of various petroleum products can be determined at atmospheric pressure using ASTM D 86, Standard
Test Method for Distillation of Petroleum Products [1] or at
reduced pressure using ASTM D 1160, Standard Test Method
for Distillation of Petroleum Products at Reduced Pressure
[2]. The 10%, 50%, and 90% (recovered) distillation points
are important control points in the production of fuel blends.
In the mid-1980s the use of automatic distillation equipment gained popularity because of increased ability to control the rate of distillation, emd efficiency in operation. Figure
1 [3] shows the classical manucJ D86 distillation set-up using
a gas burner. Figure 2 [4] shows the manual D86 distillation
apparatus assembly using electric heater. The use of an electric heater improved the ability to control the rate of distillation. However, it was still difficult to m a i n t a i n the 4 - 5
mL/min distillation rate required by the method. The advent
of automatic distillation apparatus allowed the distillation
parameters specified in the method to be controlled accurately without operator intervention. The distillation flask
and the receiving cylinder in an automatic D86 distillation
unit are essentially the same as the manual unit. Although
electric heaters eire used, the use of microprocessors to control the rate of distillation provided precise temperature control and allowed conformance to the method requirements.
Platinum resistance temperature probes or thermocouples
replaced the mercuiy-in-glass thermometers to allow unattended operation. Automatic level followers using optical
sensors removed the necessity of manually observing and
measuring recovered distillation volumes. Data obtained by
automatic distillation units are very similar to those obtained
by manual instruments. However, the data are not statisti-
675
Copyright'
2003 by A S I M International
www.astm.org
676
HANDBOOK
Thermometer
Distilling
Flask
Bath Cover
Heat
Resistant
Boards
Air Vents
SupportFIG. 1Manual D 86 distillation unit with gas burner.
(1)
(2)
(3)
where:
Cc and Cf = corrections to be added algebraically to the temperature reading in Celsius or Fahrenheit
tc = observed temperature reading in Celsius
tf = observed temperature reading in Fahrenheit
Pk barometric pressure prevailing at the time of the
test in kPa
P = barometric pressure prevailing at the time of the
test in mm Hg.
After applying the corrections, the corrected temperature
readings are rounded and reported to the nearest 0.5C
(1.0F) or 0.1 C (0.2F), as appropriate to the apparatus used.
However, other calculated values can be reported from D86
distillation data, such as percent recovery and percentages
evaporated at prescribed temperature readings.
Typical D86 results for motor gasoline, reformulated gasoline, diesel, and jet fuel are given in Table 10 [15], Table 11
[16], Table 12 [17], and Table 13 [18].
25 min.
Length of part
' bath
approx. 390
Front View
NOTE 1^Legend:
l-Condenser bath
2-Bath cover
3-Bath temperature sensor
4-Bath overflow
5-Bath drain
6-Condenser tube
7-Shield
8-Viewing window
9a-Voifage regulator
9b-Voltmeter or ammeter
9o-Power switch
9d-Power light indicator
10-Vent
11-Distillation flask
12-Temperature sensor
13-Flasl< support board
14-Flasl support platform
15-GrDund connection
16-Electric heater
17-Knob for adjusting level
of support platform
18-Power source cord
19-Reoeiver cylinder
20-Receiver cooling bath
21-Receiver cover
677
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
FBP
Sample
1
2
3
4
5
6
7
8
9
10
11
12
13*
14*
+ 1.1
(+0.9)
+0.7
+0.3
+0.5
+ 1.2
+0.3
+0.3
+ 1.7
+ 1.5
+0.9
+ 1.0
+0.3
+0.5
+ 1.9
(0.0)
+ 1.4
+0.6
+ 1.3
+ 1.2
+0.8
+0.5
+2.0
+ 11.5
+ 1.1
(+2.4)"
+0.3
+0.4
+2.2
+0.8
+ 1.6
+0.8
+ 1.3
+ 1.6
+0.8
+0.7
+ 1.8
+ 1.2
+ 1.2
+2.3
+0.4
+0.7
+ 1.6
+0.5
+ 1.0
+0.8
+ 1.3
+ 1.2
+0.7
+0.6
+ 1.5
+0.7
+0.8
+ 1.2
+0.3
+0.5
+ 1.4
+0.4
+0.8
0.3
+ 1.2
+ 1.2
+0.8
+0.7
+ 1.5
+0.4
+0.7
+ 1.2
+0.2
+0.8
+0.7
+0.6
+0.6
0.7
+ 1.0
+ 1.1
+0.8
+ 1.2
+ 1.5
+0.6
+0.6
+ 1.2
+0.9
+ 1.1
+0.8
+0.2
+0.3
+0.6
+0.9
+0.8
+ 1.0
+ 1.2
+ 1.2
+0.9
+ 1.1
+ 1.2
+ 1.4
+ 1.7
+0.7
+0.1
+0.1
+0.8
+0.6
+ 1.1
+ 1.5
+ 1.1
+0.9
+ 1.0
+ 1.0
+0.9
+ 1.0
+ 1.7
+0.7
+0.1
+0.2
+ 1.1
+0.8
+ 1.2
+ 1.6
+ 1.3
+ 1.3
+ 1.4
+0.4
+ 1.1
+0.1
+ 1.0
+0.1
+0.4
+0.9
+ 1.2
+ 1.0
+0.2
+ 1.6
+ 1.9
+0.6
+ 1.9
+0.5
+0.2
+ 1.1
+0.5
+0.4
(+4.7)"
+0.5
+0.8
+0.4
-0.1
+ 1.5
+ 1.1
-0.4
+0.9
-0.4
-0.7
+ 1.2
+0.3
0.7
( + 1.3)"
+0.1
+0.5
+0.4
+0.2
+ 1.7
+ 1.2
+0.4
+0.1
+0.1
(-0.8)
+ 1.0
0.0
-0.4
(-1.2)
-0.8
-0.9
-0.9
-0.3
-0.7
-0.8
-1.2
-2.1
-0.8
-0.9
-1.2
-0.8
1
2
3
4
5
6
7
8
9
10
11
12
13*
14*
''Points between parentheses have not been included in the precision analysis.
'Gasoline-alcohol blends.
NOTE1. Data reported are based on averages of ASTM and IP data.
2. Fourteen samples of gasoline were analyzed in 26 laboratories.
3. The bias reported below is (average of automated results)(average of manual results).
TABLE IBRelative bias between manual and automatic d 86 distillation, various samples [6]
(currently under review in ASTM Subcommittee D02.08).
Summary of Average Relative Bias in C (automanual)
ASTM Interlaboratory Crosscheck Data from 1994 to 1998
Sample
Jet A
Diesel
Mogas
Refor
12
14
13
36
#Lab A
#Lab M
99
129
76
86
26
43
17
8
IBP
-0.7
-1.9
-1.1
-1.1
5%
1.9
2.7
0.2
0.7
10%
20%
30%
40%
50%
60%
70%
80%
90%
1.1
2.1
-0.1
0.3
0.8
1.2
-0.5
0.2
0.6
1.2
0.1
-0.1
0.7
1.1
-0.7
-0.1
0.7
1.0
-0.3
-0.2
0.8
0.7
-0.3
0.4
0.9
0.7
-0.4
0.5
0.8
0.6
-0.5
0.1
0.6
0.5
-1.9
-0.5
60%
70%
80%
1.4
1.2
-0.5
0.8
1.6
1.2
-0.7
0.9
1.5
1.1
-0.9
0.2
90%
1.0
0.8
-3.5
-0.9
95%
0.3
0.3
-3.4
-2.1
FBP
-0.6
0.4
-1.0
0.4
95%
FBP
-1.1
0.8
-1.7
-0.7
#Lab A
#Lab M
IBP
5%
Jet A
Diesel
Mogas
Refor
12
14
13
36
99
129
76
86
26
43
17
8
-1.3
-3.4
-1.9
-2.0
3.3
4.9
0.3
1.4
10%
2.1
3.8
-0.2
0.6
20%
30%
40%
1.3
2.2
-0.9
0.3
1,1
2.1
0.1
-0.2
1.2
2.0
-1.2
-0.2
50%)
1.3
1.9
-0.5
-0.4
0.5
0.5
-5.2
-3.8
Sample 1
Boiling
Point
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
FBP
Manual
Automatic
225.1
268.2
288.9
321.0
347.1
370.1
392.1
416.0
440.8
472.1
518.5
547.5
239.7
270.1
290.1
324.0
349.5
373.4
395.7
420.0
443.5
472.5
514.1
544.8
Manual
Automatic
342.6
371.3
380.7
388.7
394.4
400.9
407.2
414.0
422.6
433.1
452.6
493.9
338.4
373.5
380.7
388.4
394.3
400.0
405.9
412.8
421.7
433.1
452.0
488.1
Sample 3
Manual
Automatic
321.3
363.7
378.7
397.5
412.1
426.6
439.9
453.2
467.7
486.0
511.5
547.4
330.8
364.4
379.0
397.2
411.8
425.9
439.6
452.4
467.8
485.6
514.1
538.7
Sample 2
Sample 3
Boiling
Point
Automatic
Manual
Automatic
Manual
Automatic
Manual
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
FBP
203.2
252.3
274.7
313.5
340.6
363.1
385.6
408.4
433.0
461.3
507.5
538.5
199.6
254.5
280.7
316.5
342.2
366.4
388.9
411.5
436.5
465.5
506.9
536.3
343.0
370.2
376.9
383.3
391.0
397.0
402.9
409.1
419.4
430.3
450.5
492.8
342.7
370.3
378.1
384.8
391.1
396.9
403.3
410.2
419.0
430.9
451.2
482.7
319.0
360.7
374.6
392.7
408.0
422.4
436.4
450.7
465.3
483.3
509.1
544.0
319.0
359.9
374.2
392.5
407.4
421.2
434.1
448.1
462.9
480.3
504.8
536.3
679
Group 1
Group 2
Group 3
Group 4
a65.5
>9.5
<65.5
<9.5
<65.5
<9.5
<65.5
<9.5
S250
<482
slOO
<212
>250
>482
>100
>212
>250
>482
natural
gasoline
Vapor pressure at
37.8C, kPa
100F, psi
(Test Methods
D 323, D 4953,
D 5190, D 5191,
D 5482, IP 69 or
IP 394)
Distillation, IBP "C
"F
EPC
F
250
482
Group 0
Group 1
Group 2
Group 3
Group 4
100
7C (7F)
low
A
32
125
7C (7F)
low
B
38
125
7C (7F)
low
B
38
125
7C (7F)
low
C
50
125
8C (8F)
high
C
50
0-5
32-^0
not above
ambient
13-18
55-65
not above
ambient
13-18
55-65
not above
ambient
13-18
55-65
not above
ambient
0-5
32^0
13-18
55-65
13-18
55-65
13-18"
55-65"
not above
ambient
13-ambient"
55-ambient''
cF
C
'F
Group 0
Group 1
Group 2
Group 3
Group 4
0-1
32-34
0-4
32-40
0-1
32-34
13-18
55-65
0-5
32-40
13-18
55-65
0-5
32-40
13-18
55-65
2-5
5-10
5-10
5-10
0-60
32-140
3
5
of charge
temperature
5-15
60-100
60-100
4-5
4-5
3^
4-5
5 max
4-5
4-5
5 max
5 max
5 max
5 max
''The proper condenser bath temperature will depend upon the wax content of the sample and its distillation fractions. The test is generally performed using one
single condenser temperature. Wax formation in the condenser can be deduced from (a) the presence of wax particles in the distillate coming off the drip tip, (b)
a higher distillation loss than what would be expected base on the initial boiling point of the specimen, (c) an erratic recovery rate and (d) the presence of wax particles during the removal of residual liquid by swabbing with a lint-free cloth (see 8.3). The minimum temperature that permits satisfactory operation shall be used.
In general, a bath temperature in the 0 to 4C range is suitable for kerosine, Grade No 1 fuel oil and Grade No. 1-D diesel fuel oil. In some cases involving Grade
No. 2 fuel oil. Grade No. 2-D diesel fuel oil; gas oils and similar distillates, it may be necessary to hold the condenser bath temperature in the 38 to 60C range.
680
MANUAL
HANDBOOK
Point, %
IBP
5
10
20
30-70
80
90
95
FBP
1.9
1.2
1.2
1.2
1.2
1.2
1.2
3.3
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
+ 0.86Sc
3.9
3.4
2.2
2.2
2.2
2.2
2.2
2.2
Manual
Reproducibility"
Automated
Repeatability"
op
5.6
3.1 + 1.74Sc
2.0 + 1.74Sc
2 . 0 + 1.74Sc
2.0 + 1.74Sc
2.0 + 1.74Sc
0.8 + 1.74Sc
1.1 + 1.74Sc
7.2
10
+
+
+
+
+
+
+
0.86SF
0.86SF
0.86SF
0.86SF
0.86SF
0.86SF
0.86SF
5.6
3.6
3.6
3.6
3.6
1.4
1.9
+
+
+
+
+
+
+
1.74SF
1.74SF
1.74SF
1.74SF
1.74SF
1.74SF
1.74SF
13
2.1
1.7
1.1
1.1
1.1
1.1
2.5
Automated
Reproducibility"
C
-F
3.9
+ 0.67Sc
+ 0.67Sc
+0.67Sc
+0.67Sc
+0.67Sc
+0.67Sc
+ 0.67Sc
4.4
7
3.8
3.0
2.0
2.0
2.0
2.0
4.5
+
+
+
+
+
+
+
0.67SF
0.67SF
0.67SF
0.67SF
0.67SF
0.67SF
0.67SF
4.4
3.3
3.3
2.6
1.7
0.7
2.6
-F
7.2
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
+ 2.0Sc
8.9
13
7.9
6.0
6.0
4.7
3.0
1.2
4.7
+
+
+
+
+
+
+
2.0SF
2.0SF
2.0SF
2.0SF
2.0SF
2.0SF
2.0SF
16
"Sc or SF is the average slope (or rate of change) calculated in accordance with 13.2.
Reproducibility"
"F
IBP
5-95%
FBP
% volume at
temperature reading
"Calculate Sc or Sp from 13.2.
1.0 + 0.35Sc
l.O + 0.41Sc
0.7 + 0.36Sc
1.9
1.8
1.3
0.7
0.7 + 1.92/SC
2.8
1.8
3.1
1.5
+ 0.35SF
+ 0.41SF
+0.36SF
+ 1.66/SF
+ 0.93Sc
+ 1.33Sc
+0.42Sc
+ 1.78/Sc
5.0
3.3
5.7
1.53
+
+
+
+
0.93SF
1.33SF
0.42SF
3.20/SF
Reproducibility"
op
"C
IBP
2%
5%
10%
20-70%
80%
90-95%
FBP
1.1
1.2
1.2
1.2
1.1
3.5
3.5
+ 1.08Sc
+ 1.42Sc
+ 1.42Sc
+ 1.42Sc
+ 1.08Sc
3.5
"C
6.3
6.3
2.0
2.2
2.2
2.2
2.0
+
+
+
+
+
I.OSSF
1.42SF
1.42SF
1.42SF
1.08SF
2.6
2.0
3.0
2.9
3.0
2.0
6.3
8.5
+ 1.92Sc
+ 2.53Sc
+ 2.64Sc
+ 3.97Sc
+ 2.64Sc
+ 2.53Sc
10.5
15.3
4.7
3.6
5.4
5.2
5.4
3.6
+
+
+
+
+
+
1.92SF
2.53SF
2.64SF
3.97SF
2.64SF
2.53SF
18.9
"Sc or SF is the average slope (or rate of change) calculated in accordance with 13.5.
TABLE 9Approximate thermometer reading correction.
Temperature Range
C
10-30
30-50
50-70
70-90
90-110
110-130
130-150
150-170
170-190
190-210
210-230
230-250
250-270
270-290
290-310
310-330
330-350
350-370
370-390
390-410
50-86
86-122
122-158
158-194
194-230
230-266
266-302
302-338
338-374
374^10
410-446
446-482
482-518
518-554
554-590
590-626
626-662
662-698
698-734
734-770
0.63
0.68
0.72
0.78
0.81
0.85
0.89
0.94
0.98
1.02
1.07
1.11
1.15
1.20
1.24
1.28
1.33
1.37
1.41
1.46
of
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D2.08 on VolatiHty. This standeird was originally published in
1951. The latest edition is D 1160-99.
This test method covers the determination, at reduced
pressures, of the boiling range of petroleum products that
can be partially or completely vaporized at a m a x i m u m liquid
temperature of 400C. The reduced pressure inside the apparatus during the test is measured by a Mcleod vacuum gage
or a n appropriately calibrated electronic gage such as the
Baratron. Both manual and automatic methods are specified.
The schematic diagram of a vacuum distillation apparatus is
indicated in Fig. 3 [19]. Both manual and automatic D 1160
distillation units use platinum resistance temperature probes
or thermocouples.
The specimen is distilled at an accurately controlled pressure between 0.13 and 6.7 kPa (1 and 50 m m Hg) under conditions that are designed to provide approximately one theoretical plate fractionation. The distillation pressure is
controlled by a pressure regulating system consisting of a low
CHAPTER
25: VOLATILITY
681
TABLE 10ASTM D-2 interlaboratory cross check programauto D 86 distillation for motor gasoline.
Lab Code
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
FBP
%REC
1
2
3
4
5
6
7
8
10
34.6
30.6
38
34.0
33.8
31.7
34.8
37.1
35.4
51.7
52.2
54
44.5
53.0
49.7
55.1
56.4
47.0
62.0
62.8
64
56.1
62.7
60.0
64.1
65.8
57.8
79.1
81.7
83
75.7
79.7
78.9
82.3
83.9
76.5
94.8
96.1
98
92.8
95.1
95.0
96.8
99.1
94.1
105.7
106.1
107
104.6
105.7
106.2
106.6
108.8
105.7
112.9
112.7
114
112.3
112.5
112.7
113.1
115.6
113.1
119.4
119.4
121
118.7
118.7
119.2
120.2
122.4
119.6
127.4
128.9
131
127.3
126.5
127.4
129.4
131.8
127.7
141.7
146.1
149
141.4
142.1
142.0
146.5
149.0
142.2
167.2
172.2
176
166.7
166.8
164.8
171.1
174.5
166.8
184.2
198.4
217
183.8
185.5
182.2
200.6
208.3
183.4
215.8
214.4
223
223.1
222.2
218.8
214.1
225.0
225.5
97.5
96.6
95.8
96.5
97.9
97.4
96.2
96.9
97.0
TABLE 11ASTM D-2 interlaboratory cross check programauto D 86 distillation for reformulated gasoline.
Lab Code
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
FBP
%REC
%LOSS
E200
E300
1
2
4
5
6
7
8
10
103.1
108.8
100.2
104
105.3
94.1
107.6
109.8
132.5
124.7
130.5
134
120.1
129.2
124.5
132.5
141.6
134.7
140.2
137
133.5
138.0
135.5
142.5
153.3
147.7
151.9
150
147.6
150.0
148.1
159.1
165.6
160.8
164.1
162
160.1
161.0
160.3
170.1
180.5
175.1
178.3
177
175.2
175.3
175.1
183.8
199.2
195.0
198.0
196
195.2
193.5
193.6
202.6
222.5
218.1
220.7
220
219.5
217.4
217.7
222.4
250.2
246.5
247.8
248
247.6
245.5
244.7
244.3
279.1
276.6
276.4
278
395.3
274.7
273.7
278.2
318.1
316.9
313.5
317
319.1
311.5
311.7
319.0
351.8
347.7
346.2
349
353.5
341.4
340.3
353.3
391.1
395.6
396.9
400
395.3
393.2
394.7
394.2
97.4
97.3
97.8
96.9
96.9
99.1
97.7
98.1
1.3
0.9
1.2
3.1
1.9
0.5
50.4
52.8
50.9
51.8
53
52.9
52.9
48.7
85.7
86.8
86.4
86.1
87
87.3
87.2
85.7
0.9
TABLE 12^ASTM D-2 interlaboratory cross check program^Auto D 86 distillation for diesel fuel.
Lab Code
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
FBP
%REC
1
3
4
5
8
9
10
11
13
14
177.4
182.8
176.3
177.1
183.7
179.7
178.8
179.5
182.0
169.5
203.2
205.2
201.7
202.0
228.8
230.7
226.5
228.6
228.7
227.5
227.8
232.6
231.4
229.0
243.2
244.4
240.1
243.4
243.9
241.7
242.2
247
245.9
244.0
253.8
255.2
251.3
254.9
254.9
253.4
253.3
257.4
256.6
255.0
263.3
264.6
260.6
264.1
264.7
261.9
262.8
266.9
**268.3
265.0
271.2
273.4
269.1
273.1
274.1
270.8
271.1
276.3
274.9
273.5
281.6
282.8
278.2
282.0
283.3
280.4
280.6
285.4
283.9
283.0
293.0
294.3
289.2
293.8
294.8
291.9
291.7
297.1
296.1
293.5
309.0
311.8
305.2
310.4
311.9
308.0
308.9
315.0
313.4
309.5
323.9
330.4
319.3
341.3
343.5
336.0
335.2
340.0
339.5
340.6
343.5
341.1
98.3
97.5
98.7
203.8
204.4
203.7
200.5
201.0
209.4
214.1
210.5
210.0
210.5
212.9
212.8
216.4
211.9
212.5
98.3
98.3
97.8
97.6
Lab Code
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
FBP
%REC
1
2
3
4
5
6
8
9
10
158.6
159.7
163.0
160.0
161
159.9
161.4
160.1
161.8
175.0
175.2
178.6
174.1
175
172.4
175.0
176.1
175.9
180.3
179.2
183.0
180.1
179
177.3
180.2
180.4
180.1
187.0
186.1
190.7
186.6
187
184.7
187.3
186.8
186.8
194.4
192.8
197.6
193.0
193
191.3
193.9
194.1
192.5
202.0
199.5
205.1
200.3
200
198.9
200.8
201.3
199.8
210.0
207.7
213.0
207.9
208
206.1
208.0
209.1
207.6
219.3
216.3
221.8
216.6
216
214.3
210.6
217.7
216.2
230.0
226.2
232.5
227.0
227
224.1
226.9
227.9
225.9
239.4
238
244.4
239.0
238
235.4
238.8
239.8
237.3
254.7
253.3
259.6
254.1
253
249.5
253.3
255.6
251.5
261.6
266.1
269.9
265.0
264
259.8
263.8
267.3
261.8
273.3
274
290.8
275.2
277
272.6
277.3
281.2
277.3
99.0
97.5
98.9
98.1
98
99.7
98.4
98.0
98.4
329.9
323.1
325.6
332.9
333.4
TABLE 13ASTM interlaboratory cross check programauto D 86 distillation for jet fuel.
748.1 X A
- 273.1
[1/(VT,K] + (0.3861 X A) - 0.00051606
(4)
(5)
(6)
or
A =
682
MANUAL
HANDBOOK
J_
PRT Sensor
IvjcimoiGHel Option # 2
Pressure
Reguiating System
.L
(ColdTrap
Repressi/ring
tft^Connec
Option # 1
Vacuum Source
Thermowell
Circulating
^^ ._S2?'' I
XTCooiant F i o w ^ ^ = > ~ * / U
Thermo-RegulaW Immersion Heater
where:
AET =
A=
VT,K =
p=
Standard
Test Methods
for
T
35
40
45
50
55
60
G5
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350
0
195.2
202.1
208.9
215.7
222.5
229.2
235.9
242.7
249.3
256.0
262.7
269.3
275.9
282.5
289.1
295.6
302.1
308.6
315.1
321.6
328.0
334.5
340.9
347.3
353.6
360.0
366.3
372.6
378.9
385.2
391.4
397.6
403.9
410.0
416.2
422.4
428.5
434.6
440.7
446.8
452.9
458.9
465.0
471.0
477.0
482.9
488.
494.8
500.7
506.6
512.5
518.4
524.3
530.1
535.9
541.7
547.5
553.3
559.0
564.7
570.5
576.1
581.8
587.5
0.5
195.9
202.7
209.6
216.4
223.1
229.9
236.6
243.3
250.0
256.7
263.3
270.0
276.6
283.2
289.7
296.3
302.8
309.3
315.8
322.2
328.7
335.1
341.5
347.9
354.3
360.6
366.9
373.2
379.5
385.8
392.0
398.3
404.5
410.7
416.8
423.0
429.1
435.2
441.3
447.4
453.5
459.5
465.6
471.6
477.6
483.5
4^.5
495.4
501.3
507.2
513.1
519.0
524.8
530.7
536.5
542.3
548.1
553.8
559.6
565.3
571.0
576.7
582.4
588.1
1
196.6
203.4
210.2
217.0
223.8
230.6
237.3
244.0
250.7
257.4
264.0
270.6
277.2
283.8
290.4
296.9
303.4
309.9
316.4
322.9
329.3
335.7
342.1
348.5
354.9
361.2
367.6
373.9
380.1
386.4
392.7
398.9
405.1
411.3
417.5
423.6
429.7
435.9
442.0
448.0
454.1
460.1
466.2
472.2
478.2
484.1
490.1
496.0
501.9
507.8
513.7
519.6^
525.4
531.3
537.1
542.9
548.6
554.4
560.2
565.9
571.6
577.3
583.0
588.6
1.5
197.3
204.1
210.9
217.7
224.5
231.2
238.0
244.7
251.4
258.0
264.7
271.3
277.9
284.5
291.0
297.6
304.1
310.6
317.1
323.5
330.0
336.4
342.8
349.2
355.5
361.9
368.2
374.5
380.8
387.0
393.3
399.5
405.7
411.9
418.1
424.2
430.4
436.5
442.6
448.6
454.7
460.7
466.8
472.8
478.7
484.7
490.7
496.6
502.5
508.4
514.3
520.2
526.0
531.8
537.6
543.4
549.2
555.0
560.7
566.5
572.2
577.9
583.5
589.2
2
198.0
204.8
211.6
218.4
225.2
231.9
238.6
245.3
252.0
258.7
265.3
271.9
278.5
285.1
291.7
298.2
304.7
311.2
317.7
324.2
330.6
337.0
343.4
349.8
356.2
3625
368.8
375.1
381.4
387.7
393.9
400.1
406.3
412.5
418.7
424.8
431.0
437.1
443.2
449.2
455.3
461.3
467.4
473.4
479.3
485.3
491.3
497.2
503.1
509.0
514.9
520.7
526.6
532.4
538.2
544.0
549.8
555.6
561.3
567.0
572.7
578.4
584.1
589.8
2.5
198.6
205.5
212.3
219.1
225.8
232.6
239.3
246.0
252.7
259.3
266.0
272.6
279.2
285.8
292.3
298.9
305.4
311.9
318.4
324.8
331.2
337.7
344.1
350.4
356.8
363.1
369.4
375.7
382.0
388.3
394.5
400.7
406.9
413.1
419.3
425.4
431.6
437.7
443.8
449.8
455.9
461.9
468.0
474.0
479.9
485.9
491.9
497.8
503.7
509.6
515.5
521.3
527.2
533.0
538.8
544.6
550.4
556.1
561.9
567.6
573.3
579.0
584.7
590.3
3
199.3
206.2
213.0
219.7
226.5
233.3
240.0
246.7
253.4
260.0
266.6
273.3
279.9
286.4
293.0
299.5
306.0
312.5
319.0
325.5
331.9
338.3
344.7
351.1
^7.4
363.8
370.1
376.4
382.7
388.9
395; 1
401.4
407.6
413.8
419.9
426.1
432.2
438.3
444.4
450.5
456.5
462.5
468.6
474.6
480.5
486.5
492.4
498.4
504.3
510.2
516.1
521.9
527.8
533.6
539.4
545.2
550.9
556.7
562.4
568.2
573.9
579.6
585.2
590.9
3.5
200.0
206.8
213.6
220.4
227.2
233.9
240.6
247.3
254.0
260.7
267.3
273.9
280.5
287.1
293.6
300.2
306.7
313.2
319.7
326.1
332.5
338.9
345.3
351.7
358.1
364.4'
370.7
377.0
383.3
389.5
395.8
402.0
408.2
414.4
420.5
426.7
432.8
438.9
445.0
451.1
457.1
463.1
469.2
475.2
481.1
487.1
493.0
AS&.Q
504.9
510.8
516.6
522.5
528.3
534.2
540.0
545.8
551.5
557.3
563.0
568.7
574.4
580.1
585.8
591.5
4
200.7
207.5
214.3
221.1
227.9
234.6
241.3
248.0
254.7
261.3
268.0
274.6
281.2
287.7
294.3
300.8
307.3
313.8
320.3
326.7
333.2
339.6
346.0
K2.3
358.7
3^.0
371.3
377.6
383.9
390.2
396.4
402.6
408.8
415.0
421.1
427.3
433.4
439.5
445.6
451.7
457.7
463.7
469.8
475.8
481.7
487.7
493.6
499.6
505.5
511.4
517.2
523.1
528.9
534.7
540.5
546.3
552.1
557.9
563.6
569.3
575.0
580.7
586.4
592.0
4.5
201.4
208.2
215.0
221.8
228.5
235.3
242.0
248.7
255.4
262.0
268.6
275.2
281.8
288.4
295.0
301.5
308.0
314.5
320.9
327.4
333.8
340.2
346.6
353.0
359.3
365.7
372.0
378.3
384.5
390.8
397.0
403.2
409.4
415.6
421.8
427.9
434.0
440.1
446.2
452.3
458.3
464.4
470.4
476.4
482.3
488.3
494.2
500.2
506.1
511.9
517.8
523.7
529.5
535.3
541.1
546.9
552.7
558.4
564.2
569.9
575.6
581.3
586.9
%2.6
T
36
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
1^
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350
0
180.9
187.6
194.3
201.0
207.6
214.2
220.8
227.4
234.0
240.5
247.1
253.6
260.1
266.5
273.0
279.4
285.8
292.2
298.6
305.0
311.3
317.6
323.9
330.2
336.5
342.8
349.0
355.2
361.4
367.6
373.8
379.9
386.1
392.2
398.3
404.4
410.4
416.5
422.5
428.5
434.5
440.5
446.5
452.4
458.4
464.3
470.2
476.1
481.9
487.8
493.6
499.4
505.3
511.0
516.8
522.6
528.3
534.1
539.8
545.5
551.1
556.8
562.5
568.1
0.5
181.6
188.3
195.0
201.6
208.3
214.9
221.5
228.1
234.6
241.2
247.7
254.2
260.7
267.2
273.6
280.1
286.5
292.9
299.2
30S.6
311.9
318.3
324.6
330.9
337.1
343.4
349.6
355.8
362.0
368.2
374.4
380.5
386.7
392.8
398.9
405.0
411.0
417.1
423.1
429.1
435.1
441.1
447.1
453.0
459.0
464.9
470.8
476.7
482.5
488.4
494.2
500.0
505.8
511.6
517.4
523.2
528.9
534.6
540.3
546.0
551.7
557.4
563.0
568.7
1
< 182.3
189.0
195.6
202.3
208.9
215.6
222.2
228.7
235.3
241.8
248.4
254.9
261.4
267.8
274.3
280.7
287.1
293.5
299.9
306.2
312.6
318.9
325.2
331.5
337.8
344.0
350.2
356.5
362.7
368.8
375.0
381.2
387.3
393.4
399.5
405.6
411.6
417.7
423.7
429.7
435.7
441.7
447.7
453.6
459.5
465.5
471.4
477.2
483.1
489.0
494.8
500.6
506.4
512.2
518.0
5?3.7
529.5
535.2
540.9
546.6
552.3
557.9
563.6
569.2
1.5
182.9
189.6
196.3
203.0
209.6
216.2
222.8
229.4
236.0
242.5
249.0
255.5
262.0
268.5
274.9
281.3
287.8
294.1
300.5
306.9
313.2
319.5
325.8
332.1
338.4
344.6
350.9
357.1
363.3
369.5
375.6
381.8
387.9
394.0
400.1
406.2
412.2
418.3
424.3
430.3
436.3
442.3
448.3
454.2
460.1
466.0
471.9
477.8
483.7
489.5
495.4
501.2
507.0
512.8
518.5
524.3
530.0
535.8
541.5
547.2
552.8
558.5
564.2
569.8
2
183.6
190.3
197.0
203.6
210.3
216.9
223.5
230.0
236.6
243.1
249.7
256.2
262.6
269.1
275.6
282.0
288.4
294.8
301.2
307.5
313.8
320.2
326.5
332.7
339.0
345.3
351.5
357.7
363.9
370.1
376.2
382.4
388.5
394.6
400.7
406.8
412.8
418.9
424.9
430.9
436.9
442.9
448.9
454.8
460.7
466.6
472.5
478.4
484.3
490.1
496.0
501.8
507.6
513.4
519.1
524.9
530.6
536.3
542.0
547.7
553.4
559.1
564.7
570.4
2.5
184.3
191.0
197.6
204.3
210.9
217.5
224.1
230.7
237.3
243.8
250.3
256.8
263.3
269.8
276.2
282.6
289.0
295.4
301.8
308.1
314.5
320.8
327.1
333.4
339.6
345.9
352.1
358.3
364.5
370.7
376.9
383.0
389.1
395.2
401.3
407.4
413.5
419.5
425.5
431.5
437.5
443.5
449.5
455.4
461.3
467.2
473.1
479.0
484.9
490.7
496.5
502.4
508.2
513.9
519.7
525.5
531.2
536.9
542.6
548.3
554.0
559.6
565.3
570.9
3
185.0
191.6
198.3
205.0
211.6
218.2
224.8
231.4
237.9
244.5
251.0
257.5
263.9
270.4
276.8
283.3
289.7
296.1
302.4
308.8
315.1
321.4
327.7
334.0
340.3
346.5
;K2.7
358.9
3^.1
371.3
377.5
383.6
389.7
395.8
401.9
408.0
414.1
420.1
426.1
432.1
438.1
444.1
450.0
456.0
461.9
467.8
473.7
479.6
485.4
491.3
497.1
502.9
508.7
514.5
520.3
526.0
531.8
537.5
543.2
548.9
554.5
560.2
565.8
571.5
3.5
185.6
192.3
199.0
205.6
212.3
218.9
225.4
232.0
238.6
245.1
251.6
258.1
264.6
271.0
277.5
283.9
290.3
296.7
303.1
309.4
315.7
322.1
328.4
334.6
340.9
347.1
353.4
359.6
3K.8
371.9
378.1
384.2
390.3
396.4
402.5
408.6
414.7
420.7
426.7
432.7
438.7
444.7
450.6
456.6
462.5
468.4
474.3
480.2
486.0
491.9
497.7
503.5
509.3
515.1
520.9
526.6
532.3
538.1
543.8
549.4
555.1
560.8
566.4
572.0
4
186.3
193.0
199.6
206.3
212.9
219.5
226.1
232.7
239.2
245.8
252.3
258.8
2K.2
271.7
278.1
284.5
290.9
297.3
303.7
310.0
316.4
322.7
329.0
335.3
341.5
347.8
354.0
360.2
366.4
372.5
378.7
384.8
391.0
397.1
403.1
409.2
415.3
421.3
427.3
433.3
439.3
445.3
451.2
457.2
463.1
469.0
474.9
480.8
486.6
492.5
498.3
504.1
509.9
515.7
521.4
527.2
532.9
538.6
544.3
550.0
555.7
5S^.3
567.0
572.6
4.5
187.0
193.6
200.3
207.0
213.6
220.2
226.8
233.3
239.9
246.4
252.9
259.4
26S.9
272.3
278.8
285.2
291.6
298.0
304.3
310.7
317.0
323.3
329.6
335.9
342.1
348.4
354.6
360.8
367.0
373.2
379.3
385.4
391.6
397.7
403.8
409.8
415.9
421.9
427.9
433.9
439.9
445.9
451.8
457.8
463.7
469.6
475.5
481.3
487.2
493.0
498.9
504.7
510.5
516.2
522.0
527.7
533.5
539.2
544.9
550.6
556.2
561.9
567.5
573.2
T
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350
0
162.0
168.5
174.9
181.4
187.9
194.3
200.7
207.1
213.5
219.9
226.2
232.6
238.9
245.2
251.5
257.8
264.0
270.3
276.5
282.7
288.9
295.1
301.3
307.5
313.6
319.7
325.8
331.9
338.0
344.1
350.1
356.2
362.2
368.2
374.2
380.1
386.1
392.1
398.0
403.9
409.8
415.7
421.6
427.5
433.3
439.1
445.0
450.8
456.6
462.3
468.1
473.9
479.6
485.3
491.0
496.7
502.4
508.1
513.7
519.4
525.0
530.6
536.2
541.8
0.5
1^.6
169.1
175.6
182.1
188.5
194.9
201.4
207.8
214.2
220.5
226.9
233.2
239.5
245.8
252.1
258.4
264.7
270.9
277.1
283.4
289.6
295.7
301.9
308.1
314.2
320.3
326.4
332.5
338.6
344.7
350.7
356.8
362.8
368.8
374.8
380.7
386.7
392.7
398.6
404.5
410.4
416.3
422.2
428.0
433.9
439.7
445.5
451.3
457.1
462.9
"468.7
474.4
480.2
485.9
491.6
497.3
503.0
508.6
514.3
519.9
525.6
531.2
536.8
542.4
1
163.3
169.8
176.2
182.7
189.2
195.6
202.0
208.4
214.8
221.2
227.5
233.8
240.2
246.5
252.8
259.0
265.3
271.5
277.8
284.0
290.2
296.4
302.5
308.7
314.8
320.9
327.0
333.1
339.2
345.3
351.3
357.4
363.4
369.4
375.4
381.3
387.3
393.2
399.2
405.1
411.0
416.9
422.8
428.6
434.5
440.3
446.1
451.9
457.7
463.5
469.3
475.0
480.7
486.5
492.2
497.9
503.5
509.2
514.9
520.5
526.1
531.8
537.4
542.9
1.5
163.9
170.4
176.9
183.3
189.8
196.2
202.6
209.0
215.4
221.8
228.1
234.5
240.8
247.1
253.4
259.7
265.9
272.2
278.4
284.6
290.8
297.0
303.1
309.3
315.4
321.6
327.7
333.7
^9.8
345.9
351.9
358.0
364.0
370.0
376.0
381.9
387.9
^3.8
399.8
405.7
411.6
417.5
423.3
429.2
435.1
440.9
446.7
452.5
458.3
464.1
469.8
475.6
481.3
487.0
492.7
498.4
504.1
509.i3
515.4
521.1
526.7
532.3
537.9
543.5
2
164.6
171.1
177.5
184.0
190.4
196.9
203.3
209.7
216.1
222.4
228.8
235.1
241.4
247.7
254.0
260.3
266.5
272.8
279.0
285.2
291.4
297.6
}3.8
309.9
3t'6.0
322.2
328.3
334.4
340.4
346.5
352.5
358.6
.364.6
370.6
376.6
382.5
388.5
394.4
400.4
406.3
412.2
418.1
423.9
429.8
435.6
441.5
447.3
453.1
458.9
464.6
470.4
476.1
481.9
487.6
493.3
499.0
504.7
510.3
516.0
521.6
527.3
532.9
538.5
544.1
2.5
165.2
171.7
178.2
184.6
191.1
197.5
203.9
210.3
216.7
223.1
229.4
235.7
242.1
248.4
254.7
160.9
267.2
273.4
279.6
285.8
292.0
298.2
304.4
310.5
316.7
322.8
328.9
335.0
341.0
347.1
353.1
359.2
365.2
371.2
377.2
383.1
389.1
395,0
401.0
406.9
412.8
418.7
424.5
430.4
436.2
442.0
447.9
453.7
459.4
465.2
471.0
476.7
482.5
488.2
493.9
499.6
505.2
510.9
516.6
522.2
527.8
533.4
539.0
544.6
3
165.9
172.3
178.8
185.3
191.7
198.2
204.6
211.0
217.3
223.7
230.0
236.4
242.7
249.0
255.3
261.5
267.8
274.0
280.3
286.5
292.7
298.8
305.0
311.1
317.3
323.4
329.5
335.6
341.6
347.7
353.7
359.8
365.8
371.8
377.8
383.7
389.7
395.6
401.5
407.5
413.4
419.2
425.1
431.0
436.8
442.6
448.4
454.2
460.0
465.8
471.6
477.3
483.0
488.7
494.4
500.1
505.8
511.5
517.1
522.8
528.4
534.0
539.6
545.2
3.5
166.5
173.0
179.5
185.9
192.4
'198.8
205.2
211.6
218.0
224.3
230.7
237.0
243.3
249.6
255.9
262.2
268.4
274.7
280.9
287.1
293.3
299.4
305.6
311.8
317.9
324.0
330.1
336.2
342.2
348.3
354.3
360.4
366.4
372.4
378.4
384.3
390.3
396.2
402.1
408.0
413.9
419.8
425.7
431.5
437.4
443.2
449.0
454.8
460.6
466.4
472.1
477.9
483.6
4%.3
495.0
500.7
506.4
512.0
517.7
523.3
528.9
534.6
540.1
545.7
4
167.2
173.6
180.1
186.6
193.0
199.4
205.8
212.2
218.6
225.0
231.3
237.6
244.0
250.3
256.5
262.8
269.0
275.3
281.5
287.7
293.9
300.1
306.2
312.4
318.5
324.6
330.7
336.8
342.9
348.9
354.9
361.0
367.0
373.0
37ao
384.9
390.9
396.8
402.7
408.6
414.5
420.4
426.3
432.1
438.0
443.8
449.6
455.4
461.2
466.9
472.7
478.4
484.2
489.9
495.6
501.3
506.9
512.6
518.3
523.9
529.5
535.1
540.7
546.3
4.5 ,
167.8
174.3
180.8
187.2
193.7
200.1
206.5
212.9
219.2
225.6
231.9
238.3
244.6
250.9
257.2
263.4
269.7
275.9
282.1
288.3
294.5
300.7
306.8
313.0
319.1
325.2
331.3
337.4
343.5
349.5
355.6
361.6
367.6
373.6
379.6
385.5
391.5
397.4
403.3
409.2
415.1
421.0
426.9
432.7
438.6
444.4
450.2
456.0
461.8
467.5
473.3
479.0
484.7
490.5
496.2
501.8
507.5
513.2
518.8
524.4
530.1
535.7
541.3
546.8
T
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350
0
146.8
153.1
159.5
165.8
172.1
178.4
184.6
190.9
197.1
203.3
209.6
215.8
222.0
228.1
234.3
240.4
246.6
252.7
258.8
264.9
271.0
277.0
283.1
289.1
295.2
301.2
307.2
313.2
319.1
325.1
331.0
337.0
342.9
348.8
354.7
360.6
366.5
372.3
378:2
384.0
389.8
395.6
401.4
407.2
413.0
418.8
424.5
430.3
436.0
441.7
447.4
453.1
458.8
464.4
470.1
475.7
481.3
487.0
492.6
498.2
503.7
509.3
514.9
520.4
0.5
147.4
153.8
160.1
166.4
172.7
179.0
185.3
191.5
197.7
204.0
210.2
216.4
222.6
228.7
234.9
241.0
247.2
253.3
259.4
265.5
271.6
277.6
203.7
289.7
295.8
301.8
307.8
313.8
319.7
325.7
331.6
337.6
343.5
349.4
355.3
361.2
367.1
372.9
378.8
384.6
390.4
396.2
402.0
407.8
413.6
419.3
425.1
430.8
436.5
442.3
448.0
4S3.6
459.3
465.0
470.6
476.3
481.9
487.5
493.1
498.7
504.3
509.9
515.4
521.0
1
148.1
154.4
160.7
167.0
173.3
179.6
185.9
192.1
198.4
204.6
210.8
217.0
223.2
229.4
235.5
241.7
247.8
253.9
260.0
266.1
272.2
278.2
284.3
290.3
296.4
302.4
308.4
314.4
320.3
326.3
332.2
338.2
344.1
350.0
355.9
361.8
367.6
373.5
379.3
385.2
391.0
396.8
402.6
408.4
414.2
419.9
425.7
431.4
437.1
442.8
448.5
454.2
459.9
465.6
471.2
476.8
482.5
488.1
433.7
499.3
504.9
510.4
516.0
521.5
1.5
148.7
155.0
161.4
167.7
174.0
180.2
186.5
192.8
199.0
205.2
211.4
217.6
223.8
230.0
236.1
242.3
248.4
254.5
260.6
266.7
272.8
278.8
284.9
290.9
297.0
303.0
309.0
314.9
320.9
326.9
332.8
338.8
344.7
350.6
356.5
362.4
368.2
374.1
379.9
385.8
391.6
397.4
403.2
409.0
414.7
420.5
426.2
432.0
437.7
443.4
449.1
454.8
460.5
466.1
471.8
477.4
483.0
488.6
^4.2
499.8
505.4
511.0
516.5
522.1
2
149.3
155.7
162.0
168.3
174.6
180.9
187.1
193.4
199.6
205.8
212.0
218.2
224.4
230.6
236.7
242.9
249.0
255.1
261.2
267.3
273.4
279.5
285.5
291.5
297.6
303.6
309.6
315.5
321.5
327.5
333.4
3^.3
345.3
351.2
357.1
362.9
368.8
374.7
380.5
386.3
392.2
398.0
403.8
409.5
415.3
421.1
426.8
432.5
438.3
444.0
449.7
455.4
461.0
466.7
472.3
478.0
483.6
489.2
494.8
500.4
506.0
511.5
517.1
522.6
2.5
150.0
156.3
162.6
168.9
175.2
181.5
187.8
194.0
200.2
206.5
212.7
218.9
225.0
231.2
237.4
243.5
249.6
255.7
261.8
267.9
274.0
280.1
286.1
292.1
298.2
304.2
310.2
316.1
322.1
328.1
334.0
339.9
345.9
351.8
357.7
363.5
369.4
375.3
381.1
386.9
392.7
398.5
404.3
410.1
415.9
421.6
427.4
433.1
438.8
444.5
450.2
455.9
461.6
467.3
472.9
478.5
484.2
489.8
495.4
501.0
506.5
512.1
517.7
523.2
3
150.6
156.9
163.3
169.6
175.8
182.1
188.4
194.6
200.9
207.1
213.3
219.5
225.7
231.8
238.0
244.1
250.2
256.4
262.4
268.5
274.6
280.7
286.7
292.7
298.8
304.8
310.8
316.7
322.7
328.7
334.6
340.5
346.4
352.4
358.2
364.1
370.0
375.8
381.7
387.5
393.3
399.1
404.9
410.7
416.5
422.2
428.0
433.7
439.4
445.1
450.8
456.5
462.2
467.8
473.5
479.1
484.7
490.3
495.9
501.5
507.1
512.7
518.2
523.7
3.5
151.2
157.6
163.9
170.2
176.5
182.7
189.0
195.3
201.5
207.7
213.9
220.1
226.3
232.4
238.6
244.7
250.9
257.0
263.1
269.1
275.2
281.3
287.3
293.3
299.4
305.4
311.4
317.3
323.3
329.3
335.2
341.1
347.0
352.9
358.8
364.7
370.6
376.4
382.3
388.1
393.9
399.7
405.5
411.3
417.0
422.8
428.5
434.3
440.0
445.7
451.4
457.1
462.7
468.4
474.0
479.7
485.3
490.9
496.5
502.1
507.6
513.2
518.8
524.3
4
151.9
158.2
164.5
170.8
177.1
183.4
189.6
195.9
202.1
208.3
214.5
220.7
226.9
233.1
239.2
245.3
251.5
257.6
263.7
269.7
275.8
281.9
287.9
293.9
300.0
306.0
312.0
317.9
323.9
329.9
335.8
341.7
347.6
353.5
359.4
3^.3
371.2
377.0
382.8
388.7
394.5
400.3
406.1
411.9
417.6
423.4
429.1
434.8
440.5
446.3
451.9
457.6
463.3
468.9
474.6
480.2
485.8
491.4
497.0
502.6
508.2
513.8
519.3
524.9
4.5
152.5
158.8
165.1
171.4
177.7
184.0
190.3
196.5
202.7
208.9
215.1
221.3
227.5
233.7
239.8
246.0
252.1
258.2
264.3
270.4
276.4
282.5
288.5
294.5
300.6
306.6
312.6
318.5
324.5
330.4
336.4
342.3
348.2
354.1
360.0
365.9
371.7
377.6
3^.4
389.3
395.1
400.9
406.7
412.4
418.2
423.9
429,7
435.4
441.1
446^8
452.5
458.2
463.9
469.5
475.2
480.8
486.4
492.0
497.6
503.2
508.8
514.3
519.9
525.4
T
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
290
295
300
305
310
315
320
325
330
335
340
345
350
0
131.0
137.1
143.3
149.4
155.6
161.7
167.8
173.9
180.0
186.0
192.1
198.2
204.2
210.2
216.2
222.2
228.2
234.2
240.2
246.1
252.1
258.0
263.9
269.9
275.8
281.7
287.5
293.4
299.3
305.1
310.9
316.8
322.6
328.4
334.2
340.0
345.7
351.5
357.3
363.0
368.7
374.5
380.2
385.9
391.5
397.2
402.9
408.5
414.2
419.8
425.5
431.1
436.7
442.3
447.9
453.4
459.0
464.6
470.1
475.6
481.2
486.7
492.2
497.7
0.5
131.6
137.8
143.9
150.1
156.2
162.3
168.4
174.5
180.6
186.6
192.7
198.8
204.8
210.8
216.8
222.8
228.8
234.8
240.8
246.7
252.7
258.6
264.5
270.5
276.4
282.2
288.1
294.0
299.8
305.7
311.5
317.4
323.2
329.0
334.8
340.6
346.3
352.1
357.8
363.6
369.3
375.0
380.7
386.4
392.1
397.8
403.5
409.1
414.8
420.4
426.0
431.6
437.2
442.8
448.4
454.0
459.6
465.1
470.7
476.2
481.7
487.2
492.7
498.2
1
132.2
138.4
144.5
150.7
156.8
162.9
169.0
175.1
181.2
187.3
193.3
199.4
205.4
211.4
217.4
223.4
229.4
235.4
241.4
247.3
253.3
259.2
265.1
271.0
276.9
282.8
288.7
294.6
300.4
306.3
312.1
317.9
323.8
329.6
335.3
341.1
346.9
352.7
aSb.A
364.1
369.9
375.6
381.3
387.0
392.7
398.4
404.0
409.7
415.3
421.0
426.6
432.2
437.8
443.4
449.0
454.5
460.1
AIS5.7
471.2
476.7
482.3
487.8
493.3
498.8
1.5
132.8
139.0
145.1
151.3
157.4
163.5
169.6
175.7
181.8
187.9
193.9
200.0
206.0
212.0
218.0
224.0
230.0
236.0
242.0
247.9
253.9
259.8
265.7
271.6
277.5
283.4
289.3
295.2
301.0
306.9
312.7
318.5
324.3
330.1
335.9
341.7
347.5
353.2
359.0
364.7
370.4
376.2
381.9
387.6
393.3
%8.9
404.6
410.2
415.9
421.5
427.1
432.8
438.4
444.0
449.5
455.1
460.7
466.2
471.8
477.3
482.8
488.3
493.8
499.3
2
133.4
139.6
145.8
151.9
158.0
164.1
170.2
176.3
182.4
188.5
194.5
200.6
206.6
212.6
218.6
224.6
230.6
236.6
242.6
248.5
254.5
260.4
266.3
272.2
278.1
284.0
289.9
295.8
301.6
307.4
313.3
319.1
324.9
330.7
336.5
342.3
348.1
353.8
359.6
365.3
371.0
376.7
382.4
388.1
393.8
399.5
405.2
410.8
416.5
422.1
427.7
433.3
438.9
444.5
450.1
455.7
461.2
466.8
472.3
477.8
483.4
488.9
494.4
499.9
2.5
134.1
140.2
146.4
152.5
158.6
164.7
170.8
176.9
183.0
189.1
195.1
201.2
207.2
213.2
219.2
225.2
231.2
237.2
243.2
249.1
255.1
261.0
266.9
272.8
278.7
284.6
290.5
296.3
302.2
308.0
313.9
319.7
325.5
331.3
337.1
342.9
348.6
354.4
360.1
365.9
371.6
377.3
383.0
388.7
394.4
400.1
405.7
411.4
417.0
422.6
428.3
433.9
439.5
445.1
450.6
456.2
461.8
467.3
472.9
478.4
483.9
489.4
494.9
500.4
3
134.7
140.8
147.0
153.1
159.2
165.4
171.5
177.5
183.6
189.7
195.7
201.8
207.8
213.8
219.8
225.8
231.8
237.8
243.8
249.7
255.6
261.6
267.5
273.4
279.3
285.2
291.1
296.9
302.8
308.6
314.4
320.3
326.1
331.9
337.7
343.4
349.2
355.0
360.7
366.4
372.2
377.9
383.6
389.3
395.0
400.6
406.3
411.9
417.6
423.2
428.8
434.4
440.0
445.6
451.2
456.8
462.3
467.9
473.4
479.0
484.5
490.0
495.5
501.0
3.5
135.3
141.5
147.6
153.7
159.9
166.0
172.1
178.1
184.2
190.3
196.3
202.4
208.4
214.4
220.4
226.4
232.4
238.4
244^4
250.3
256.2
262.2
268.1
274.0
279.9
285.8
291.6
297.5
303.4
309.2
315.0
320.8
326.7
332.5
338.2
344.0
349.8
355.5
361.3
367.0
372.7
378.4
384.2
389.8
395.5
401.2
406.9
412.5
418.1
423.8
429.4
435.0
440.6
446.2
451.8
457.3
462.9
468.4
474.0
479.5
485.0
490.5
496.0
501.5
4
135.9
142.1
148.2
154.3
160.5
166.6
172.7
178.8
184.8
190.9
196.9
203.0
209.0
215.0
221.0
227.0
233.0
239.0
244.9
250.9
256.8
262.8
268.7
274.6
280.5
286.4
292.2
298.1
303.9
309.8
315.6
321.4
327.2
333.0
338.8
344.6
350.4
356.1
361.9
367.6
373.3
379.0
384.7
%0.4
396.1
401.8
407.4
413.1
418.7
424.3
430.0
435.6
441.2
446.7
452.3
457.9
463.4
469.0
474.5
480.1
485.6
491.1
496.6
502.1
4.5
136.5
142.7
148.8
155.0
161.1
167.2
173.3
179.4
185.4
191.5
197.5
203.6
209.6
215.6
221.6
227.6
233.6
239.6
245.5
251.5
257.4
263.4
269.3
275.2
281.1
286.9
292.8
298.7
304.5
310.4
316.2
322.0
327.8
333.6
3^.4
345.2
350.9
356.7
362.4
368.2
373.9
379.6
385.3
391.0
396.7
402.3
Afy&.Q
413.6
419.3
424.9
430.5
436.1
441.7
447.3
452.9
458.4
464.0
469.5
475.1
480.6
486.1
491.6
497.1
502.6
0
109.0
114.9
120.8
126.7
132.6
138.5
144.3
150.2
156.0
161.9
167.7
173.6
179.4
185.2
191.0
196.8
202.6
208.3
214.1
219.9
225.6
231.4
237.1
242.8
248.5
254.3
260.0
2K.7
271.3
277.0
282.7
288.4
294.0
299.7
305.3
310.9
316.5
322.2
327.8
333.4
338.9
344.5
350.1
355.7
361.2
366.8
372.3
377.8
383.4
388.9
394.4
399.9
405.4
410.9
416.4
421.8
427.3
432.7
438.2
443.6
449.1
454.5
459.9
465.3
0.5
109.6
115.5
121.4
127.3
133.2
139.0
144.9
150.8
156.6
162.5
168.3
174.1
180.0
185.8
191.6
197.4
203.1
208.9
214.7
220.4
226.2
231.9
237.7
243.4
249.1
254.8
260.5
266.2
271.9
277.6
283.3
288.9
294.6
300.2
305.9
311.5
317.1
322.7
328.3
333.9
339.5
345.1
350.7
356.2
361.8
367.3
372.9
378.4
383.9
389.4
394.9
400.4
405.9
411.4
416.9
422.4
427.8
433.3
438.7
444.2
449.6
455.0
460.4
4^.8
1
110.2
116.1
122.0
127.9
133.7
139.6
145.5
151.4
157.2
163.1
168:9
174.7
180.5
186.3
192.1
197.9
203.7
209.5
215.3
221.0
226.8
232.5
238.2
244.0
249.7
255.4
261.1
266.8
272.5
278.2
283.8
289.5
295.1
300.8
306.4
312.0
317.7
323.3
328.9
334.5
340.1
345.6
351.2
356.8
362.3
367.9
373.4
378.9
384.5
390.0
395.5
401.0
406.5
412.0
417.4
422.9
428.4
433.8
439.3
444.7
450.1
5.6
461.0
466.4
1.5
110.7
116.7
122.6
128.5
134.3
140.2
146.1
151.9
157.8
163.6
169.5
175.3
181.1
186.9
192.7
198.5
204.3
210.1
215.8
221.6
227.3
233.1
238.8
244.5
250.3
256.0
261.7
267.4
273.0
278.7
284.4
290.0
295.7
301.3
307.0
312.6
318.2
323.8
329.4
335.0
340.6
346.2
351.8
357.3
362.9
368.4
374.0
379.5
385.0
390.5
396.0
401.5
407.0
412.5
418.0
423.5
428.9
434.4
439.8
445.3
450.7
A56A
461.5
466.9
2
111.3
117.2
123.1
129.0
134.9
140.8
146.7
152.5
158.4
164.2
1701
175.9
181.7
187.5
193.3
199.1
204.9
210.7
216.4
222.2
227.9
233.7
239.4
245.1
250.8
256.5
262.2
267.9
273.6
279.3
285.0
290.6
296.3
301.9^
307.5
313.2
318.8
324.4
330.0
335.6
341.2
346.8
352.3
357.9
363.4
369.0
374.5
380.0
385.6
391.1
396.6
402.1
407.6
413.1
418.5
424.0
429.5
434.9
440.4
445.8
451.2
456.7
462.1
467.5
2.5
111.9
117.8
123.7
129.6
135.5
141.4
147.3
153.1
159.0
164.8
170.6
176.5
182.3
188.1
193.9
199.7
205.5
211.2
217.0
222.7
228.5
234.2
240.0
245.7
251.4
257.1
262.8
268.5
274.2
279.9
285.5
291.2
296.8
302.5
308.1
313.7
319.3
325.0
330.6
336.1
341.7
347.3
352.9
358.4
364.0
369.5
375.1
380.6
386.1
391.6
397.1
4(^.6
408.1
413.6
419.1
424.6
430.0
435.5
440.9
446.3
451.8
457.2
482.6
468.0
3
112.5
118.4
124.3
130.2
136.1
142,0
147.8
153,7
159,5
165,4
171,2
177.0
182.9
188,7
194,5
200,3
206,0
211.8
217.6
223.3
229.1
234.8
240.5
246.3
252.0
257.7
263.4
269.1
274.8
280.4
286.1
291.7
297.4
303.0
308.7
314.3
319.9
325.5
331.1
336.7
342.3
347.9
353.4
359.0
364.5
370.1
375.6
381.2
386.7
392.2
397.7
403.2
408.7
414.2
419.6
425.1
430.6
436.0
441.5
446.9
452.3
457.7
463.1
468.6
3.5
113.1
119.0
124.9
130.8
136.7
142.6
148.4
154.3
160.1
166.0
17f.8
177.6
183.4
189.2
195.0
200.8
206.6
212.4
218.1
223.9
229.6
235.4
241.1
246,8
252.5
258.3
263.d
269.6
275.3
281.0
286.7
292.3
298.0
303.6
309.2
314.9
320.5
326.1
331.7
337.3
342,8
348,4
354,0
359,5
365.1
370.6
376.2
381.7
387.2
392.7
398.2
403.7
409.2
414.7
420.2
425.6
431.1
436.6
442.0
447.4
452.9
458.3
463.7
469.1
4
113.7
119.6
125.5
131.4
137.3
143.1
149.0
154.9
160.7
166.6
172.4
178.2
184.0
189.8
195.6
201.4
207.2
213.0
218.7
224.5
230.2
236.0
241.7
247.4
253.1
258.8
264.5
270.2
275.9
281.6
287.2
292.9
298.5
304.2
309.8
315.4
321.0
326.6
332.2
337.8
343.4
349.0
354.5
360.1
3K.7
371.2
376.7
382.3
387.8
393.3
398.8
404.3
409.8
415.3
420.7
426.2
431.6
437.1
442.5
448.0
453.4
458.8
464.2
4^.6
4.5
114.3
1202
126.1
132.0
137.9
143.7
149.6
155.5
161.3
167.1
173.0
178.8
184.6
190.4
196.2
202.0
207.8
213.5
219.3
225.0
230.8
236.5
242.3
248.0
253.7
259.4
265.1
270.8
276.5
282.1
287.8
293.4
299.1
304.7
310.4
316.0
321.6
327.2
332.8
338.4
344.0
349.5
355.1
360.7
366.2
371.8
377.3
382.8
388.3
393.8
399.3
404.8
410.3
415.8
421.3
426,7
432,2
437,6
443,1
448,5
453,9
459,4
464.8
470,2
689
Reproducibility
0.13kPa(l mmHg)
17
3.3
15
7.1
56
31
49
27
IBP
FBP
Volume
Recovered
5-50%
60-90%
5-50%
60-90%
5-50%
60-90%.
5-50%
60-90%
C/V%
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0
2.4
2.9
3.2
3.4
3.6
3.8
3.9
4.0
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.8
4.9
5.0
5.0
5.1
5.1
5.2
5.2
5.3
5.3
5.4
5.4
5.5
5.5
2.5
3.0
3.3
3.5
3.7
3.9
4.0
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.8
4.9
5.0
5.1
5.1
5.2
5.2
5.3
5.4
5.4
5.5
5.5
5.6
5.6
5.7
5.7
1.9
2.4
2.8
3.1
3.3
3.6
3.8
3.9
4.1
4.3
4.4
4.5
4.7
4.8
4.9
5.0
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
6.0
6.0
6.1
6.2
6.3
2.0
2.5
2.9
3.2
3.5
3.7
3.9
4.1
4.3
4.4
4.6
4.7
4.8
5.0
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
5.3
6.3
6.4
6.5
6.5
10
13
16
16
21
23
25
27
29
30
32
34
35
37
38
40
41
43
44
46
47
48
50
51
52
54
55
56
57
3.9
6.0
7.6
9.4
11
12
13
15
16
17
18
19
20
23
22
23
24
25
25
26
27
28
29
30
30
31
32
33
33
34
7.0
9.3
11
12
14
15
16
16
17
18
19
19
20
21
21
22
22
23
23
24
24
25
25
26
26
27
27
27
28
28
5.4
7.2
8.5
9.8
11
11
12
13
13
14
15
15
16
16
16
17
17
18
18
19
19
19
20
20
20
21
21
21
22
22
Repeatability
15.9
8.0
5.5
3.8
3.8
5.2
4.7
6.5
4.4
7.3
6.5
9.5
10 mm Hg Pressure
Reproducibility
29.9
17.5
16
12.2
12
9.6
8.8
9.5
11.1
13.1
24.8
37.4
Repeatability
Reproducibility
35.4
11.1
8.0
10.4
7.1
8.6
10.2
12.8
11.3
14.1
25.5
19.7
16.7
6.8
3.7
4.3
3.2
2.9
3.1
3.7
3.4
3.8
5.0
6.4
TABLE 22Cross reference of international distillation standards relative to ASTM distillation test methods.
ASTM
Designation
U.S.
D86
D 1160
D2892
D5236
Distillation
Pressure
Atmospheric
Vacuum
Vacuum
Vacuum
ISO
IP
BS
AFNOR
DIN
Europe
3405
6616
8708
U.K.
123
U.K.
7392
France
M07-002
Germany
51 751
51 356
51567
51 567
FTM
JIS
791-1001
Japan
K2254
K2258
690
HANDBOOK
(7)
= C + 0.033 (760 - P)
(8)
Cleveland
Pensky-Martens
Open
Closed
70 mL
75 mL
slice
Stirring
Rate
N/A
N/A
N/A
90-120 r p m
D 93 Proc. B
Pensky-Martens
Closed
75 mL
>110X
250 r p m
D 1310
D3278
D3828
D3941
Tag
Setaflash
Small Scale
Equilibrium
Method
Continuously
Closed Cup
Open
Closed
Closed
Closed
Closed
Closed
50 mL
2 mL
2mL
50 mL
75 m L
ImL
All
All
All
All
All
All
D6450
Apparatus
Tag
Cup
Type
Closed
Sample
Size
Expected
Flash
Point
50 mL
<60C
aeox
N/A
ranges
ranges
ranges
ranges
ranges
ranges
N/A
N/A
N/A
N/A
90-120 r p m
Heating
Rate
rC/min
3C/mln
14-17C/min
5-6C/min
l-1.5C/min
rC/min
N/A
N/A
N/A
N/A
5.5 0.5
C/min
Flash Pt.
(FP) Test
Initiation
5C below FP
5C below FF
28C below FF
23 5 ^
below FF
23 5 ^
below FF
10C below FF
Target FF
Target FF
Target FP
Target FF
18C below FF
Repeat
FP
Test
Every
Report to
Nearest
0 . 5 X rise
1.0Crise
1.0C rise
1.0C rise
0.5''C
0.5C
1.0C
0.5C
2.0C rise
0.5C
1.0C rise
N/A
N/A
N/A
N/A
l.O-Crise
0.5^
0.5C
0.5C
0.5C
0.5C
0.5-0
691
TABLE 24Comparison of the scope and precision of the different ASTM flash point test methods.
ASTM
Designation
D56
Apparatus
Tag
Scope
D92
D 93 Proc. A
Cleveland
Pensky-Martens
D 93 Proc. B
Pensky-Martens
D1310
Tag
D3278
Setaflash
D3828
Small Scale
D3941
Equilibrium
method
Liquids with
specimen and vapor
temperature
approximately in
equilibrium
D6450
Continuously
Closed Cup
Fuel oils,
lubricating oils,
other solvents, and
liquids
Liquids, viscosity
<5.5 mm^/s at 40C
or 9.5 mm^/s at
25C.
Petroleum products
Distillate fuels
(diesel, kerosene,
heating oil, turbine
fuels, new
lubricating oils, and
other homogeneous
petroleum liquids
not covered by
Proc. B
Temperature
Range
Below 93C
79-400''C
40-360C
Repeatability
(95%
Confidence)
Expected
Flash Point
Reproducibility
(95%
Confidence)
<60C
>60-C
1.2''C
1.6C
4.3C
5.8C
All ranges
8C
0.035 X C
X = reported
result inC
18C
0.078 X C
X = reported
result in C
40-360''C
Residual
fuels
Others
2C
5C
6C
10C
- 1 8 to 165C
0-110C
2C
5C
1.7C
3.3''C
4C
7C
Paints, enamels,
lacquers, varnishes.
and related
products with
viscosity, 150 St at
25C
Petroleum products
-18to93C
93 to 165C
Solvents
Resins/paints
20-70C
above TCC
O.S'C
0.022 M"-^ C
M = mean of
two results
0-1 l O X
All ranges
2C
3C
10-250C
All ranges
1.9C
3.rc
Ambient to
300C
3.3X
5.0C
Test Method
Reference Value
C
Expanded
Uncertainty (C)
# of Independent
Observations
17
0.8
1.0
21
1.2
6
0.7
17
RM8518
n-Undecane
14
2.5
1.4
21
6
1.6
RM8519
2.6
13
n-Tetradecane
17
2.7
RM 8520
2.4
13
n- Hexadecane
16
2.8
Uncertainty: The uncertainty of each value in this Report is the numerical value of an expanded uncertainty V = kuc, with U determined from a
combined standard uncertainty Uc, and a coverage factor k equal to a t-factor from the ^distribution with degrees of freedom equal to the number
of independent observations minus 1. This expanded uncertainty defines a range of values for the certified value within which the true value is believed to lie, at a confidence level of 95%.
RM8517
n-Decane
D56
D93
D 3278/D 3828
D56
D92
D93
D 3278/D 3828
D92
D93
D92
D93
50.9
52.8
49.7
67.1
73.2
68.7
65.9
115.5
109.3
138.8
133.9
692
MANUAL
HANDBOOK
D 56/ D 93
n-Decane
n-Undecane
n-Tetradecane
n-Hexadecane
0.964
0.977
1.065
1.057
1.036
Flome Size
Bead
D 3278/D 93
D 3828/D 93
0.941
0.982
Both
ThermomeJer
y \ Thermometer
D 92/D 93
Flome Tip
Oil
Chomber
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D2.08 on Volatility. It was originally published in 1921. The
latest edition is D 92-98b.This open cup tester has been used
in the United States since 1908. In early models, testing was
conducted by passing a small test flame across the top of the
cup by hand. Later on, this was converted to the use of a
swinging arm, which controlled the movement of the test
flame at a defined height above the top of the cup. Figure 5
[25] shows the schematic diagram of a manual Cleveland
Open Cup Apparatus.
In addition to determining the flash point of a liquid material, D 92 EJSO determines the fire point. Fire point is defined
as the lowest temperature corrected to a barometric pressure
of 101.3 kPa (760 m m Hg) at which application of an ignition
source causes the vapors of the test specimen to ignite and
sustain burning for a m i n i m u m of 5 s under specified conditions of test. The fire point determination is an extension of
the flash point test. After the flash point is determined, heating of the specimen is continued at a rate of 5-6C/min. The
test flame is applied at 2C intervals until the test specimen
ignites and sustains burning for a minimum of 5 s. Just like
flash point, the fire point is also corrected for barometric
pressure using the same equation utilized for flash point.
ASTM D 93, Standard Test Method for Flash Points
Pensky-Martens
Closed Cup Tester
FIG. 4D 56 tag closed cup tester (manual).
Test Method
by
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D2.08 on Volatility. It was originally published in 1918 and is
by
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D2.08 on Volatility. It was originally published in 1921. The
latest edition is D 93-00. It was developed in Germany in 1870
by Meirtens, and was based on the original tester by Pensky.
Its development in 1870 was for flash points well above 100C
to test lubricating oils and other similar materieds such as bitumen products. A schematic diagram of a manual PenskyMartens Closed Cup Flash Tester is given in Fig. 6 [26].
Test Method D 93 Procedure A covers the determination of
flash points of relatively non-viscous, homogeneous materials. Test Method D 93 Procedure B, on the other hand, is
meant to measure viscous, nonhomogeneous materials like
residual oils, materials that tend to form surface film when
heated, and liquids that contain suspended solids. A 1994 in-
693
THCRMOMETEII
A8TM NO. l i e
IP > C
TEST FLAMC
APPLICATOR
TEST CUP
HEATIN* PLATE
ORIFICE
MCTAL aCAO
TO AS SUPPLY
HEATER PLANE TVPE
OR ELECTRIC RESISTANCE TVPE
inches
millimetres
ADiameter
BRadius
CDiameter
D
E
FDiameter
min
max
min
max
3.2
152
1.6
4.8
nominal
nominal
2
7
nominal
0.126
6
0.063
0.189
nominal
nominal
0.078
0.276
nominal
6
0.8
0.236
0.031
terlaboratory study [36,37] indicated that samples with kinematic viscosity greater than 13 mm^ls at 40C gave a lower
observed flash point when tested by Procedure A compcired
to the flash point determined by Procedure B. A possible explanation is a lag in the temperature detected by the temperature measuring device as the kinematic viscosity of the sample increases, especially when equilibration of the vapor and
the bulk of the sample is not established before the flash
point is detected. Therefore, viscosity effects must be taken
into account when deciding on the appropriate procedure for
D 93 flash point determination.
ASTM D 1310, Standard Test Method for Flash Point
and Fire Points of Liquids by Tag Open Cup Apparatus
This test method is under the jurisdiction of ASTM Committee D-01 on Paints and Related Coatings, Materials, and Applications, and is the direct responsibility of Subcommittee
D1.22 on Health and Safety. It was originally published in
1952. The latest edition is D 1310-01. The modem Tag open
cup tester was derived from the Tagliabue Open cup Tester
patented in 1862.
ASTM D 3278, Standard Test Method for Flash Point by
Setaflash Closed Cup Apparatus
This test method is under the jurisdiction of ASTM Committee D-1 and is the direct responsibility of Subcommittee
D1.22. It was originally published in 1973. The latest edition
is D 3278-96. The original closed cup miniflash point tester
was invented by T. Kidd in the early 1960s. It was commer-
cialized by Stanhope-Seta Ltd. during 1967 to 1969, and became known as the Setaflash flash point tester. The Setaflash
flash test method differs from the other flash point methods
because the temperature equilibrium between the specimen
and the vapor above it is allowed to be established prior to
testing for a flash point. A fresh specimen is used for each test
temperature, unlike D 56, D92, and D 93, where multiple
flash point testing is done on a given specimen at various test
temperatures. A schematic diagram of the Setaflash apparatus is shown in Fig. 7 [28].
ASTM D 3828, Standard Test Method for Flash Point by
Small Scale Closed Cup Tester
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee D
2.08. It was originally published in 1979. The latest edition is
D 3828-98. The apparatus used in this test method is the
same as that described in D 3278. Just like the Setaflash test
method, this method allows temperature equilibrium
between the specimen and the vapor above it to be established prior to testing for a flash point. This test method is
applicable to petroleum products not covered within the
scope of D 3278.
ASTM D 3941, Standard Test Method for Flash Point by
the Equilibrium Method with a Closed Cup Apparatus
This test method is under the jurisdiction of ASTM Committee D-01 and is the direct responsibility of Subcommittee D 1.22. It was originEdly published in 1980. The latest
694
HANDBOOK
SHUTTER
HANDLE (OPTIONAL)
(MUST NOT TIP EMPTY CUP)
THERMOMETER
DISTANCE PIECE
D
TEST CUP
mm
n*
F MIN THICKNESS
OVER CUP AREA
lE.METAL SURROUNDING
THE CUP
A
B
C
0
e
F
max
in.
min
max
4.37
5.16 0.172 0.203
41,94 42.06 1.651 1.6S6
1.58
3.18 0.062 0.125
9.52
0.375
Sr.23 57.86 2.253 2.278
6.35
0.25
HEATER FLAME-TYPE
OR ELECTRIC RESISTANCE
TYPE (FLAME TYPE SHOWN)
AHinge
BUd
CPilot flame jet
DTest flame jet
EFiling orifice
FTest flane gas control screw
GShutter guide
HShutter knob
JShutter
KUdlock
LUd sealing 0-ring
MThermometer
NSample cup
P^Thermometer well
RTest flame gage
30.45
7.65
7.60
30/W
m^
12.47
12.42
5.10
5.05
Li|:W
SHUTTER
(1.22 THICK NOM.)
48.42
46.37
4.00
10.00
7.65
7.60
IT^iZZZ^^
16.00
10.18
IO.I3
p
7.00 OIA.
NOM.
42.00
41.00
49.70
49.40
5.10
TYP.
5.05
12.47
12.42
LID
( 2 . 0 0 THICK NOM.)
TABLE 27Cross reference of international flash point methods versus ASTM flash point test methods.
ASTM
u.s
D56
D92
D93
D 1310
D3278
D3828
D3941
D6450
ISO
IP
DIN
AFNOR
Europe
U.K.
304
36
34
Germany
France
303
303
55 680
55 680
2592
2719
3679
3679
1523
170 (Abel)
304
51 376
51 758
51 755
(Abel-Pensky)
FTM
EN
SIS
791-1101
791-1103
M07-019
K2265-1996
K2265-1996
K2265-1996
456
M07-036
ns
Japan
K2265-1996
K2265-1996
K2265-1996
Europe
150 223
696
HANDBOOK
Crude Distillation
Crude oil is a complex mixture of mostly organic molecules
with minute quantities of inorganic materials. The organic
molecules are mostly hydrocarbons, with minor sulphur, nitrogen, and oxygen components, and trace quantities of metals such as vanadium and nickel. In the assay or preliminary
characterization of crude oil, atmospheric and reduce pressure distillations are performed in order to determine the
yields of various boiling ranges.
Two test methods are used in the distillation of crude oils,
ASTM D 2892, Standard Test Method for Distillation of
Crude Petroleum (15-Theroetical Plate Column) [39], and
ASTM D 5236, Standard Test Method for Distillation of
Heavy Hydrocarbon Mixtures (Vacuum Potstill Method)
[40]. Crude oil distillation is one of a number of tests conducted on a crude oil to determine its market value. The fractions produced during crude oil distillation can be used alone
or in combination with other fractions to produce samples
for analytical studies, engineering, and product quEility evaluations. The precision values for these two methods are summarized in Table 28.
ASTM D 2892, Standard Test Method for Distillation of
Crude Petroleum (15-Theoretical Plate Column)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee D02.08. It was originally published in 1970. The latest
edition is D 2892-99a. It describes the procedure for the distillation of stabilized crude petroleum to a final cut temperature of 400C AET (Atmospheric Equivalent Temperature).
AET is the atmospheric equivalent temperature converted
from the observed vapor temperatures and was previously
discussed in the ASTM D1160 section. Equations 4, 5, and
6, as well as Tables 14-19, are applicable for D 2892 also.
This test method employs a fractionating column having an
efficiency of 14-18 theoretical plates operated at a reflux ratio of 5:1., thus corresponding to the standard laboratory
distillation efficiency referred to as 15/5. Figure 8 [37]
shows the schematic diagram of the apparatus used for this
test method. Distillation yields by mass or volume are calculated from the data and reported to the nearest 0.1%. Vapor temperatures are reported to the neeirest 0.5C. TypiceJ
D2892 distillation results for two different crude oils are
given in Tables 29 [41] and 30 [42].
CONOENSOR
SOI.ENOID
li
COLUMN.WIT
MANTLE
VACUUM CONNECTION
(WHEN USED)
A P SENSOR
PRODUCT
: COOLER
RECEIVER
TEMPERATURE
PROBE
stTirri--'
I-
N 2 BUBBLER
STIRRING MOTOR
iWethod
Procedure or Cuts
Repeatability
D2892
15/5 Distillation
Under determination
Under determination
D5236
Vacuum Potstill
Atmospheric Pressure
Reduced Pressure
10 vol %
20 vol %
30 vol %
40 vol %
50 vol %
60 vol %
70 vol %
80 vol %
90 vol %
6.rc
6.rc
4.9C
4.5C
5.7C
4.rc
4.8C
4.9C
4.4C
Reproducibility
1.2 mass %
1.4 mass %
16.9C
12.8C
13.5X
11.2''C
14.2C
8.4C
11.4C
5.rc
4.4''C
1.2 vol %
1.5 vol %
697
TABLE 29D 2892 crude distillation results for a new grade oil.
Boiling Range
(AET, C)
Weight
in
Grams
Init. to 20
21-50
93
163
200
250
280
316
330
343
343 +
Recov
Loss
88
91
212
452
199
260
188
278
208
90
1266
3332
6
Wt%
Volume (mL)
2.6
2.7
6.4
13.6
6.0
7.8
5.6
8.3
6.2
2.7
38.0
146.6
144.1
300.9
593.3
247.5
312.6
221.3
323.0
237.0
102.0
1358.4
3987
No Loss
Charge
LV %
Crude
Cum
LV%
Mid
LV%
API
Gravity
Density at
15C
3.7
3.6
7.5
14.9
6.2
7.8
5.5
8.1
6.0
2.6
34.1
3.7
3.6
7.5
14.9
6.2
7.8
5.5
8.1
6.0
2.6
34.1
3.7
7.3
14.8
29.7
35.9
43.8
49.3
57.4
63.4
65.9
100.0
1.8
5.5
11.1
22.3
32.8
39.8
46.5
53.4
60.4
64.7
82.0
104.3
92.5
69.3
54.2
44.4
38.5
34.9
32.8
29.8
28.8
20.2
37.7
0.6001
0.6315
0.7046
0.7618
0.8039
0.8317
0.8479
0.8608
0.8765
0.8820
0.9320
0.8357
0.2
Charge Weight = 3345
Weight of Water = 7
T A B L E 3 0 D 2 8 9 2 C r u d e d i s t i l l a t i o n r e s u l t s for l i g h t s o u r b l e n d oil
Boiling Range
(AET, C)
Weight
in
Grams
Init. to 20
21-50
100
125
150
175
205
220
235
265
295
319
343
343+
Recov
Loss
530
1709
2063
1077
1559
1289
1896
815
945
1940
1948
1870
1538
15105
34333
68
Wt%
Volume (mL)
1.5
5.0
6.0
3.1
4.5
3.8
5.5
2.4
2.9
5.7
5.7
5.4
4.5
44.0
937.1
2605.2
2812.9
1443.3
2035.2
1647.7
2383.1
1009.0
1216.8
2330.6
2286.9
2157.1
1753.3
15921.8
40540.1
No Loss
Charge
LV %
Crude
Cum
LV%
Mid
LV%
API
Gravity
Density at
15C
2.3
6.4
6.9
3.6
5.0
4.1
5.9
2.5
3.0
5.7
5.6
5.3
4.3
39.3
2.3
6.4
6.9
3.6
5.0
4.1
5.9
2.5
3.0
5.7
5.6
5.3
4.3
39.3
2.3
8.7
15.7
19.2
24.3
28.3
34.2
36.7
39.7
45.4
51.1
56.4
60.7
100.0
1.2
5.5
12.2
17.5
21.7
26.3
31.3
35.4
38.2
42.6
48.3
53.7
58.6
80.4
118.7
84.2
61.4
58.1
53.1
49.3
46.3
43.6
41.6
38.4
34.5
31.6
29.7
17.6
35.4
0.5656
0.6560
0.7334
0.7462
0.7660
0.7823
0.7956
0.8077
0.8169
0.8324
0.8518
0.8669
0.8772
0.9487
0.8469
0.2
698
MANUAL
HANDBOOK
There are other ASTM test methods related to the measurement of vapor pressure. Among these are: ASTM D 4953, Standard Test Method for the Vapor Pressure of GasoHne and
Gasohne-Oxygenate Blends (Dry Method) [46]; ASTM D 5190,
Standard Test Method for the Vapor Pressure of Petroleum
Products (Automatic Method) [47]; ASTM D 5191, Standard
Test Method for the Vapor Pressure of Petroleum Products
(Mini Method) [48]; and ASTM D 5482, Standard Test Method
for the Vapor Pressure of Petroleum Products (Mini MethodTO VACUUM PUKPINO LIME
RE*0 TKAP
TO VACUUM GAUGE
C080EN8ER>
VAPOR THERMOCOUPLE
VACUUM ADAPTER
FLASK THERMOCOUPLE
PLASK MAHTLES
OISTILLATIOH FLASK
MAGHETIC STIRRER
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1930. The latest edition
is D 323-99.
This test method covers procedures for the determination
of vapor pressure of gasoline, volatile crude oil, and other
volatile p e t r o l e u m products. Because the external atmospheric pressure is counteracted by the atmospheric pressure
initially present in the vapor chamber, the Reid vapor pressure is an absolute pressure at 37.8C. The Reid vapor pressure differs from the true vapor pressure of the sample due to
some small sample vaporization and the presence of water
TABLE 31D 5236 crude distillation results for a new grade oil bottoms.
Boiling
Range
(AET, C)
Weight
Grams
Wt%
Volume (mL)
Init. to 375
399
450
482
525
550
565
WETT
565 +
Recov
Loss
28
261
247
130
144
66
36
5
338
1255
2
2.2
20.8
19.7
10.4
11.5
5.3
2.9
0.4
26.9
31.4
292.2
273.2
141.7
155.5
70.7
38.4
5.3
337.5
1345.9
in
0.2
Charge Weight = 1253
API = 20.2
No Loss
Charge
LV%
Crude
Cum
LV%
Mid
LV%
API
Gravity
Density at
15C
2.3
21.7
20.3
10.5
11.6
5.3
2.9
0.4
25.1
0.8
7.4
6.9
3.6
3.9
1.8
1.0
0.1
8.6
66.7
74.1
81.0
84.6
88.6
90.3
91.3
91.4
100.0
66.3
70.4
77.6
82.8
86.6
89.4
90.8
91.4
95.7
27.0
26.9
24.9
22.6
21.2
20.0
19.3
18.9
9.7
20.1
0.8921
0.8931
0.9041
0.9175
0.9260
0.9336
0.9375
0.9402
1.0015
0.9324
699
TABLE 32D 5236 crude distillation results for a light sour blend bottoms.
Boiling Range
(AET, C)
Weight
in
Grams
Init. to 399
427
454
482
510
538
565
WETT
565 +
Recov
Loss
363
635
363
355
305
314
245
10
1150
3740
5
Wt%
Volume (mL)
9.7
17.0
9.7
9.5
8.2
8.4
6.6
0.3
30.7
403.3
702.4
397.0
385.6
328.6
335.1
258.1
10.5
1121.8
3942.4
No Loss
Charge
LV%
Crude
Cum
LV%
Mid
LV%
API
Gravity
Density at
15C
10.2
17.8
10.1
9.8
8.3
8.5
6.5
0.3
28.5
4.1
7.1
4.0
3.9
3.3
3.4
3.6
0.1
11.4
64.2
71.3
75.3
79.2
82.5
85.9
88.5
88.6
100.0
62.1
67.7
73.3
77.3
80.9
84.2
87.2
88.6
94.3
25.6
24.9
23.2
22.1
20.9
19.4
17.5
17.0
6.4
17.5
0.9000
0.9041
0.9144
0.9207
0.9282
0.9369
0.9492
0.9521
1.0251
0.9486
0.1
TABLE 33Comparison of ASTM vapor pressure and vapor/liquid ratio test methods.
ASTM
Designation
Reid Method
D 323 Proc. B
D 323 Proc. C
D 323 Proc. D
Reid Method
Reid Method
Reid Method
D 4953 Proc. A
D 4953 Proc. B
Dry Reid
Method
Dry Reid SemiAutomatic
Automatic
Method
Mini-Method
D5190
D5191
D5482
D6377
D6378
Scope
Test Method
D 323 Proc. A
Mini-Method,
Atmospheric
Expansion
Method
Triple
Expansion
Method
Vapor
Pressure
Range
Test
Temperature
Vapor to
Liquid
Ratio
All at 37.8C
4:1
Vapor
Pressure
Resuh
<180kPa
<180kPa
> 8 0 kPa
@ 50 kPa
Aviation gasoline
Gasoline and gasolineoxygenate blends, other aircontaining volatile petroleum
products
35-100 kPa
37.8C
4:1
Vapor
Pressure
//
7-172 kPa
37.8C
4:1
DVPE*
"
"
7-130 kPa
7-llOkPa
37.8C
37.8^
4:1
4:1
DVPE*
DVPE*
5-80C
4:1 to 0.021:1
4:1
Crude Oils
Volatile petroleum products,
hydrocarbons, and
hydrocEirbonoxygenate mixtures
7-150 kPa
37.8C
Vapor
Pressure
Vapor
Pressure
D5188
Evacuated
Chamber
Method
101.3 kPa
36-80C
8:1 to 75:1
V/L
Temperature
D2533
Evacuated
Chamber
Method
Gasoline
101.3 kPa
36-80C
20:1
V/L and
Temperature
D 1267
LP-Gas
Method
37.8-70C
Vapor
Pressure
*DVPE = dry vapor pressure equivalent (see discussion under individual test method)
vapor ind air in the confined space. The true vapor pressure
of the sample is the pressure exerted only by the molecular
species in the sample on the walls of the container. The vapor
pressure obtained by this method includes the vapor pressure
due to water vapor and air.
Figure 10 [45] shows the schematic diagram of the vapor
pressure apparatus for Procedure A, C, and D. Figure 11 [45]
illustrates the apparatus for Procedure B. The liquid chamber
of the vapor pressure apparatus is filled with the chilled sample and connected to the vapor chamber that has been heated
to 37.8C in a bath. The assembled apparatus is immersed in
a bath maintained at 37.8C until a constant pressure is ob-
served. The pressure reading, suitably corrected for any difference between the vapor pressure gage and calibration
manometer reading, is reported to the nearest 0.25 kPa (0.05
psi) as the Reid vapor pressure.
ASTM D 4953, Standard Test Method for the Vapor
Pressure of Gasoline and Gasoline-Oxygenate Blends
(Dry Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1989. The latest edition
is D 4953-99.
Reid Method
D4953
Dry Reid
Method
D5190
Procedure/Model
Metliod Name
D323
A
B
A
A
C
D
A
B
B
B
(Gasohne)
(Gasoline)
Repeatability
Range
35-100 kPa (5-15 psi)
35-100 kPa (5-15 psi)
0-35 kPa (0-5 psi)
110-180 kPa (16-26 psi)
180kPa(>26psi)
50 kPa (7 psi)
Automatic
Method
Mini-Method
D5191
psi)
psi)
psi)
psi)
0.00807(DVPE + B)
B = 124 kPa (18.0 psi)
1.31 kPa (0.19 psi)
1.79 kPa (0.26 psi)
0.0161(DVPE + B)
B = 124 kPa (18.0 psi)
2.69 kPa (0.39 psi)
4.14 kPa (0.60 psi)
To be determined
kPa
kPa
kPa
kPa
kPa
kPa
3.65
4.00
2.14
3.58
(Gage)
(Herzog)
(Precision)
Reproducibility
5.2 kPa (0.75 psi)
4.5 kPa (0.66 psi)
2.4 kPa (0.35 psi)
2.8 kPa (0.40 psi)
4.9 kPa (0.70 psi)
1.0 kPa (0.15 psi)
5.52 kPa (0.80 psi)
5.38 kPa (0.78 psi)
2.90 kPa (0.42 psi)
4.27 kPa (0.62 psi)
3.2
1.2
0.7
2.1
2.8
0.7
(0.46
(0.17
(0.10
(0.30
(0.40
(0.10
kPa
kPa
kPa
kPa
psi)
psi)
psi)
psi)
psi)
psi)
(0.53
(0.58
(0.31
(0.52
Mini-Method,
Atmospheric
VPCRx,
Expansion
Method
Herzog SC970
ABB 4100
D6378
VPx,
Expansion
Method
Petroleum
Products
D5188
Evacuated
Chamber
Evacuated
Chamber
LP-Gas
Method
V/L
0.6 C
0.9 C
1.0 C
1.4 C
12kPa(1.8psi)
1.3 C
1.6 C
18kPa(2.8psi)
D5482
D6377
D2533
D 1267
Vapor Chambar
Key
A
B, C, D
E
F, G
H
I
J
Glycerol Mercury
V/L
'Coupling
C
0.015 VPCR4
0.055 VPCRo 1
0.065 VPCRo 02
Crude
Coupling
tiquid Choinbtf
(Oni Opening)
in.
10 Ve
2 Vs
16
Vi
%
%
Vt
non
na
"CI
~or
CHAPTER
This test method is a modification of D 323, providing two
procedures to determine the vapor pressure of gasoline and
gasohne-oxygenate blends. Procedure A utilizes the same apparatus and essentially the same procedure as D 323 with the
exception that the interior surfaces of the liquid and vapor
chambers are maintained completely free of water. Procedure B utilizes a semi-automatic apparatus as shown in Figure 11 [46] with the liquid and vapor chambers identical in
volume to those in Procedure A. The apparatus is suspended
in a horizontal bath and rotated while attaining equilibrium.
Either a Bourdon gage or pressure transducer can be used
with this procedure. Just like Procedure A, the interior surfaces of the liquid and vapor chambers are maintained free of
water. The vapor pressure determined by this method differs
from the true vapor pressure of the sample due to some small
sample vaporization and includes the vapor pressure of the
air in the confined space.
The liquid c h a m b e r of the vapor pressure a p p a r a t u s is
filled with a chilled sample and connected to the vapor chamber that has been heated to 37.8C in a bath. The assembled
apparatus is immersed in a bath maintained at 37.8C until
constant pressure is observed. The pressure reading, suitably
corrected for any difference between the gage or pressure
transducer and manometer reading, is reported to the nearest 0.25 kPa (0.05 psi) as the Dry Reid vapor pressure.
Data from a 1991 interlaboratory cooperative program [55]
indicated a statistically significant bias between Procedure A
and Procedure B. The relative bias between procedures can
be corrected by applying the following equation:
For Procedure B, Gage:
25: VOLATILITY
701
FLOW SYSTEM
J*-f^*-VENTED
""^
40-80 RSI
<d. @M
PRESSURE-VAC
FOR
CAUBRATION
Z1
(9)
(10)
(11)
where:
X = m e a s u r e d total vapor pressure, in units consistent
with A, ctnd
A = 1.984 kPa (0.281 psi).
The chilled sample cup of the automatic vapor pressure instrument (Fig. 12 [47]) is filled with the chilled sample and
coupled to the instrument inlet fitting. The sample is automatically forced from the sample chamber to the expansion
(12)
where:
X = m e a s u r e d total vapor pressure, in units consistent
with A, and
A = 3.78 kPa (0.548 psi).
A similar correlation equation was developed by the U.S.
Environmental Protection Agency (EPA) using its own data.
The equation they use to correlate D 5191 results to D 4953,
702
HANDBOOK
Procedure B is:
D V P E , D5191 = (0.956 X ) - A
(13)
where:
X = measured total vapor pressure, in units consistent
with A, and
A = 2.39 kPa (0.347 psi).
Another correlation equation to correlate D 5191 results to
D 323 was developed by the California Air Resources Board
(CARB). It is given by the equation:
DVPE, D 5191 = (0.972 X ) - A
(14)
where:
X = measured total vapor pressure, in units consistent
with A, and
A = 4.93 kPa (0.715 psi)
A known volume of chilled, air-saturated sample is introduced into an evacuated, thermostatically controlled test
chamber, the internal volume of which is five times that of
the total specimen introduced into the chamber. After injection into the test chamber, the test specimen is allowed to
reach thermal equilibrium at 37.8C. The resulting rise in
pressure in the chamber is measured using a pressure transducer sensor and indicator. The total pressure measured is
converted to a DVPE using Eq 12. The DVPE is reported to
the neeirest 0.1 kPa (0.01 psi) without reference to the temperature.
ASTM D 5482, Standard Test Method for the
Vapor Pressure of Petroleum Products
(Mini-Method-Atmospheric)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1993. The latest edition
is D 5482-99.
This test method is a modification of D 5191. In this test
method, the test chamber is not evacuated but rather at atmospheric pressure at the start of the test. This test method
is suitable for gasoline samples that contain oxygenates. This
method is suitable for calculation of a dry vapor pressure
equivalent (DVPE) using an equation derived from a 1991 interlaboratory cooperative study [55].
DVPE, D 5482) = (0.965 X ) + A
(15)
where:
X = measured total vapor pressure, in units consistent
with A, and
A = 0.538 kPa (0.078 psi) for Herzog Model SC970
A = 1.937 kPa (0.281 psi) for ABB Model 4100
A known volume of chilled, air-saturated sample is introduced into a thermostatically controlled test chamber at atmospheric pressure, the internal volume of which is five
times that of the total specimen introduced into the chamber.
After injection into the test chamber, the test specimen is allowed to reach thermal equilibrium at 37.8 C. The resulting
rise in pressure in the chamber is measured using a pressure
transducer sensor and indicator. The total pressure mea-
sured is converted to a DVPE using Eq 15. The DVPE is reported to the nearest 0.1 kPa (0.01 psi) without reference to
the temperature.
ASTM D 6377, Standard Test Method for the Vapor
Pressure of Crude Oil, VPCRx (Expansion Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1998. The latest edition
is D 6377-98.
This test method covers the use of automated vapor pressure instruments to determine the vapor pressure exerted by
crude oils at temperatures between 5 and 80C. Employing
a measuring chamber with a built-in piston, a sample of
known volume is drawn from a pressurized sampling system (floating piston cylinder) into the temperature controlled chamber at 20C or higher. After sealing the chamber, the volume is expanded by moving the piston until the
final volume produces the desired V/L value. The temperature of the chamber is then regulated to the measuring temperature. After temperature and pressure equilibrium, the
measured pressure is recorded as the VPCRx of the sample.
The results are reported to the nearest 0.1 kPa with the test
temperature and vapor-liquid ratio. For results related to
ASTM D 323, the final volume of the measuring chamber
shall be five times the test specimen volume and the measuring temperature shall be 37.8C. The relative bias between the Reid vapor pressure (RVP) obtained by D 323 and
the value obtained by this method can be corrected by using the correlation equation:
RVPE, D323 = A X VPCR4(37.8-(C) + B
(16)
where:
A = 0.752
B = 6.07 kPa (0.88 psi)
ASTM D 6378, Standard Test Method for the Vapor
Pressure, VPx, of Petroleum Products, Hydrocarbons,
and Hydrocarbon-Oxygenate
Mixtures
(Triple-Expansion
Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally pubhshed in 1998. The latest edition
is D 6378-98.
This test method is similar to D 6377 with the exception
that expansion is done in three steps to a final volume of
(x -I-1) times that of the test specimen. After each expansion,
the total pressure is determined. The partial pressure of the
dissolved air and the solubility of air in the specimen are calculated from the three resulting pressures. The temperature
of the chamber is then increased to a specified value and total pressure is determined. The vapor pressure (VPx) is calculated by subtracting the partial pressure of the dissolved
air in the liquid, which has been gas-corrected for temperature, from the total pressure. In this test method, air saturation prior to the measurement is not required. Results are reported to the nearest 0.1 kPa with the test temperature and
vapor-liquid ratio. The vapor pressure determined by this
method at a vapor-liquid ratio of 4:1 of gasoline and gasolineoxygenate blends at 37.8C can be correlated to the DVPE
value determined by ASTM D 5191. The bias of the results ob-
(17)
where:
A = 1.027 kPa (0.15 psi).
ASTM D 5188, Standard Test Method for the
Vapor-Liquid Ratio Temperature
Determination
of Fuels (Evacuated Chamber Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1991. The latest edition
is D 5188-99.
This test method covers the determination of the temperature at which the vapor formed from a selected volume of
volatile petroleum products saturated with air at 0-1 C produces a pressure of one atmosphere in an evacuated chamber
of fixed volume. This test method is suitable for gasoline
samples that contain oxygenate. A known volume of chilled,
air-saturated sample is introduced into an evacuated, thermostatically controlled test chamber of known volume. The
sample volume is ceJculated to give the desired vapor-liquid
ratio for the chamber in use. After injection, the chamber
temperature is adjusted until a stable chamber pressure of
101.3 kPa is achieved.
The tendency of a fuel to vaporize in automotive engine
fuel systems is indicated by the vapor-liquid ratio of that fuel.
Automotive fuel specifications generally include T(V/L =20)
limits to ensure products of suitable volatility performance.
For high ambient temperature, a fuel with a high value of
T(v/L =20) indicating a fuel with a low tendency to vaporize, is
generally specified. Conversely, for low ambient temperatures, a fuel with a low T(V/L =20) value is specified.
ASTM D 2533, Standard Test Method for the
Vapor-Liquid Ratio of Spark-Ignition Engine Fuels
(Evacuated Chamber Method)
This test method is under the jurisdiction of ASTM Committee D-02 and is the direct responsibility of Subcommittee
D02.08. It was originally published in 1966. The latest edition
is D 2533-99.
This test method covers a procedure for measuring the volume of vapor formed at atmospheric pressure from a given
volume of gasoline. The ratio of these volumes is expressed as
the vapor-liquid (V/L) ratio of the gasoline at the temperature
of the test.
A measured volume of liquid fuel at 34-40F (0-4C) is
introduced through a rubber septum into a glycerol or mercury filled burette. The charged burette is placed in a temperature-controlled water bath. The volume of the vapor in
equilibrium with liquid fuel is measured at the desired temperature or temperatures and the specified pressure (usually
760 mm Hg). The vapor-liquid (V/L) is then calculated. If it
is desired to know the temperature corresponding to a given
V/L, the vapor-liquid ratio is determined at several temperatures, and the selected pressure. The results are plotted
and the temperature read at the given V/L. The vapor-liquid
ratio is reported to the nearest 0.1 unit and the corresponding temperature reading to the nearest 0.1 C (0.2F). If
other than 760 mm Hg the pressure in millimeters of mer-
703
LPGVPcorr, kPa
- ( 7 6 0 - P i ) 0.1333
(CAGE)
(STRAIGHT-THROUGH
VALVE)
B (LOWER
CHAMBER)
(BLEEDER
VALVE
COUPLING)
F (INLET
VALVE)
C (UPPER C H A M B E R )
(19)
(20)
(18)
704
MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
TABLE 35Cross reference of international vapor pressure standards relative to ASTM distillation test methods.
ASTM
Designation
U.S.
D323
D4953
D5190
D5191
D5482
D6377
D6378
D5188
D2533
D 1267
ISO
IP
BS
AFNOR
DIN
Europe
3007
U.K.
69
U.K.
2000
France
M07-007
Germany
51754
4256
161
L P G V P c o r r to 750 mm Hg = L P G V P c o r r , k P a
(21)
- (29.92 - Pz) 3.3864
= LPGVPcorr, psi - (29.92 - P2) 0.4912
(22)
for Vapor
JIS
791-1201
Japan
K2258
51 616
Other International
Determination
FTM
Pressure
por/Liquid ratios cem be determined using a variety of techniques a n d instrumentation. For safety in handling and
transporting veirious fuels cmd lubiicemts, a variety of flash
point test methods are available.
For the most part, this chapter on volatility characteristics
of fuels and lubricants has dealt mainly with ASTM standard
test methods that are used worldwide. However, there are
other international standards that correspond to the ASTM
standards described herein that are used and are applicable
in other parts of the world. The discussions on the different
ASTM test methods mentioned in this chapter are fairly brief,
by design a n d space constraints. For m o r e details, it is
strongly recommended that the readers refer to the actual
ASTM test methods themselves.
ASTM STANDARDS
No.
D 0056
D 0086
D 0092
D 0093
D 0323
D 1160
D 1310
D 2533
D 2892
CONCLUSION
D 3278
Volatility parameters of petroleum products and lubricants
are important parameters that are related to the performance
characteristics and safety in handling and transporting these
materials. Optimum distillation and vapor pressure veJues
are paramount in the proper and efficient operation of various engines fueled by different petroleum products u n d e r
different conditions. Distillation can be carried out either at
atmospheric or reduced pressures. Vapor pressure and Va-
D 3828
D 3941
D 4953
Title
Standard Test Method for Flash Point by Tag Closed
Cup Tester
Standard Test Method for Distillation of Petroleum
Products
Standard Test Method for Flash and Fire Points by
Cleveland Open Cup Tester
Standard Test Method for Flash Point by PenskyMartens Closed Cup Tester
S t a n d a r d Test Method for Vapor Pressure of
Petroleum Products (Reid Method)
Standard Test Method for Distillation of Petroleum
Products at Reduced Pressure
S t a n d a r d Test Method for Flash Point and Fire
Points by Tag Open Cup Apparatus
Standard Test Method for the Vapor-Liquid Ratio of
Spark-Ignition Engine Fuels
S t a n d a r d Test Method for Distillation of Crude
Petroleum (15-Theoretical Plate Column)
Standard Test Method for Flash Point by SetaFlash
Closed Cup Apparatus
S t a n d a r d Test M e t h o d for Flash Point by Small
Scale Closed Cup Tester
Standard Test Method for Flash Point by the Equilibrium Method with a Closed Cup Apparatus
S t a n d a r d Test Method for the Vapor Pressure of
Gasoline and Gasoline-Oxygenate Blends (Dry
Method)
D 5190
D 5191
D 5236
D 5482
D 6377
D 6378
D 6450
OTHER STANDARDS
No.
ISO 1523
ISO 2592
ISO 2719
ISO 3007
ISO 3405
ISO 3679
ISO 4256
ISO 6616
ISO 8708
AFNOR M07-002
AFNOR M07-007
AFNOR M07-019
AFNOR M07-036
DIN 51 356
DIN 51 376
DIN 51 567
DIN 51 616
DIN 51 680
DIN 51 751
DIN 51 754
DIN 51 755
DIN 51 758
JIS K2254
JIS K2258
JIS K2265
SIS 150 223
BIS 2000
BS 7392
IP 034
IP 036
IP 123
IP 303
IP 304
IP 069
IP 161
IP 170 (Abel)
FTM 791-1001
Title
Flash Point, Equilibrium Method, Close
Cup
Flash Point, Cleveland Open Cup
Flash Point, Pensky-Martens, Closed Cup
Reid Vapor Pressure
Distillation, Atmospheric Pressure
Flash Point, SetaFlash, Closed Cup
Vapor Pressure, LPG
Distillation, Reduced Pressure
Crude Distillation, 15/5
Distillation, Atmospheric Pressure
Reid Vapor Pressure
Flash Point, Pensky-Martens, Closed Cup
Flash Point, Abel-Pensky
Distillation, Reduced Pressure
Flash Point, Cleveland Open Cup
Crude Distillation, 15/5
Vapor Pressure, LPG
Flash Point, SetaFlash, Closed Cup
Distillation, Atmospheric Pressure
Reid Vapor Pressure
Flash Point, Abel-Pensky
Flash Point, Pensky-Martens, Closed Cup
Distillation, Atmospheric Pressure
Distillation, Reduced Pressure
Flash Point, Tag, Closed Cup
Flash Point, Abel-Pensky
Reid Vapor Pressure
Distillation, Atmospheric Pressure
Flash Point, Pensky-Martens, Closed Cup
Flash Point, Cleveland Open Cup
Distillation, Atmospheric Pressure
Flash Point, SetaFlash, Closed Cup
Flash Point, Tag, Closed Cup
Reid Vapor Pressure
Vapor Pressure, LPG
Flash Point, Abel
Distillation, Atmospheric Pressure
FTM 791-1101
FTM 791-1103
FTM 791-1201
705
REFERENCES
[1] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, pp. 16-37
[2] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, pp. 416^33
[3] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 18
[4] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 19
[5] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 34
[6] ASTM Research Report RR: D2-xxxx "Comparison of ASTM
Crosscheck D 86 Resuhs (Automatic versus Manual) for Various
Samples," ASTM International, West Conshohocken, PA, to be
submitted.
[7] ASTM Research Report RR: D2-1362 "Interlaboratoty Study to
Determine Precision of Automatic D 1160 and Comparison with
Manual D 1160 Results," ASTM International, West Conshohocken, PA, 1995.
[8] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 20
[9] Annual Book of ASTM Standards,Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 21.
[10] Annual Book ofASTM Standards,Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 22.
[11] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 26.
[12] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 27.
[13] Annual Book ofASTM Standards,Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 28.
[14] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 24.
[15] ASTM D-2 Interlaboratory Crosscheck Program, Motor Gasoline, ASTM International, West Conshohocken, PA, June 1999,
p. 35.
[16] ASTM D-2 Interlaboratory Crosscheck Program, Reformulated
Gasoline, ASTM InternationeJ, West Conshohocken, PA, June
1999, p. 57.
[17] ASTM D-2 Interlaboratory Crosscheck Program, Diesel Fuel,
ASTM International, West Conshohocken, PA, June 1999, p. 57.
[18] ASTM D-2 Interlaboratory Crosscheck Program, Jet Fuel, ASTM
International, West Conshohocken, PA, June 1999, p. 37.
[19] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 423.
[20] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 431.
[21] Annual Book of ASTM Standards,Vol. 5.01, ASTMlntemational,
West Conshohocken, PA, 1999, p. 417^22.
[22] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, p. 427.
[23] Section 173.120, Ch. 1, 49 CFR, (10-1-97 edition). Codes of Federal Register, Washington DC, p. 446.
[24] Annual Book of ASTM Standards, Vol. 5.01, West Conshohocken, PA, 1999, pp. 1-10.
[25] Annual Book of ASTM Standards, Vol. 5.01, West Conshohocken, PA, 1999, pp. 44-51.
[26] Annual Book of ASTM Standards, Vol. 5.01, West Conshohocken, PA, 1999, pp. 52-61.
[27] Annual Book of ASTM Standards, Vol. 6.01, West Conshohocken, PA, 1997, pp. 126-132.
MNL37-EB/Jun. 2003
Elemental Analysis
R. Kishore Nadkami ^
2003 by A S I M International
Preparation
www.astm.org
708
HANDBOOK
Compounds
Ba
Ca
Cd
Cr
Hg
Mg
Mo
Ni
P
Pb
Sb
Se
Si
Sn
Zn
Metaldialkyldithiophosphates
Naphthenate
Dialkyldithiocarbamates.
Dialkylphosphorodithionates
Selenides
Silicone Polymers
Organo Compounds
Dialkyldithiophosphates, dithiocarbamates,
phenolates
Wear Indication
Ag
Al
B
Cd
Cr
Cu
Fe
Mg
Mo
Na
Ni
Pb
Sb
Si
Sn
Ti
W
Zn
indicates failure or excessive wear of a specific engine component. Table 2 summarizes the typical wear metals and the
t3rpe of engine wear they may indicate, since in some cases,
more than one source may exist for certain elements.
Elemental analysis of used oils is generally performed using atomic spectroscopy techniques, particularly ICP-AES in
recent years, because of its capability of simultaneous determination of multielements. The U.S. Air Force for a n u m b e r
Performance
CHAPTER
low biased results. Also, particulates that reach the source
may not be "totally" atomized. To overcome this particle size
effect, the so-called particle size independent methods have
been developed, which consist of heating the oil in a small
amount of minerad acids and then diluting with an appropriate organic solvent [13].
At present, in the D2 committee, the only available method
for the determination of wear metals in used oils is D 5185,
which is a n ICP-AES method. Two methods based on the
rotrode technology have also been recently published: D 6595
and D 6728.
D02 Test Methods
There are about 80 test methods under the jurisdiction of
Subcommittee 3 on Elemental Analysis (see Table 3). These
m e t h o d s could be roughly classified according to their
principle chemical/physical technique that is utilized in the
analysis of samples.
Classical
Wet Chemistry
Methods
These methods are based on the gravimetric-titrimetric finish for the final determination of the species of interest. Although at one time widely used, they have been largely displaced by spectrometric techniques particularly for metals in
most m o d e m laboratories. Many times these methods are
considered as the referee methods; however, the expertise in
conducting these tests is hard to find today. These methods
include:
Analysis
Phosphorus
Vanadium
Nitrogen
Lithium/Sodium
Chlorine
Lead
Sulfur, active
Sulfur, mercaptan
Bomb
Combustion
ASTM
Technique
D1091
D3231
D4047
D 1548
D3228
D3340
D 4929A
D5384
D3341
D3348
D4952
D3227
Methods
ASTM
Detection Technique
Chlorine
Hydrogen
Sulfur
D808
D 1018
D 129
D 1266
D1552
D2784
Gravimetry
Gravimetry
Gravimetry
Gravimetry or Titrimetry
Titrimetry or IR Detection
Titrimetry or Turbidimetry
26: ELEMENTAL
ANALYSIS
709
Absorption
Spectrometry
(AAS)
Graphite Furnace
(GFAAS)
Atomic
Absorption
ASTM
D 5184B
D 3237
D 3831
D 3605
D 4628
D 5056
D 5863
Spectrometry
Subject
tration of the metals in this matrix necessitates very large dilutions. The technique uses m u c h smaller sample than that
required for flame AAS, but it takes longer time for analysis.
Matrix interferences are also m o r e significant t h a n with
flame AAS, and this translates into poorer precision (and accuracy).
CHAPTER
Most applications of GFAAS in the petroleum products
area have been in research. Recently, a method to measure
copper in jet fiiels by GFAAS has been published (D 6732).
Inductively
Coupled Plasma-Atomic
Spectrometry
(ICP-AES)
Emission
26: ELEMENTAL
ANALYSIS
711
Wavelength, nm
328.07
308.22;
249.77
455.40;
393.37;
214.44;
228.62
276.65;
324.75;
259.94
766.49
279.55;
257.61;
202.03;
589.00
341.47;
214.91;
220.35;
190.00;
231.15;
288.16;
283.99;
334.94;
292.40;
206.20;
309.27; 396.15
233.53; 493.41
317.93; 315.88
226.50; 228.80
283.56; 267.71
327.40
285.21; 279.08
357.60; 293.30
204.60; 281.62
231.60;
178.29;
283.31
180.73;
206.84
251.61
189.99;
337.28;
309.31;
213.86;
216.56
177.51
182.04
242.95
350.50
311.07
202.55
ASTM
D 4951
D 5185
D 5184A
D 5600
D 5708
712
HANDBOOK
reviewed in Ref. 2. There are, however, no test methods available in Subcommittee 3 jurisdiction at present that utilize ion
chromatography for the elemental analysis.
MicroElemental Analysis Methods
ASTM
D5291
D 4929B
D4629
D5762
D5622
D3120
D4045
D5453
D6667
Technique
IR or GC
Microcoulometry
Chemiluminescence
Chemiluminescence
Reductive Pyrolysis
Oxidative Microcoulometry
Hydrogenolysis and
Rateometric Colorimetry
UV Fluorescence
UV Fluorescence
Test Method
Repeatability
Reproducibility
Carbon
Chlorine
Hydrogen
Nitrogen
D5291
D 4929B
D5291
D4629
D5291
D5762
D5622
D3120
D4045
D5453
(X + 48.48) 0.0072
0.7 (X)O-*
(X''-^) 0.1162
0.15 (X)''-^''
0.1670
0.009 (X)
0.06 - 0.81%
28%
0.16 V ^
0.1867(X)"^
(X +48.48) 0.018
1.0 (X)"-^'
(X-5) 0.2314
0.85 iXf-^'*
0.4456
0.291 (X)
0.26 - 0.81%
38%
Oxygen
Sulfur
0.26 VJ
0.2217(X)0-^
CHAPTER
topic interferences are well-known and suitable alternate
interference-free g a m m a rays can be used for quantitative
analysis. The literature until the late '80s has been reviewed
earlier [2].
26: ELEMENTAL
ANALYSIS
713
ASTM
D 5059
D 4927
D 2622
D 4294
D 6443
D 6481
D 6334
D 6445
Methods
There are two methods available for the determination of hydrogen content of aviation turbine fuels, and of light and
middle distillates, gas oils and residua (D 3701 and D 4808,
respectively), based on nuclear magnetic resonance.
Perhaps the oldest methods used in the elemental analysis
of petroleum products are those for the determination of ash
714
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
D 4628 (AAS)
Barium
Calcium
Magnesium
Phosphorus
Sulfur
Zinc
0.011
0.0050
0.0037
0.0054
D 4927 (XRF)
A
B
0.0027
0.0047
0.0015
0.0034
0.0065
0.0047
0.002
0.0042
0.0042
0.0019
Reproducibility
D 4927 (XRF)
ICP-AES
D4951
D5185
D 4628 (AAS)
0.011
0.0058
0.0032
0.0026
0.016
0.0022
0.0023
0.0032
0.0061
0.0071
0.0132
0.0066
0.04
0.017
0.015
0.012
ICP-AES
D4951
D5185
0.006
0.018
0.016
0.016
0.011
0.020
0.0051
0.018
0.019
0.012
0.019
0.0083
0.012
0.010
0.061
0.0072
0.034
0.0119
0.0147
0.0136
0.021
0.0166
and sulfated ash (D 482 and D 874, respectively). The methods need a minimal a m o u n t of apparatus, perhaps available
in any laboratory. Because of their apparent simplicity, the
tests, however, may give an erroneous impression about the
composition of complex products. The sulfated ash method
(D 874), in particular, is fraught with drawbacks resulting in
extremely erroneous d a t a inconsistent with the chemical
composition of the additive products. This happens because
of the formation of a n u m b e r of nonstoichiometric compounds rather than only sulfates during sulfation and combustion [6]. It has been suggested that this empirical test be
replaced by m o d e m instrumented analysis, such as AAS, ICPAES, or XRF, which give m u c h more precise information on
the metal content of the petroleum additive products.
Kerosene
Lube additive
Lubricating oil
Petroleum coke
Reference Fuel
NIST Designation
8505
2723; 2724a
1624c
1618
1634c
1619a; 1620b; 162Ie;
1622e; 1623c; 2717
1616a; 1617a
1848
1818a
1819a
1836
1083; 1084a; 1085a
2718; 2719
2712-2715
Certification
Vanadium
Sulfur
Sulfur
Vanadium and Nickel
Trace elements
Sulfur
Sulfur
Additive Elements
Chlorine
Sulfur
Nitrogen
Wear Metals
Trace Elements
Lead
these aneJyzed samples as reference materials need to be considered with caution. These are consensus values and not certified values. Experience in these programs has shown that a
large degree of uncertainty is associated with the calculated
mccin vjJues. Hence, such materials are better suited EIS quality
control materials rather than as primary reference standards.
ASTM Proficiency Testing
A n u m b e r of cross-checks Eire conducted by the coordinating
Subcommittee 92 on a four-month cycle. This program has
been extremely popular worldwide providing the participating laboratories with a measure as to how well they are performing against their counterparts in the oil industry as well
as against the precision stated in the ASTM test methods. A
large n u m b e r of Subcommittee 3 test methods are utilized in
these exercises (Table 8). The reproducibilities obtained in
these programs have genercdly been poorer than those specified in the ASTM test methods. With recent changes in the
statistical calculations to delete the outliers, the precisions
have improved and are somewhat consistent with the published reproducibilities. To help the laboratories improve
their test precision, Subcommittee 3 is adding non-mandatory "helpful hints to the analyst" sections a n d mandatory
quality control sections to the test methods under its jurisdiction.
International Test M e t h o d s Harmonization
With the increasing globalization of commerce in the petrochemicals industry, many national standeirds bodies are heir-
715
Future Developments
A n u m b e r of new test methods for elemental analyses are being developed in the D02 Subcommittee 3. Many are for the
determination of trace elements and some for specific analysis in a specific matrix. Some of the work underway at the industry request includes:
lead, m a n g a n e s e , p h o s p h o r u s , and silicon in n a p h t h a ,
gasoline, and light petroleum products by ICP-AES;
phosphorus in reformulated gasoline by WDXRF;
sulfur and trace metals in petroleum coke by XRF;
chlorine in gasohol;
hydrogen by pulsed NMR;
TABLE 9 --International equivalent test methods for elemental analysis of petroleum products."
Analysis
ASTM (D)
IP
DIN (51-)
Ash
Lead-AAS
ICl
Volumetric
WDX
Metals-AAS
ICP
XRF
Nitrogen-Kjeldahl
Chemilum
Phosphorus in Lubes
Si/Al in Fuels
Sulfated Ash
Sulfur-Bomb
EDX
High Temp.
Lamp
Mercaptan
Microculometry
Oxidative microculometry
WDX
Wickbold
Vanadium
V, Ni by AAS
482
3237
3341
2547
2599
4628
4951
4927
3228
4629
4047
5184
874
129
4294
1552
1266
3227
3120
3246
2622
2785
1548
3605
4
428
270
248
228
308
437
407
575
6245
EN 237
2083
769T2
391
EN 237
379
149
377
163
61
336
ISO
3830
JIS (K-)
AFNOR
2272
M07-045
EN 237
M07-014
2255
M07-082
2609
2609
M07-058
391
790
575
4265
10478
3987
2272
577
107
342
8754
3012
16591
2276
373
400T6
14596
4260
790T3
8691
243
M07-025
M07-031
M07-022
M07-052
T060-142
2541
413
T60-143
T60-109
M07-027
Quality
Control
A good quality control or quality assurance program is essential in obtaining reliable data. It has, however, been seen
that many laboratories do not incorporate this step in their
analytical sequence. To help the laboratories improve their
performance, a nonmandatory section on quality control is
being added to most of the applicable Subcommittee 3 test
methods. It is hoped that this will encourage the laboratories
to institute quality control practices as an integral and pivotal
part of their testing protocols.
Concluding Remarks
Most of the test methods used for the elemental analysis of
petroleum products are based on m a t u r e analytical techniques a n d i n s t r u m e n t a t i o n . No one technique can be a
panacea for analyzing all elements in all materials. An ideal
analytical technique should have high sensitivity, broad linear dynamic range, high precision, no matrix interferences,
m i n i m u m sample preparation, and be inexpensive to acquire
and operate, useful for all elements, simple to operate, rapid,
nondestructive, etc. [31]. Few, if any, of the methods can
meet all these criteria. The analyst has to make a wise choice
as to the best available technique for a specific analysis in a
particular matrix.
REFERENCES
[1] Role of Trace Metals in Petroleum, T. F. Yen, Ed., Ann Arbor Science Publishers, Ann Arbor, MI, 1975.
[2] Nadkami, R. A., "Overview," Modem Instrumental Methods of
Elemental Analysis of Petroleum Products and Lubricants, ASTM
STP 1109, R. A. Nadkami, Ed., ASTM International, West Consiiohocken, PA, 1991, p. 1.
[3] Significance of Tests for Petroleum Products, ASTM STP 7C, K.
Boldt, and B. R. Hall, Eds. ASTM International, West Conshohocken, PA, 1977.
[4] Manual on Significance of Tests for Petroleum Products, ASTM
MNLl, G. V. Dyroff, Ed. ASTM International, West Conshohocken, PA, 1989.
[5] Modern Instrumental Methods ofElemental Analysis of Petroleum
Products and Lubricants, ASTM STP 1109, R. A. Nadkami, Ed.,
ASTM International, West Conshohocken, PA, 1991, p. 19.
[6] Nadkami, R. A., Ledesma, R. R., and Via, G. H., "Sulfated Ash
Test Method: Limitations of Reliability and Reproducibility,"
SAE Technical Paper No. 952548, Society of Automotive Engineers, Warrendale, PA, 1995.
[7] Eisentraut, K. J., Newman, R. W., Saba, C. S., Kauffman, R. E.,
and Rhine, W. E., Analytical Chemistry, Vol. 56, 1984, p. 1086A.
[8] Niu, W., Haring, R., and Newman, R., American Laboratory,
Vol. 19, No. 11, 1987, pp. 40.
[9] Carter, J. M., Batie, W., and Bemhard, A. E., Modem Instrumental Methods of Elemental Analysis of Petroleum Products and
Lubricants, ASTM STP 1109, R. A. Nadkami, Ed., ASTM International, West Conshohocken, PA, 1991, p. 70.
[10] Lukas, M., and Anderson, D. P., Modem Instrumental Methods of
Elemental Analysis of Petroleum. Products and Lubricants, ASTM
STP 1109, R. A. Nadkarni, Ed., ASTM Intemational, West Conshohocken, PA, 1991, p. 83.
[11] Nygaard, D., Bulman, P., and Alavosus, T., Modem Instrumental
Methods of Elemental Analysis of Petroleum Products and Lubricants, ASTM STP 1109, R. A. Nadkarni, Ed., ASTM International, West Conshohocken, PA, 1991, p. 77.
[12] Williams, M. C, Modem Instrumental Methods of Elemental
Analysis of Petroleum Products and Lubricants, ASTM STP 1109,
R. A. Nadkami, Ed., ASTM Intemational, West Conshohocken,
PA, 1991, p. 96.
[13] Kauffman, R. E., Saba, C. S., Rhine, W. E., and Eisentraut, K. J.,
Analytical Chemistry, Vol. 54, 1982, p. 975.
[14] Sychra, V., Lang, I., and Sebor, G., Progress in Analytical Atomic
Spectroscopy, Vol. 4, 1981, p. 341.
[15] Noble, D., Analytical Chemistry, Vol. 66, No. 2, 1994, p. 105A.
[16] Bansal, J. G. and McElroy, F. C, "Accurate Elemental Analysis
of Multigrade Lubricating Oils by ICP Method: Effect of Viscosity Modifiers," SAE Technical Series Paper 932694, Society for
Automotive Engineers, Warrendale, PA, 1993.
[17] Jansen, E. B. M., Knipscheer, J. H., and Nagtegaal, M., Journal
of Analytical Atomic Spectroscopy, Vol. 7, 1992, p. 127.
[18] Mackey, J. R., Watt, S. T., Cardy, C. A., Smith, S. I., and Meunier, C. A., Modem Instrumental Methods of Elemental Analysis
of Petroleum Products and Lubricants, ASTM STP 1109, R. A.
Nadkami, Ed., ASTM Intemational, West Conshohocken, PA,
1991, p. 62.
[19] Gonzales, M., and Lynch, A. W., Modem Instrumental Methods
of Elemental Analysis of Petroleum Products and Lubricants,
ASTM STP 1109, R. A. Nadkami, Ed., ASTM Intemational, West
Conshohocken, PA, 1991, pp. 62.
[20] Hausler, D. and Carlson, R., Spectrochemica Acta Reviews, Vol.
14, 1991, p. 125.
[21] Botto, R. I., Spectrochimica Acta Reviews, Vol. 14, 1991, p. 141.
[22] Botto, R. I., Journal of Analytical Atomic Spectrometry, Vol. 8,
1993, p. 51.
[23] Botto, R. I. and Zhu, J. J., Journal of Analytical Atomic Spectrometry, Vol. 11, 1996, p. 675.
[24] Al-Swaidan, H. M., Analytical Letters. Vol. 21, 1988, p. 1487.
[25] McElroy, F. C, Mennito, A., Debrah, E., and Thomas, R., Spectroscopy, Vol. 13, No. 2, 1998, p. 42.
[26] Newman, A., Analytical Chemistry, Vol. 69, 1997, p. 493A.
[27] Sieber, J. R., Salmon, S. G., and Williams, M. C, Modem Instrumental Methods of Elemental Analysis of Petroleum Products
and Lubricants, ASTM STP 1109, R. A. Nadkami, Ed., ASTM Intemational, West Conshohocken, PA, 1991, p. 118.
[28] Shay, J. Y. and Woodward, P. W., Modem Instrumental Methods
of Elemental Analysis of Petroleum Products and Lubricants,
ASTM STP 1109, R. A. Nadkami, Ed., ASTM Intemational, West
Conshohocken, PA, 1991, pp. 128.
[29] Wheeler, B. D., Modem Instrumental Methods of Elemental Analysis of Petroleum Products and Lubricants, ASTM STP 1109, R. A.
Nadkami, Ed., ASTM Intemational, West Conshohocken, PA,
1991, p. 136.
[30] Vrebos, B., Spectroscopy, Vol. 12, No. 6, 1997, p. 54.
[31] Hieftje, G. M., Journal of Analytical and Atomic Spectrometry,
Vol.4, 1989, p. 117.
[32] Nadkami, R. A., Guide to ASTM Test Methods for the Analysis of
Petroleum Products and Lubricants, Manual 44, ASTM Intemational, West Conshohocken, PA, 2000.
MNL37-EB/Jun. 2003
the current procedures are needed. An alternative to the current method for rating the ignition quality of diesel fuel is
presented and described.
FUEL INJECTION
Combustion in a diesel engine occurs when fuel is injected at
very high pressure (up to 200 MPa) through a small orifice or
multiple orifices in the injection nozzle into the combustion
chamber, that contains air that has been compressed to high
pressure and temperature. The high-pressure injection process results in a break-up of the fuel injection jets into small
droplets due to the shear forces induced between the high velocity jets and the relatively quiescent air in the combustion
chamber. The fuel droplets, consisting of drops in sizes ranging from approximately ten micrometers to several hundred
micrometers, traverse the combustion chamber at high velocity. The droplets go through a process of heating and evaporation due to heat transfer from the hot air, and deceleration due to aerodynamic drag. The evaporation process leads
to a preferential disappearance of the small droplets and
rapid mixing of the vaporized fuel with the air resulting in the
formation of a very fuel-rich mixture in the tip of the fuel jets.
The challenge for diesel engine designers is to match the
combustion chamber size and shape with the characteristics
of the fuel injection spray jets. The fuel jets must traverse the
combustion chamber in order to reach the air in all parts of
the combustion chamber. At the same time, the fuel must vaporize, mix with the air, and start to react. If the fuel jet penetrates too far, the fuel interacts with the wall, resulting in degraded mixing, low temperature combustion on the walls,
and high u n b u m e d hydrocarbon and smoke emissions. If the
717
Copyright'
2003 by A S I M International
www.astm.org
HANDBOOK
Flash, C, min
Water, v%
T90, C m a x
K. Vis.,(min) mm^/s@40C
K.Vis.,(max) mm^/s@40C
Ash, %inass,inax
Copper Corrosion
Cetane Number, m i n
Cetane Index
Aromatics, % vol, max
Cloud Pt, C, max
Sulfur, % mass, max
Ramsbottom Carbon on 10%
residue, mass %
Method
Low S
No. 1
SNo.2
No. 1
No. 2
No. 4
D93
D1796
D86
D445
D445
D482
D130
D613
D976
D1319
D2500
D2622
D524
38
0.05
288
1.3
2.4
0.01
3
40
40
35
6
0.05
0.15
52
0.05
338
1.9
4.1
0.01
3
40
40
35
6
0.05
0.35
38
0.05
288
1.3
2.4
0.01
3
40
52
0.05
338
1.9
4.1
0.01
3
40
55
0.05
0.15
0.35
fuel vaporizes and mixes too close to the nozzle, the mixture
will be overly rich, leading to high unbumed hydrocarbons
and smoke emissions.
The fuel properties that have the greatest effect on injection include viscosity, density, and surface tension. Viscosity,
a measure of the fuel's resistance to flow shear, impacts the
fuel spray characteristics through flow resistance inside the
injection system and in the nozzle holes. Higher viscosity
generally results in reduced flow rates for equal injection
pressure and degraded atomization.
Diesel fuel injection systems are designed to precisely meter the required volume of fuel into the combustion chamber
during each appropriate part of the compression portion of
the combustion cycle of the engine operation. All diesel injection systems meter the fuel on a volume basis, so that fuel
density affects the mass of fuel injected. Increased density beyond specification results in higher than designed fuel injection rates due to the direct relationship between mass, volume, and density.
Surface tension, or the tendency of the fuel to adhere to itself at the fuel-air interface, affects the tendency of the fuel to
form drops at the jet-air interface. Increased surface tension
tends to degrade atomization rates. It should be noted, however, that the surface tension of most hydrocarbons is very
similar one to another. Based on this fact, surface tension
does not play a first order role in the jet break-up and atomization process, at least on a comparative basis.
Low
5.5
24.0
0.01
30
6
COMBUSTION
IGNITION
Dec [1] theorizes that ignition occurs in the rich region at
the tip of the fuel jet, when the fuel's vapors achieve temperatures sufficient for decomposition and oxidation. In a
diesel engine, the fuel does not ignite instantaneously. The
time elapsed from injection to ignition is known as the ignition delay time. The ignition delay time occurs because a
certain amount of time is required for the fuel to vaporize
and ignite. A very simplistic view of the ignition process
separates the physical and chemical aspects of the ignition
process. The time necessary for the fuel to vaporize and mix
is known as the physical delay, while the chemical delay is
the time required for the onset of chemical reactions lead-
(1)
CHAPTER
27: DIESEL
(2)
dU/dt = m Cv dT/dt
(3)
and,
where,
m = mass trapped in the cyUnder (air + fuel mass)
Cv = specific heat at constant volume of mixture
T = temperature in the combustion chamber.
Also it is assumed that,
(4)
dW/dt = P dV
CHARACTERISTICS
719
Figure 1 is a heat release rate diagram for an engine condition in which there is a fairly large premixed b u m fraction.
Also plotted in Fig. 1 is the injection pressure as it was measured simultaneously with the cylinder pressure. The inflection in the injection pressure at 178 indicates the point in
time when the injection nozzle valve opens and fuel starts to
be injected into the cylinder. This is noted as the start of injection. Also indicated are the premixed and the diffusion
b u r n phases, or fractions. The time from the start of injection
to the start of the premixed b u m phase is called the ignition
delay time. Note that during this delay period a significant
quantity of fuel is injected, vaporized, and mixed with the hot
air in the cylinder. When ignition does occur, this premixed
fuel ignites spontaneously.
FUEL COMBUSTION
where.
P = instantaneous pressure in the cylinder
V = instantaneous volume in the cylinder.
Assuming Ideal Gas behavior,
PV=mRT
or,
dT/dt = (1/mR) (p dV/dt + V dp/dt)
where.
R = Gas Constant.
EMISSIONS
Combustion temperatures are important because they dominate the rate of formation of NOx emissions. NOx is important because it reacts with the unburned hydrocarbons in the
atmosphere to form smog. Most of the NOx emissions result
from a chemical kinetic process, known as the Zeldovich [3]
Thermal NOx emissions mechanism, where,
(5)
It can be seen that the apparent heat release rate during combustion, dQ/dt, can be computed using Eq 5, the measured
cylinder pressure, and using the geometric relationship between cylinder volume and crankangle. The computation is
performed using cylinder pressure data that is resolved based
on crankangle [3]. The pressure is measured using a high
speed piezoelectric pressure transducer installed in one of
the engine's cylinders. The pressure data is recorded simultaneously with a record of the crankangle position.
N2 + O = NO -h N
N + O2 = NO -h O
The rate constants for the two reactions are exponential functions of the temperatures in the combustion chamber. These
20000
0.20
u>
I<
tu
s
X
0.15 -
15000 .S
lU
10000
0.10
UJ
z
<
Iz
<
oc
v>
0)
3
lU
- 5000
0.05
0.
o
111
"N .
0.00
Premixed
^-Diffusion-^
Start of Injection
-0.05 1
90
n-
(6)
*T**i
105 120 135 150 165 180 195 210 225 240 255 270 285
-5000
720
MANUAL
HANDBOOK
0.30
0)
0)
a
0.25
ID
0.20
25000
0.10
z
<
1-
0.05
<
1(/z>
0.00
a.
3
OT
V)
10000 Ui
0.15
UJ
"5
15000
1X
If)
3
20000
a.
z
5000
_-^\-
-0.05
-5000
90
105 120 135 150 165 180 195 210 225 240 255 270 285
H
U
lU
-5
Z
1.5
1.75
1.85
CHARACTERISTICS
721
D I E S E L F U E L I G N I T I O N QUALITY
Current Practice (Cetane Number)
Diesel fuel specifications currently include only two specified
properties that are related directly to combustion. Heat of
Combustion, and cetane number. Heat of Combustion is a
fundamental property of the fuel, based on the Heat of Formation of the individual molecules. Its determination is fairly
straightforward following ASTM D 240, which employs a
bomb calorimeter. The procedure consists of completely
burning a weighed sample of the unknown fuel in a combustion bomb that is contained in a controlled temperature bath.
The Heat of Combustion is determined by measuring the
temperature increase of the bath.
Cetane number, on the other hand, as determined following ASTM D 613, is not a fundamental property of the fuel.
Cetane number is a defined parameter designed to provide an
indication of the ignition quality of diesel engine fuels.
Higher cetane number means that the fuel has better ignition
qUcJity than fuels with lower cetane numbers. Cetane number is determined in an engine test in which the ignition quality is rated versus those of blends of two reference fuels. The
history and method of ASTM D 613 and cetane numbers are
described in the following paragraphs.
In 1932, Boerlage and Broeze [7] proposed that the ignition
quality of a fuel be based on a comparison of its ignition delay time in a diesel engine to that of a blend of two reference
fuels. They developed the "cetene scale" in which a fuel was
assigned a "cetene number." The reference fuels were two
pure hydrocarbons, cetene (C16H32) and mesitylene. Cetene
burned readily in conventional engine, while mesitylene did
not bum at all.
nil
HANDBOOK
11 u
7//////1
1
PRE-CHAMBER
w/rr/rrz/rm
In 1935, ASTM adopted this form of diesel fuel rating system using hexadecane (C16H34) and alpha-methylnaphthalene ( d iH]o) as the reference fuels. The former was assigned
a cetane number of 100, while the latter was given a cetane
number of 0 [8]. In 1962, ASTM added heptamethylnonane,
(C16H34) to the cetane scale as an intermediate, low ignition
quality fuel with a defined cetane number of 15 [9].
The standard apparatus for determining and comparing ignition delay times is a Coordinated Fuels Research (CFR)
diesel engine developed by the Waukesha Motor Company. It
is a one-cylinder, four-stroke cycle engine with a cylindrical
prechamber chamber design (see Fig. 5) and a compression
ratio capability ranging from 6:1 to 28:1.
The ASTM D 613 test procedure consists of running the test
fuel at specified conditions of speed, load, and intake temperature. The injection timing is adjusted so that the start of
injection is 13 Before Top Dead Center (BTDC). The compression ratio is adjusted until ignition occurs at TDC. The
test fuel is then replaced with blends of the reference fuels
until one is determined to have a slightly higher compression
ratio and one with a slightly lower compression ratio than the
test fuel. The cetane number of the test fuel is determined by
linear interpolation of the cetane numbers of the reference
fuels. As an example, typical U.S. diesel fuel has a cetane
number of 45. The 45 cetane number reference fuel is a blend
consisting of 64.7 vol.% hexadecane and 35.3 vol.% heptamethylnonane .
Unfortunately, a number of problems are associated with
using the CFR engine for evaluating ignition delay time and
thus cetane number. It has been criticized for a variety of significant shortcomings. The primary complaint is a failure of
cetane number to consistently provide an accurate measurement of ignition quality. The specific shortcomings of the current cetane procedure were extensively discussed during a
CRC-hosted workshop, Diesel Fuel Combustion Performance,
held in Atlanta, Georgia in 1984 [10]. It appears that the main
CHAPTER
2 7: DIESEL
80
880
WOO
t040
1080
fS
FUEL COMBUSTION
CHARACTERISTICS
723
P r o p o s e d Alternatives to ASTM D 6 1 3
Due to the issues discussed above, including the time Eind expense required to conduct D 613 cetane n u m b e r determinations, a n u m b e r of edtemative methods have been proposed.
The proposed methods have included numerous correlations
with other physical a n d chemical properties, constantvolume combustion b o m b based methods, and correlative
techniques based on NMR and FTIR analysis of the test fuel.
Hardenberg and Hase [22] tried to use activation energy as
an indicator of cetane number. Collins a n d Unzelman [32]
used API gravity a n d mid-point temperature. Klopfenstein
R Rvtaranca FtMl
0 " Unknown Furt
"^n^^
-1HU_^,
I
12
13
It
17
COMPRESSION RATIO
724
HANDBOOK
CHARACTERISTICS
725
Inlet
Tc Chamber Surface
Tc High Temperature
Policeman
Injection Nozzle
Body
Tc Nozzle Tip
Exhaust
10
726
MANUAL
HANDBOOK
for the IQT, where the cetane n u m b e r is plotted versus the ignition delay time.
The test method consists of charging the fuel reservoir on
the injection p u m p with the unknown fuel. This requires approximately 50 mL sample of fuel to accomplish both the system flush as well as fuel charge for testing. The system is then
set for initiation a n d the test sequence is automatically
started. The sequence consists of venting the vessel and pressurizing to the initial pressure. After a short stabilization
time the test fuel is injected and the pressure and needle lift
histories are recorded and used to define the ignition delay
N-cetane: 100 CN
E
3
O
ffi
Heptamethylnonane: 15 CN
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
70
\ r
65
0)
iqtvscl-613
IQTCNvsColH
Col22vsd613
Col17vsCol16
Col 25 vs Col 24
Ji 60
E
3
^k.
Z
c
55
0)
50
w^
CO
(D 45
a
^"^^
40
35
35
40
45
50
55
60
65
70
ASTM STANDARDS
No.
D86
D93
D130
D240
D445
D482
D524
D613
D975
D976
D1319
D1796
D2500
D2622
D5291
E659
Title
Standard Test Method for Distillation of Petroleum
Products at Atmospheric Pressure
Standard Test Method for Flash-Pont by PenskyMartens Closed Cup Tester
Standard Test Method for Detection of Copper Corrosion from Petroleum Products by the Copper Strip
tarnish Test
Standard Test Method for Heat of Combustion of
Liquid Hydrocarbon Fuels by Bomb Calorimeter
Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids (the Calculation of
Dynamic Viscosity)
Standard Test Method for Ash from Petroleum Products
S t a n d a r d Test Method for R a m s b o t t o m Carbon
Residue of Petroleum Products
Standard Test Method for Cetane Number of Diesel
Fuel Qil
Standard Specification for Diesel Fuel Oils
Standard Test Methods for Calculated Cetane Index
of Distillate Fuels
Standard Test Method for Hydrocarbon Types in
Liquid Petroleum Products by Fluorescent Indicator
Adsorption
Standard Test Method for Water and Sediment in
Fuel Oils by the Centrifuge Method (Laboratory Procedure)
Standard Test Method for Cloud point of Petroleum
Products
Standard Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescence
Spectrometry
Standard Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in
Petroleum Products and Lubricants
Standard Test Method for Autoignition Temperature of Liquid Chemicals
727
REFERENCES
[1] Dec, J. and Espey, C, "Chemlluminescence Imaging of Autoignition in a DI Diesel Engine," SAE Paper 982685, Society of
Automotive Engineers, Warrendale, PA, 1998.
[2] Bowman, C. T., "Kinetics of Pollutant Formation and Destruction in Combustion," Progress in Energy Combustion Science,
Vol. 1, 1975, pp. 3 3 ^ 5 .
[3] Heywood, J. B., Internal Combustion Engine Fundamentals, McGraw-Hill, NY, 1988.
[4] "Air Quality Criteria for Particulate Matter," U.S. EPA, EPA
600/p-99/002aB, March 2001.
[5] Naegeli, D. W. and Moses, C. A., "Effects of Fuel Properties on
soot Formation in Turbine Combustion," SAE Paper 781026,
Society of Automotive Engineers, March 1978.
[6] Ryan, T. W., Ill, "Emissions Performance of Fischer Tropsch
Diesel Fuel," presented at the Intertech Gas to Liquids Conference, 17-19 May 1999, San Antonio, TX.
[7] Boerlage, G. D. and Broeze, J. J., "Ignition Quality of Diesel Fuels as Expressed in Cetane Numbers," SAE Journal, Vol. 27,
1932, pp. 283-293.
[8] Schweitzer, P. H., "Methods of Rating Diesel Fuels," Chemical
Reviews, Vol. 22, 1938.
[9] Henein, N. A., Fragoulis, A. N., and Luo, L., "Correlations Between Physical Properties and Autoignition Parameters of Alternate Fuels," SAE Paper 850266, Society of Automotive Engineers, Warrendale, PA, 1985.
[10] Diesel Fuel Combustion Performance Workshop, CRC, Atlanta,
GA, 1984.
[11] Gulder, O. L., Glavincevski, B., and Burton, G. F., "Ignition
Quality Rating Methods for Diesel Fuels-A Critical Appraisal,"
SAE SP, Qct. 1985.
[12] LeBreton, M. D., "Repeatability Test on the CFR Cetane Engine," SAE 841340, Society of Automotive Engineers, Warrendale, PA, 1984.
[13] Glavincevski, B., Gulder, O. L., and Gardner, L., "Cetane Number Estimation of Diesel Fuels from Carbon Type Structural
Composition," SAE Paper 841341, Society of Automotive Engineers, Warrendale, PA, 1984.
[14] Needham, J. R. and Doyle, D. M., "The Combustion and Ignition
Quality of Alternative Fuels in Light Duty Diesels," SAE Paper
852102, Society of Automotive Engineers, Warrendale, PA,
1985.
[15] Hum, R. W. and Hughes, K. J., "Combustion Characteristics of
Diesel Fuels as Measured in a Constant-Volume Bomb," SAE
Transactions, Vol. 6, No. 1, p. 24.
[16] Hardenberg, H. O. and Ehnert, E. R., "Ignition Quality Determination Problems with Alternative Fuels for Compression Ignition Engines," SAE Paper 811212, Society of Automotive Engineers, Wartendale, PA, 1981.
[17] Tavacha, J. W. and Cliffe, J. O., "The Effects of Cetane Quality
on the Performance of Diesel Engines," SAE Paper 821232, Society of Automotive Engineers, Warrendale, PA, 1982.
[18] Siebers, D. L., "Ignition Delay Characteristics of Alternative
Diesel Fuels: Implications on Cetane Number," SAE Paper
852102, Society of Automotive Engineers, Wartendale, PA,
1986.
[19] Indritz, D., "What is Cetane Number," Symposium on the Chemistry of Cetane Number Improvement, ACS, Miami, FL, April,
1985.
[20] Yu, T. C, Uyehara, Q. A., Meyers, P. S., Collins, R. N., and Mahadevan, K., "Physical and Chemical Ignition Delay in an Operating Diesel Engine Using the Hot-Motored Technique," SAE
Transactions, Vol. 64, 1962, p. 690.
[21] Tsao, K. C, Myers, P. S., and Uyehara, O. A., "Gas Temperatures
During Compression in Motored and Fired Diesel Engines,"
SAE Transactions, Vol. 70, 1962, p. 136.
[36] Bowden, J. N. and Frame, E. A., "Effect of Orgsinic Sulfur Compounds on Cetane Number," ACS, April, 1985.
[37] Bailey, B. K., Russell, J. A., Wimer, W. W., and Buckingham, J.
P., "Cetane N u m b e r Prediction Modeling," SwRI Report No.
SwRI 9435, Southwest Research Institute, San Antonio, TX,
1986.
[38] Fodor, G. E., "Analysis of Petroleum Products by Midband Infrared Spectroscopy," SAE Paper 941019, Society of Automotive
Engineers, Warrendale, PA, 1994.
[39] UUman, T., "Investigation of the Effects of Fuel Composition o n
Heavy-Duty Diesel Engine Emissions," SAE Paper 892072, Society of Automotive Engineers, Warrendale, PA, 1989.
[40] UUman, T., Mason, R. L., and Montalvo, D. A., "Effects of Fuel
Aromatics, Cetane Number, and Cetane Improver on Emissions
from a 1991 Prototype Heavy-Duty Diesel Engine," SAE Paper
9072171, Society of Automotive Engineers, Warrendale, PA,
1990.
[41] Ryan, T. W., Olikara, C , Buckingham, J., and Dodge, L. G., "The
Effects of Fuel Properties on Emissions from a 2.5 gm NOx
Heavy-Duty Diesel Engine," SAE Paper 982491, Society of Automotive Engineers, Warrendale, PA, Oct., 1998.
[42] Ryan, T. W., "Correlation of Physical and Chemical Ignition Delay to Cetane Number," SAE Paper 852103, Society of Automotive Engineers, Warrendale, PA, 1985.
[43] Ryan, T. W. and Stapper, B., "Diesel Fuel Ignition Quality as Determined in a Constant Volume Combustion Bomb," SAE Paper
870586, Society of Automotive Engineers, Warrendale, PA,
1987.
[44] Ryan, T. W. and Callahan, T. J., "Engine and Constant Volume
B o m b Studies of Diesel Ignition and Combustion," SAE Paper
881626, Society of Automotive Engineers, Warrendale, PA,
1988.
[45] Ryan, T. W., "Development of a Portable Fuel Cetane Quality
Monitor," Belvoir Fuels and Lubricants Research Report No.
277, Southwest Research Institute, San Antonio, TX, 1992.
[46] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
in the Ignition Quality Tester (IQT)," SAE Paper 961182, Society of Automotive Engineers, Warrendale, PA, 1996.
[47] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
in the Ignition Quality Tester (IQT)-Part II," SAE Paper 971636,
Society of Automotive Engineers, Warrendale, PA, 1997.
[48] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
in the Ignition Quality Tester (IQT)-Part III," SAE Paper 1999010, Society of Automotive Engineers, Warrendale, PA, 1999.
MNL37-EB/Jun. 2003
Engineering Sciences of
Aerospace Fuels
Eric M. Goodger^
NOMENCLATURE
A/F air-fuel ratio o n volume basis
a/f air-fuel ratio on mass basis
ARP Aerospace Recommended Practice (SAE)
BOCLE ball-on-cylinder lubricity evaluator
C velocity of air
CI/LIA corrosion inhibitor/lubricity improving additive
CNG compressed natural gas
CU conductivity unit (microsiemens/meter)
D(X-Y) dissociation enthalpy between a particular XY
bond
E overall energy
E activation energy
E(X-Y) m e a n empirical dissociation enthalpy between
many X-Y bonds
FBP final boiling point
FSII fuel system icing inhibitor
H, h enthalpy, specific enthalpy
\Ha
standard enthalpy of atomization
AHf standard enthalpy of formation
AH standard enthalpy of reaction
Hi total thermochemical enthalpy at temperature T
based on standard initial temperature of 298.15 K
HFRR high frequency reciprocating wear rig
HiTTS high temperature thermally stable
lATA INTERNATIONAL AIR TRANSPORT ASSOCIATION
IBP initial boiling point
Id density impulse
Is specific impulse
JFTOT jet fuel thermal oxidation tester
K partial pressure equilibrium constant
K' concentration equilibrium constant
LNG liquefied natural gas
M molar mass, g/mol
MTBE methyl tertiary butyl ether
m mass, kg
NG natural gas
NIR near infrared spectroscopy
n.f.e.e. non-flow energy equation
p pressure
Q, q heat transfer, specific heat transfer
R gas constant
Ro universal gas constant
' Managing Editor, Landfall Press, 28E Jessopp Road, Norwich, Norfolk, NR2 3QB, UK.
GENT requirements in terms of the levels of energy to be provided for the purpose, subject to the constraints of mass and
volume available for carriage of the fuel within the vehicle. In
this study, the following definitions are employed, with the
maximum levels of net specific energy shown in parentheses:
Conventional fuels - aviation fuel mixtures of a hydrocarbon nature invariably derived from petroleum
(44 MJ/kg)
High-performance fuelshydrogen, and individual hydrocarbon materials of particularly high energy content
(120 MJ/kg)
Substitute high-performance fuelsmaterials based on
non-cryogenic compounds of C, H, O, N, boron, etc.
(68 MJ/kg)
The performance of a bulk fuel in practice is a function of
both the properties of the fuel in question and the conditions
729
Copyright'
2003 by A S I M International
www.astm.org
ENGINE THERMODYNAMICS
The strength of the bonds between individual atoms comprising a fuel molecule represents stored chemical energy,
and this energy is required to be released and transformed in
some way to produce propulsive thrust, the customary chain
of conversions following the energy route from chemical to
heat to mechanical. These events take place in a heat engine,
and the b r a n c h of engineering science that includes such
heat-to-work conversions is known as Thermodynamics.
Although the actual processes involved throughout a practical heat engine are quite complex, a simplified overview is
adopted by providing a thermodynamic basis of gases associated with idealized conditions and processes, then incorporating the necessary effects of reality since reeil gases do not
follow exactly these idealized processes. The science of thermodynamics is built on the concept of a perfect gas that follows certain laws absolutely during changes in its major
properties of pressure (p), temperature (T), and volume (V)
[Appendix 1]. Fortuitously, the complete range of properties
of such a gas at any given state can be fixed by specifying two
(unrelated) properties only. This makes it possible to represent the complete state of the gas by means of a unique point
on a two-dimensional graph of one property plotted against
another (e.g., p against V). Furthermore, when the state of the
gas changes in etn ideal (reversible) manner, this process of
change can be represented by a unique line on the graph.
Even further, when a n u m b e r of different changes follow
each other in such a m a n n e r as to return to the original state,
they form a closed loop, which represents a cycle that could
be repeated indefinitely. Careful selection of the cyclic loop
processes can therefore provide a heat transfer into the gas
together with a work transfer outwards, thus giving the basis
of an ideal cyclic heat engine [Appendix 2]. Such a cycle, even
though idccJ, is subject to the fundamental laws of thermodjTiamics which stipulate that, although energy cannot be
created or destroyed, not all the heat input can be converted
to work because part of the heat must be rejected at a lower
temperature. Hence, the net heat input must equal the work
output, but the word net must be included or implied.
Ideal gas cycles conceived by sequencing various processes
include the following:
1. CamotMeiximum efficiency between given temperature
limits, but insufficiently practical since work output low.
work output
= 1
heat input
''Brayton
E}4}ansion
Compression
Heat rejection
Heat
addition
in
Z
rejection
3to4
4to1
Heat
addition
Turbine
Compressor
Heat
rejection
a) Closed circuit (industrial)
Heat
addition
^3
/|
1/
Propulsive gases
1
b) Open circuit (propulsion)
FIG. 2Schematic of gas turbine engines utilizing the Brayton cycle on a steady-flow basis.
Chlorine trifluoride
Id
LH2
N2H4
(CH3)2N2H4
Unsymmetrical dimethylhydrazine
60/40 mass mixture of UDMH and
diethylenetriamine (NH2CH2CH2)2NH
rocket propellant narrow-cut kerosine
LNH3
C2H50H
LB2H6
LF2
L02
N204
H202
HN03
CIF4
732
MANUAL
HANDBOOK
identify the candidate fuels available, examining their properties with a view to their meeting this requirement.
Diffuser
Air-
t-Exhaust jet
Air-
(1)
Oxidant
Fuel
Ramjet with supersonic nozzle
Fuel
Oxidant
t-
Fuel
b)
Fuel
b)
Storage Stability
a)
Rocl<et
CH4
Condensed
molecular
H-c-H
Plane
structural
(XTJD:)
S^-
SCIENCES
OF AEROSPACE FUELS
733
Series
molecular
formula
Description
Cg example
Condensed
formula
General properties
Plane structural
formula
HHHHHH
Paraffins
Alkanes
I I I I II
Olefins
Alkenes
CjjH2u
I I I I II
C=C-C-C-C-C-H Unstable
I I II
HHHH
Hex-1-ene
Naphthenes Cyclanes
Aromatics
(CH2)jj
Aromatics CjjH2ii.6
etc.
Closed-chain saturated
C5HJ2
Closed-chain resonance
stabilized
CgHg
H2
H2
Benzene
Physical State
The variations in boiling and freezing points show that increase in molecular size incurs a progressive change from gas
to liquid to solid. Although hydrocarbon molecules are generally not polar, in that they do not tend to have their centers
of negative and positive charges so displaced as to give a permanent electrostatic field around them, they do exhibit weak
forces of inter-molecular attraction because of the orbital
movements of the myriad of electrons surrounding the host
of atomic nuclei. With small molecules (e.g., the paraffins
CH4 to CaHg) these attractions are so small that the molecules
are free to move independently, and the bulk material exists
as a gas at normal temperature and pressure. With larger
molecules (e.g., C4H10 to C16H34), the attractions are sufficient to hold the molecules together to give bulk liquids. The
even larger molecules (C17H36 plus) are so strongly attracted
as to be firmly locked together as solids. Similar arguments
Stable
apply to the molecules of the other hydrocarbon series. Liquid density also increases progressively with molecular size.
Spontaneous Ignitability
Molecules will commence oxidation only when sufficient energy is supplied to rupture one of the internal bonds, permitting a combination with an oxygen atom (see the section on
Oxidation Heat Release and its Appendix). This preliminary
product is liable to be unstable, so initiate a chain of reactions until eventually full combustion occurs with the formation of CO2 and H2O. This initial energy may be supplied as
heat, leading to thermal agitation of the molecules and consequent bond rupture. The minimum temperature at which
this chain process leads to ignition is known as the spontaneous ignition temperature, SIT (sometimes described as autoignition temperature, AIT). The larger molecules, being
more unwieldy, are less able to withstand thermal agitation
Member
name
Formula
H/C
molar
Molar
mass
g/raol
Liquid
density
Paraffins
methane
CH4
16.04
0.415''
-161.5 -184.0
bp
C
fp
20C
540
17.19
-74.90
-0.80
Maximum
combution
temperature
C
50.05
20.77
1974
ethane
C2H6
30.07
0.561''
-88.3
-172.0
515
16.05
-84.72
-1.43
47.52
26.66
2009
propane
C3H8
2.67
44.10
0.585''
-44.5
-190.0
450
15.63
-102.92
-2.05
46.39
27.14
2016
butane
C4H10
2.5
58.12
O.6OO''
-0.6
-135.0
405
15.42
-124.82
-2.66
45.77
27.46
2020
pentane
C5H12
2.4
72.15
0.626
36.2
-131.5
260
15.29
-146.54
-3.27
45.38
28.41
2022
hexane
^6^14
2.3
86.18
0.660
69.0
-94.3
255
15.14
-167.30
-3.89
45.13
29.79
2023
ethene
C2H4
2.0
28.05
0.384''
-103.8 -169.4
490
14.75
52.32
-1.32
47.19
18.20
2147
Olefins
propene
C3H6
2.0
42.08
0.610''
-47.0
-185.2
460
14.75
20.43
-1.93
45.81
27.94
2089
but-1-ene
C4H8
2.0
56.11
0.631''
-6.3
-185.4
385
14.75
1.17
-2.54
45.35
28.62
2075
pent-1-ene
275
14.75
-20.93
-3.16
45.03
28.86
2066
14.75
-77.29
-3.10
44.23
23.22
2037
C5H10
2.0
70.14
0.641
34.0
-139.0
Naphthenes cyclopentane
C5H10
2.0
70.14
0.751
49.5
-93.9
cyclohexane
C6H12
2.0
84.16
0.778
80.7
6.6
280
14.75
-123.22
-3.69
43.86
34.12
2032
benzene
C6H6
1.0
78.11.
0.878
80.1
5.5
577
13.24
82.98
-3.17
40.61
35.66
2093
toluene
C7H8
1.14
92.14
0.866
110.5
-95.0
592
13.47
50.03
-3.77
40.97
35.48
2075
1.25
106.17
0.868
140.2
-31.3
563
13.64
18.06
-4.38
41.25
35.82
2069
-259
574
8.42
2171
72.4S
2036
Aromatics
Parent
hydrogen
H2
00
2.02
0.070''
carbon
C(gr)
12.01
2.2IS
elements
-252:7
3667 sublimes
34.19
-0.24
120.24
11.48
-0.3
32.76
b = at boiling point
s = solid
without rupture, and thus exhibit lower levels of SIT. Furthermore, molecules that are m a d e more compact by isomerization (rearrangement geometrically with n o loss or
gain of any atoms) show higher levels. These two p h e n o m e n a
are illustrated by the following examples:
Methane
CH4
Normal Octane
n-CgHig
H
H H H H
1 1
1 1 1 11
HCCCCC-CCH
1
1
H H H H H H H H
540
230
H
HCH
SIT
H H H
Isooctane
i-CgHig
(2,2,4-trimethylpentcine)
H
HCH
HC
CH
(4)
and.
HCH
H
467
(2)
Hence,
HCH
H
Stoichiometry
"C
(A/F)s
(5)
CHAPTER
28: ENGINEERING
CO2
(6)
SCIENCES
OF AEROSPACE
FUELS
735
736
HANDBOOK
Fuel
Aviation
gasoline
0.72
46 - 145
-70
0.5
-40 470
14.9
26-4
44.2
31.8
Wide cut
ftiel
0.78
73 - 235
-62
1.5
-10 270
14.5
24-4
43.6
34.0
Aviation
kerosine
0.80
1.8
43
254
14.8
22-4
43.4
34.7
High flash
fuel
0.82
185-244 -51
2.3
63
250
14.7
22-4
43.2
35.4
Gas oil
0.84
180-360 -30
6.0
70
247
14.6
21-3
42.9
36.0
2027
Methanol
CH3OH
0.79
64.8
-95.5
0.8
11
385
6.5
16.0
1969
MTBE
CH3OC4H9 0.75
55.0
-109
435
26.0
2002
Nitfomethane
1.14
CH3NO2
101
-17
0.6
35
419
1.7
10.9
12.5
2412
1.01
113.5
1.0
52
270
4.3
18.3 - 0
16.7
16.9
2219
Pentaborane
B5H9
0.63
58.4
-46.6
0.6
13.1
45-?
67.8
42.7
2527
95
-134
0.5
14.8
47.1
32.0
2025
2022
Hydrazine
N9H4
Triethyl
borane
(^2^5)36
0.68
CHAPTER
28: ENGINEERING
area
length .
.
.^ .
X ^r in units of Poise
velocity
SCIENCES
OF AEROSPACE
FUELS
737
Solidification
Comparable with the range of boiling points resulting from
progressive heating of a commercial fuel mixture as the several components distill in turn, a range of solidification temperatures can be expected from progressive cooling as each
component crystallizes as wax. Eventually a temperature is
reached where the viscosity approaches infinity as the fuel solidifies completely. The relevant solidification temperatures
can be determined and expressed in several ways. Generally,
the sample is cooled until the first appearance of wax crystals
then, in order to avoid spurious results from supercooling, it
is allowed to warm until the wax just disappears. (Thermodynamically, the temperatures of appearance and disappearance of wax must be different.) In ASTM D 2386, Freezing
Point of Aviation Fuels, the sample is stirred and the result
designated as the freezing point. D3rnamic methods are also
available, as in ASTM D 4305, Filter Flow of Aviation Fuels at
Low Temperatures, in which the sample is cooled under pre-
738
MANUAL
HANDBOOK
reflected from the ends of the tube, and in extreme cases may
even experience detonation involving a combination of shock
wave a n d flame. These tests are not standardized, b u t
adopted in combustion laboratories and on chamber rigs by
engine manufacturers.
The data in Table 4 show certain differences in flammable
mixture limits, with those for hydrogen and pentaborane being particularly wide. Also, the maximum flame velocity for
hydrogen is relatively high.
S p o n t a n e o u s Ignitability
In the standard ASTM E 659, Autoignition Temperature of
Liquid Chemicals, a small charge of liquid fuel is delivered as
a droplet by means of a syringe into a heated open flask, and
the delay noted before the onset of ignition. The method comprises repeated tests at progressively lower temperatures until the m i n i m u m level is found to promote ignition (the spontaneous ignition temperature, or SIT). The associated delay
period is a maximum, and usually comprises several seconds
under the test condition of atmospheric pressure. The levels
of SIT for the conventional hydrocarbons vary inversely with
density but tend to be higher for the substitute fuels.
Stoichiometry
As an extension of the treatment of hydrocarbons in the section on Stoichiometry, the stoichiometric combustion equation for the substitute fuels provides the following general expression:
CaHbOcNd + ms (O2 + 3.76 N2) = nj CO2 + Uz H2O + Us N2
From molar balances of the four elements,
m . = a + 0.25 b - 0.5 c
Hence, stoichiometric air-fuel molar ratio
= (A/F), = 4.76 a
1.19 b - 2 . 3 8 c
TABLE 5Relative stoichiometric calorific and specific impulse values of elements, non-carbon hydrides and organometsdlics [5].
Sp. En.
En. Dens.
Rel. Fuel
Density
Impulse (Sfd)
100
(43.4 MJ/kg)
276
153
133
57
72
43
38
168
156
98
125
100
(34.7 MJ/L)
24
353
400
124
241
33
48
90
123
103
86
100
(l.OSkNs/L)
19
119
193
48
96
63
67
58
73
69
60
Rel. Fuel
Material
Symbol
Av. kero.
Hydrogen
Beryllium
Boron
Magnesium
Aluminum
Ammonia
Hydrazine
Dlborane
Pentaborane
TEA
Aluminum borohydrlde
H2
Be
B
Mg
Al
NH3
N2H4
B2H6
B5H9
A1(C2H5)3
A1(BH4)3
Rel. Fuel
Specific
Impulse (Sf)
Rel. Air
Specific
Impulse (So)
100
(25.5 kN s/kg)
254
54
65
25
29
83
53
108
92
66
89
100
(1.76 kN s/kg)
105
116
105
122
122
88
93
107
106
108
107
Calorific Values
Whereas the oxidation heat release was treated thermochemically in the Oxidation Heat Release section leading to the
derivation of AHr, the thermodynamic approach permits an
application to practical test methods in the laboratory. The
thermodynamic laws of gases (Appendix 6) give rise to the
following energy equation:
Q W = At/
Q - W = AH
where
Q = heat transfer
W = work transfer
At/ = change in internal energy
AH = change in enthalpy, where H = U +pV, andp V = flow
energy.
Since it is far easier to measure heat transfer than work
transfer, conditions are selected where work transfer is zero
so that these expressions simplify to
Q = AC/ in non flow case at constant volume, and
Q = AH in steady flow case at constant pressure.
With gaseous fuels, the enthalpy released on combustion is
determined as the energy density (MJ/L) by burning at constant pressure through a steady flow calorimeter. The heat so
released is measured from the rise in temperature of the flowing cooling water. The test result is corrected for the standardized volume of fuel gas burnt, together with the expansion of both the cooling water and the flue gases.
With liquid fuels, specific energy is determined by burning
a known mass of fuel in a stainless steel b o m b located in a
water-filled calorimeter u n d e r non-flow constant volume
conditions, as in ASTM D 4809, Heat of Combustion of Liquid H y d r o c a r b o n Fuels by B o m b Calorimeter (Precision
Method). The b o m b is pressurized to 3.0 MPa (30 atm) with
water-saturated oxygen gas to ensure complete combustion.
The combustion heat so produced raises the temperature of
the caJorimeter water by about 3K, as measured by a platinum resistance or thermistor instrument. The mathematical
product of this temperature rise and the thermal capacity of
the calorimeterdetermined previously using benzoic acid
of known specific energyprovides a value of the quantity
of heat absorbed. Division by the initial mass of the sample
thus gives the specific energy of the sample fuel at constant
volume.
Because the final temperature of this test is only marginally
above ambient, the water produced by combustion of the hydrogen content of the fuel condenses to the liquid phase,
adding its latent enthalpy of vaporization to the combustion
energy. Consequently, the resulting specific energy is described as the "gross" value. In contrast, the combustion products leaving the working section of any heat engine must, of
necessity, still be hot, following the second law of thermodynamics that permits partial conversion only of heat to work.
Hence the combustion water leaves in the vapor phase, and
the "net" value of specific energy is more meaningful in engine
practice. This is routinely derived by subtracting the latent enthalpy of the combustion water using the following expression, which also converts the non-flow constant-volume result
to steady-flow constant-pressure:
Net specific energy @ 25C and constant pressure, in units
of MJ/kg = gross specific energy @ 25C & constant volume
0.2122 (mass % hydrogen in sample)
These experimental results, of course, will not tally exactly
with values of AHr because initial and final temperatures differ in the former case, and are c o m m o n in the latter (Table 3).
In order to improve accuracy, n u m e r o u s corrections are
made to allow for the enthalpies of formation of nitric and
sulfuric acids produced on combustion, and for the heat input from the burnt firing wire. Further refinements to correct
for heat transfers into and out of the CcJorimeter during the
test are represented by the adiabatic method and the isoperibol method, both of which incorporate an outer water bath.
In the former method, the temperature of the outer bath automatically matches that of the calorimeter water, so minimizing any heat interchange. In the latter method, the outer
bath is maintained at some selected constant temperature so
that heat interchange may be c o m p u t e d accurately, the
whole instrument being heavily insulated. In this latter case,
the local environment (the outer bath) is isothermal but the
external environment (the laboratory) is not, hence the use of
the term isoperibol rather than isothermal.
Because of the requirements of test time and practiced expertise in the above methods, attention has turned towards
methods of estimating specific energy based on statistical
correlation between accurate values of related properties.
ASTM D 3338, Estimation of Net Heat of Combustion of Aviation Fuels, involves correlation between aromatic content,
density, and averages of distillation temperatures at stated
recoveries, whereas alternative methods are based on density, aniline point, and/or sulfur content. Such methods are
dependent on the combined accuracies of the test results involved, and are therefore less precise than those obtained by
direct calorimetric determination.
The results presented in Table 4 for the petroleum fuels reflect the density effect of reducing specific energy and increasing energy density shown for the individual hydrocarbons in Table 3. The former effect, again, is understandable
from the reducing level of hydrogen content, whereas the latter is underscored by the fact that energy density is the direct
arithmetical product of specific energy and density, and
whereas the former falls by a mere 20% over the density range,
the latter rises by about 50% and is therefore the dominant
term in the product, as seen in Fig. 5. A special requirement
arises in the case of ramjet powered aircraft. These are essentially high-speed vehicles, hence fuel storage volume is at a
p r e m i u m to minimize drag, and energy density becomes the
criterion. The customary rise with increasing density is shown
in Fig. 6 for some specially selected high-performance fuels
indicating the expected need for high density.
Substitute fuels of higher energy density can be achieved
by replacing the c a r b o n in the h y d r o c a r b o n with some
HANDBOOK
Hydrogen 15
content 14 %Mass IS 1=
- 45 Specific
- 44 energy
43 MJ/kgnet
Energy 35
density
density
MJ/Lnet ^^ =
=-^
- 4
.
0
Viscosity
est @ 40C
Temperature C
>i
^ 40-
H-cot d
Shelldyne M
Adamantines
_
Pertiydrofluoranthene
l-Methyipertiyfluorene
icalin 4 ^ '*
Cyciododecarres
Energy-dense cyclics
An interesting conclusion concerns the level of specific energy available from unit masses of stoichiometric fuel-air
mixtures. Although hydrogen enrichment of a fuel tends to a
higher specific energy on a fuel mass basis, the stoichiometric air-fuel mass ratio also rises, consequently more air is
available to share the energy output. Hence, the stoichiometric mixture values of specific energy vary little from about 2.9
MJ/kg (net). This means that, in general, whereas the fuel carrying capacity of a vehicle is largely affected by specific energy of the fuel, the performance of the engine is not.
7^
XT
0.4
0.8
Density kg/L at 15C
1.2
"7
1.6
element contributing more calorific value to the resultant liquid hydride. Examples of such fuels include hydrides of
boron, beryllium, lithium, magnesium, aluminium, and titanium, plus compounds of hydrogen, carbon, and boron as included in Table 4.
The isobaric adiabatic reaction temperature for a commercial fuel mixture cannot be calculated without knowledge of
the individual chemical constituents and their proportions.
However, a broad assessment can be made on the assumption of an average molecular formula in each case.
The combustion temperature values included in Table 4
have been computed on the following basis:
Fuel
Aviation gasoline
Aviation kerosine
Gas oil
Cl2.5H24.4
C15H27.3
C7.3H15.3
Smoke Tendency
f AT sample - \T tetralin \
Luminometer Number = 100 U j f-octane - AT tetralin I
Correspondence has been found between smoke point cUid
luminometer n u m b e r over a wide range of kerosines.
^ Photocell
/
Chimney
Ignition
"niemiocouple
Reflecting scale
Luminometer Configuration
^''*''"
Flame-height
adjuster
Sample teo-ootane
J ^standard
1
1
1
U
1
/\
rs'A
Luminometer No = 100
/Ars-AT|.\
^ATU-ATL;
742
MANUAL
HANDBOOK
Flame Stabilization
In the aero gas turbine combustor, the flame is required to be
stabiHzed in a defined location against the entry stream of air
over a wide range of conditions, consequently a balcince must
be maintcuned at all times between the velocities of the flame
and the approaching mixture. The flame velocities of most fuels in laminar flow eire in the order of 0.5 m/s only and, although increased markedly by temperature and turbulence,
the velocity of the incoming mixture, emd thus the eiir, must be
reduced by some form of betffle in order to achieve velocity balance. In the gas turbine chamber, the velocity of the entering
air is reduced initially by diffusion. The air then goes through
a process of flow reversal by being fed around the outside of the
flame tube before entering through side apertures and encountering a low-pressure region in the core of an air swirl.
The result is a stabilized toroidal vortex of swirling air, the inner surface of which flows upstream. Introduction of the fuel
into this surface promotes a region of flame-air velocity balcince. In advanced aero gas turbine engines, a technique of premixing and prevaporization is used in order to control emissions more effectively. In rocketry, sprays of the liquid fuel Eind
oxidant may be ctrranged to impinge for thorough mixing.
Air D i l u t i o n
In contrast to piston engines where the working surfaces (piston crowns) are subjected to combustion temperatures for
only short periods of time, the blades on a gas-turbine disk operate continuously in a high-temperature environment, and
are also subjected to centrifugeJ stresses. Consequentiy, the
products from the flame must be cooled sufficiently to suit the
metallurgy of the turbine blades. Customarily, some 28% of
the chamber air is used for combustion in the primary zone,
which gives a flame temperature of about 2050C. The remaining air is introduced progressively downstream, first as
secondary Eiir to reduce the temperature of the combustion
products to about 1450C in order to offset the effects of dissociation, and then as dilution air to bring the turbine entry
temperature (TET) down further to the m a x i m u m level of
about 1000C. Higher TET values of 1350C and above are acceptable by intemeJ cooling of the nozzle guide vjines and turbine blades with air bled from the compressor. Despite fuel
residence times within the chamber of a few milliseconds only,
combustion efficiencies under design conditions are high, typically 99.5% or above. Even exhaust smoke that is just visible
represents a combustion inefficiency of no more than 0.01%.
Pattern factor =
Stream thrust
~ra
:~
Air mass flow rate
N s/kg (relates to engine thrust)
Steam thrust
-=5
5
;
Yuei mass flow rate
, J
.^ .
,
cSteam thrust
Fuel density impulse = Sf^ = Fuel volume flow rate
p
= -y- ~ Sfpf
N s /L (relates to volume limitation)
where py = fuel density, kg/L.
Relative vsJues of the specific impulse parameters are included in Table 5 for selected elements, non-carbon hydrides,
and organometallies. These show a broad interrelationship
with Ccdorific values, but eJso some significant differences.
Data for representative monoreactants are shown in Table 6.
Formula
(kg/L)
Id*
(N s/L)
(CH3)2N2H2
N2H4
CH3NO2
H2O2
C(N02)4
0.78
1.008
1.12
1.44
1.638
1530
1958
3126
2330
2907
(N s/kg)
Reaction
Temp.
*(K)
1961
1942
2491
1618
1775
1154
905
264
1278
2170
Combustion Emissions
Aero gas turbine emissions are of concern for their direct effects on airport environments, and their cumulative effects at
altitude. The m a i n emissions are CO and UHC at idle/taxiing
conditions, NOx (= NO + NO2) and smoke at high power during take-off and climb, and CO2 a n d H2O throughout.
Some ccirbon monoxide forms in the primary zone of the
gas turbine c h a m b e r but then tends to be oxidized by the secondary air. However, u n b u m t hydrocarbons may comprise
u n b u m t fuel and also partially reacted fuel in the form of
methane and related light hydrocarbons. They normally arise
through over-large spray droplet sizes and/or the chilling effects of mixing with air at low power output.
Nitric oxide occurs in atmospheric air flame-heated to
above 1800 K, a n d also following the three different sources
of thermal NO at high temperatures, prompt NO at fuel-rich
low temperatures, and fuel NO from fuel-bound nitrogen
at fuel-lean high temperature. Some of the NO oxidizes to
NO2 at full load, and more at low-temperature idle. The effects of NOx from subsonic aircraft operating in the troposphere (approximately 6-14 km altitude) are to increase the
level of ozone, which acts as a powerful greenhouse gas.
With supersonic aircraft operating in the tropopause/stratosphere (approximately 18-23 k m altitude), o n the other
hand, the ozone shield from harmful ultraviolet solar radiation is destroyed by the regeneration reactions of NO2 back
to NO.
Smoke comprises finely divided peirticles of carbon-rich
soot, and forms within fuel-rich regions of the flame such as
the core of the fuel spray, but is largely consumed downstream. ASTM D 1322 and D 1740 are used to measure combustion emissions.
The fuel parameters likely to improve emissions summarize as follows:
PhysiccJ: Low viscosity to generate small droplets in fuel
sprays. High volatility to assist rapid vaporization.
Chemical: Low carbon content a n d low aromatics to reduce smoke. Addition of organobarium or mcinganese to
reduce smoke.
The most effective hardware methods of reducing emissions appear to center on improvements in fuel prepeiration
a n d aeration in the combustor, plus the use of fuel staging,
variable chamber geometry, and lean premix vaporization.
-2
0.2
0.6
1
1.0
1.4
1.8
744
MANUAL
HANDBOOK
pumping rates, line velocities, bottom loading (no splash filling), and settling times have been generally adopted by the
major fuel suppliers as standard practice for the safe handling of such products.
The electrical conductivity of a fuel is determined by applying a voltage across two electrodes immersed in the sample, and recording the resulting current, as in ASTM D 4308,
Electrical Conductivity of Liquid Hydrocarbons by Precision
Meter. An alternative method, ASTM D 2624, Electrical Conductivity of Aviation a n d Distillate Fuels, applies to fuels
containing a static dissipator additive. Civil and military requirements differ because of the different additives used. For
example, experience shows a m i n i m u m conductivity of 50
units to be safe for civil jet fuels, whereas military fuels require higher conductivity, and this offsets the slight synergism possible between the additives FSII and CI/LIA. A
m a x i m u m limit is also set for jet kerosines (450 CU), all limits applying at the point, time, and temperature of delivery to
the user.
The conductivity of a fuel in a storage tank may be measured directly by portable meters manufactured commercially. The Maihak instrument has a conductivity cell on the
end of a cable wound onto a drum. The cell is lowered into
the tank through the sampling hatch, and the direct-reading
meter attached to the drum. With the pocket-sized Emcee instrument, the conductivity cell may be detached from the cable and fitted directly to the meter to give a laboratory model
for use with a fuel sample in a beaker. Alternatively, the cell
may be attached to the end of a probe and inserted into the
tank for measurements at a series of levels (e.g., top, middle,
and bottom) to check for homogeneity of the contents.
An additional measure of safety is the use of static dissipator additives (e.g., Stadis 450 for jet fuels). Complex polymeric materials containing nitrogen and sulphur are used to
render the bulk fuel sufficiently conducting to provide rapid
dissipation of the charge to an appropriate earthing surface
[1]. Incorporating this additive into an aviation kerosine
would raise the conductivity from 1 to about 150 CU, lowering the half-value time from 12-0.08 s.
Lubricity
Lubricity, sometimes described as film strength, can be defined as the ability to lubricate with a low tendency to generate friction, wear and/or scuffing. Lubrication takes the three
basic forms:
hydrodynamic (with n o surface contact, as controlled by
viscosity)
mixed (with limited surface contact)
boundary (with predominantly surface contact).
In the latter instance, lubricity applies particularly to fuel
pumping equipment operating at high pressure, where potential surface contact predominates. Although not included in
current specifications for jet fuels, the ability to maintain
boundary lubrication in the close cleEirances between reciprocating elements or highly-loaded gears in fuel pumps is imperative to avoid adhesive wear (surface scuffing or welding) and
oxidative wear (corrosion and abrasion). This was manifested
indirectly in aviation under the following circumstances:
sticking and hang-up of fuel control systems using widecut fuel
CHAPTER
28: ENGINEERING
SCIENCES
OF AEROSPACE
FUELS
745
746
MANUAL
HANDBOOK
tance-heated to 260C that experiences a skewed normal temperature distribution along its length, and downstream a
heated stainless-steel cloth precision filter of 17/Am nominal
porosity fitted with a differential gauge. The fuel sample flows
at 3 mL/min for 2.5 h along the outer surface of the tube: in
aircraft practice, the fuel flows within the tubing but external
flow is used in the test so that any deposits can be examined
visually. Any pressure drop across the filter indicates the presence of solid particulates, b u t examination of the upstream
heater tube was found to be necessary since tube deposits
were sometimes evident in the absence of filter blockage. The
sample is reported as either a pass or fail, determined jointly
by the intensity of tube deposition against set color standards
(ranging over a ten-step basis from 0, < 1 , 1, < 2 , 2, < 3 , 3, < 4 ,
4, >4) and/or level of pressure drop across the filter u p to a
maximum of 25 m m Hg. Among abnormal surface colors is
blue/gray, usually associated with copper contamination.
The JFTOT has also been used at t e m p e r a t u r e s above
260C in order to find the breakpoint, that is, the temperature
at which the fuel fails both the specified tube rating and mEixi m u m pressure drop (25 m m Hg) criteria. The currently determined brccikpoint for a typical UK aviation turbine fuel
ranges from about 280-310C, and hydrotreated fuels have
been found more stable t h a n sweetened fuels in which trace
contaminants are converted rather than removed. Generally,
breakpoint has also been found to correlate directly with hydrogen content a n d smoke point. In order to provide a
database, the US DOD is collecting information on thermal
stability results at a test temperature raised from 260-275C.
In the near future, USAF is expected to develop a "JP-8 +
100" fuel, being a JP-8 fuel with a 100F (56 K) improvement
in break point by means of a package of anti-oxidant, metcJ
deactivator, detergent, and dispersant additives. These especially stable products are now described as High Temperature Thermally Stable (HiTTS) fuels.
Thermal stability is degraded in the presence of olefins,
copper, and other metcJs, and of sulfur. Copper is a particularly potent oxidation catalyst and, even at the parts per billion level of concentration, has given rise to a n u m b e r of
problems through carryover when jet fuels were subjected to
copper sweetening. However, with the adoption of alternative methods of treatment, a limit on copper content is no
longer specified, reliance being placed on the results of the
JFTOT. Should a jet fuel contain copper, it can be chelated
(neutralized by axi isolating coating) by means of a metal deactivating additive such as a propanediamine. However, excessive use of MDA can passivate the tube surface of the
JFTOT and give rise to misleading results.
Water Contamination
Even with the strictest housekeeping discipline, traces of water invariably collect in liquid fuels during storage smd transfer. Apart from accidental ingress through carry-over from
water-washing in the refinery, or defective tank vents or
seams (pEirticularly in sea-going vessels), the main source is
the humidity of the atmosphere above the fuel surface. Water
dissolves in hydrocarbons to a n extent dependent upon temperature, any additional water existing freely as dispersed
droplets. The agitation of fuels by pumping through valves
and pipeline systems tends to disintegrate the water droplets.
18ij
Thus, settling rates are proportional to the square of the diameter of the contaminating particle, emd the density difference between the peirticle and the fuel.
As well as increasing the concentration of free water, cooling a distillate fuel from 0C to about 30C gives rise to the
progressive formation of ice crystals that tend to remain in
suspension. Supercooling may occur, but impact or contamination promotes instant freezing of both water and some hydrocarbon hydrates. A loose network of ice particles builds
u p on filter surfaces, resulting in an increased pressure differential and, eventually, complete blockage. In general, the
icing problem in civil aviation is met by the use of fuel-filter
heating, whereas military practice is to additize the fuel with
a fuel system icing inhibitor, FSII (diethylene glycolmonomethylether) u p to 0.15% by volume.
Since water, carbon, and nitrogen are essential ingredients
to life, microbiological activity is possible at the water-hydrocarbon interface. The most c o m m o n aerobic micro-organism to flourish under these conditions is Cladosporium
resinae (Lindau) de Vries. This is a fungus comprising long
threads that produce spores too small (approximately 3 ^^m)
to be filtered out. The threads branch heavily to form a visible tangled greenish-black mat or "mycelium," the mechanical strength of which is sufficient to cause filter blockage cind
malfunction of fuel-contents gauges. The fungus is able to extract the carbon from a hydrocarbon fuel such as kerosine,
and to generate products which, in association with water,
corrode through the WEJIS of aluminium fuel systems, promoting leakage. These tanks are now designed to give free access of all internal water to a drain plug, Eind/or with probes
into the low points to pick up collected water so that it CEin be
injected into the m a i n fuel delivery system to the engine.
Biostats are materials that inhibit the growth of bacteria
and fungi, whereas biocides are materials that kill them. In
military aviation practice, the fuel system icing inhibitor to
prevent water freezing problems is also relied upon as a biostat. In civil aviation, on the other hand, where filter heating
is used instead, biocidal shock treatment is given every few
months when the aircraft is out of service, by the addition of
u p to 270 p p m of a boron compound, which is left to act for
three days.
In addition to the corrosive action of the products of microorganisms discussed above, direct contact of metaJ with water and dissolved air leads to the formation of rust. Materials
employed as corrosion inhibitors are polcir in nature with hydrophilic heads and oleophilic/hydrophobic tails that accu-
CHAPTER
28: ENGINEERING
m u l a t e as an oil m o n o m o l e c u l a r layer preventing watermetal contact. As indicated in the earlier section on lubricity,
experience showed these corrosion inhibitors to serve a second purpose in improving lubricity by the same molecular
action, consequently such materials have become known as
corrosion inhibitor/lubricity improving additives, CI/LIA.
Other problems associated with water during the pumping of
fuels include the augmentation of static charging, as discussed ecirlier, and also foaming in the presence of heat.
With aviation kerosines, free water concentrations existing
as dispersed droplets become visible as a cloud (the specification calling for the fuel to be "clear") at concentrations
varying from 30-50 p p m mass depending inversely on
droplet size. The former figure is recognized by lATA as the
m a x i m u m permissible at the time a n d temperature of delivery, whereas a maximum of 15 p p m is assured by the use of
filter/separators and monitors in the supply system.
The concern with jet fuels is the potential for certain surfactants to disarm water separation equipment resulting in
the unexpected delivery of water to aircraft. A test was needed
initially to guard against the carry-over of powerful surfactants from the refinery, particularly when sulfonation techniques were much in use. ASTM D 2550, Water Separation
Characteristics of Aviation Turbine Fuels, employs a separometer to determine the efficiency by which a fuel-water
emulsion can be separated by a coalescer, assessment being
based on passing a prepared water-fuel emulsion through a
standard glass-fiber coalescer and measuring the turbidity of
the effluent by light transmission. An arbitrary scale described
as WSIM (i.e. Water Separation Index Modified) indicates 100
for clear fuel, and less for any remaining water droplets. A
small-scale version of this apparatus, D 3948, "Determining
Water-Separation Characteristics of Aviation Turbine Fuels
by Portable Separometer," comprises a portable micro-separometer with a high-speed mechanical stirrer, giving a numericaJ rating designated MSEP. However, the situation is
complicated by the fact that certain mandatory fuel additives,
either singly or in combination, depress WSIM number without, in reality, interfering with the water separator.
Tanks for kerosine usually have fixed roofs, coned to shed
rainwater and snow, with free-vents to assist drying. A coned o w n b o t t o m of m i n i m u m slope 1 in 30 leads t o a water
s u m p a n d drain valve, and a floating suction line ensures
freedom from water entrainment during offtake. After filling,
a period of 1 h is usually considered sufficient for water
droplet settlement, irrespective of tank depth.
Health Issues in Handling
The major physiological reactions on exposure to the highperformance transport fuels may have localized and/or systemic (remote) effects, a n d are tabulated under the following
headings:
Ingestionswallowing of liquid into the digestive tract
Inhalationin-breathing of vapor into the lungs
Aspirationintroduction of liquid into the lungs either
through inhalation or by vomiting
Externalcontact with skin and, particularly, eyes.
Furthermore, some materials are slow t o eliminate (for example, methanol), whereas others are cumulative (for example, decaborane).
SCIENCES
OF AEROSPACE
FUELS
747
FUTURE TRENDS
Extrapolation of past experience into the future suggests continuing use of conventional fuels for as long as is practicable,
supplemented by virtually identical fuels derived from
sources other than petroleum. Subsequently, recourse will
need to be made to substitute materials, as discussed below:
Reformulation (Short Term)
In the automotive world, the fuel approach to emission reduction is a process of reformulation. This entails tighter
controls on vapor pressure, and on the m a x i m u m permitted
concentrations of aromatics, olefins, and sulfur. With jet fuels on the other hand, component concentrations are already
very closely controlled, but the "product giveaway" (the difference between the actual property and its specified limit)
has h a d to be reduced progressively for reasons of economics. Nevertheless, recent reviews show modest improvement in aromatic content a n d smoke point despite small adverse changes in sulfur, freeze point, emd flash point. As the
sources of crude oil change because of shifting markets a n d
availabilities, the product processes will have to be continually adjusted t o achieve the necessary specification, and these
will no doubt involve some form or reformulation to a greater
or lesser extent.
Supplemental Fuels (Medium Term)
Both natural gas and coal can be converted to "syngas" (CO +
H2), which in turn can be synthesized to distillate-type liquids either through WEIX, which is then hydroconverted catalytically, or via a methanol stage. Alternatively, coal can be
de-ashed a n d its molecular components reduced in size sufficiently to give liquids directly without the additional energy
required for the more extensive reduction to gaseous dimensions. Hydrogenation of the aromatic components then gives
the saturates^paraffins a n d naphthenes.
More exotic alternative sources of hydrocarbons include
shale oil, tar, coal, peat, and biomatter generally. The first
two have not yet emerged as conventioned fuel sources with
established production rates, and therefore cannot be assigned meaningful (reserves-production) ratios, but large deposits are known to exist worldwide.
748
MANUAL
HANDBOOK
ing either pre-vaporization within the hot flame zone or
relatively fine atomization. They are burnt with minimal
radiation at virtually constant pressure, with flame stability and temperature distribution across the combustor section controlled by engine design. Combustion efficiency is
at a premium, despite the very short residence time of the
fuel molecules within the combustor, not only for fuel
economy, but also for minimal emissions. In addition, handling properties are required to meet the wide range of
temperatures and pressures pertaining throughout the supply system a n d within the aircraft itself during service. All
these requirements combine to comprise a relatively extensive specification list of some 28 items or more, as summarized in Table 7, yet without precluding either availability or economics.
TABLE 7Major features of representative U.S. jet fuel specifications (certain variations apply depending on type
and concentrations of additives, etc.).
Property
Color, Saybolt, min
Total acid no. mg KOH /g,
max
Aromatics, % vol., max
Olefins, % vol., max
Sulfur, total, % mass, max
Sulfur, mercaptan, % mass.
max
Initial boiling point, C
10% vol. recovered, C
20% vol. recovered, C
50% vol. recovered, C
90% vol. recovered, C
E n d point C, max
Flash point C, min
Reid vapour pressure @
38.7C, kPa
Density 15C, kg/L
Freezing point, C, max
Viscosity @ -20C, mm^/s,
max
Specific energy, net, MJ/kg,
mm
Hydrogen content, % mass.
min
Smoke point, m m , m i n
Copper strip corrosion, max
Thermal stability (JFTOT)
Change in pres. drop, m m
Hg, max
Tube deposit code
TDR spun mcix
Existent gum;, mg/100 mL,
Wide-cut
Gasoline
MIL-DTL-5624T
JP-4
NATO F-40
Kerosine
MIL-T-813133D
ASTM D-1655
JetA-l"
NATO F-35
High-flash
Kerosine
MIL-DTL-5624
JP-5
NATO F-44
Report
0.015
Report
0.015
Report
0.015
25.0
25.0
5.0
0.30
0.002
0.40
0.002
Report
Report
m i n 100
min 125
Report
270
Report
max 205
Report
Report
Report
300
38
Thermally
stable fuel
TMIL-DTL-25524E
JPTS
Low volatility
fuel
MIL-DTL-38219D
JP-7
-1-24
0.015
-1-25
23.0-27.0
5.0-20.0
0.40
0.002
0.3
0.001
0.1
0.001
Report
max 206
Report
Report
Report
300
60
min. 157
max 193
0.751-0.802
-58
0.775-0.840
-47
8.0
0.788-0.845
-46
8.5
0.767-0.797
-53
12 @ - 4 0
min 182
min 196
m i n 206
Report
max 260
288
60
max 20.7 @ 149C
& 3 3 1 @260C
0.779-0.806
-43.3
8.0
42.8
42.8
42.6
42.8
43.5
13.5
13.4
13.3-13.5
14.0
14.40
20.0
1
25.0
1
18.0-21.0
1
25.0
lb
lb
25.0
25.0
25.0
25
25.0
<3
<3
<3
12
5.0
12
5.0
max 204
max 238
260
43
14-21
7.0
7.0
7.0
High density
synthetic
MIL-P-87107B
JP-10
54.4
0.935-0.943
-79
40@-54, 10@-18
42.1 (E.D. 39.4 MJ/L)
10
2
5.0
max
1.0
1.0
1.0
0.3/0.5
0.3/0.5
1.0
Particulate matter, mg/L,
max
10
15
15
Filtration time, minutes,
max
lb
lb
lb
lb
lb
Water reaction interface
rating, max
Microscparator rating, min
70/90
70/85
70/90
85
Report
Electrical conductivity.
150-600
50-450
pS/m,
"Known as F-34 (JP-8) when additized with FSII and CI /LIA. The Jet Fueling System Check List embodies the most stringent requirements of Jet A-1, the British
DEF STAN 91-91, and the lATA Guidance Material for Aviation Turbine Fuels.
NOTE1. Distillation tests incorporate limits of 1.5% for both residue and loss.
2. Types and concentrations of additives are also specified.
CHAPTER
28: ENGINEERING
ASTM STANDARDS
No.
D 86
D 93
D 341
D 381
D 445
D 1298
D
D
D
D
D
1322
1740
2386
2533
2550
D 2624
D 3241
D 3338
D 3825
D 3948
D 4305
D 4308
D 4809
D 5001
E 659
Title
Distillation of Petroleum Products at Atmospheric
Pressure
Flash-Point by Pensky-Martens Closed Cup Tester
Standard Viscosity-Temperature Charts for Liquid
Petroleum Products
Gum Content in Fuels by Jet Evaporation
Kinematic Viscosity of Transparent a n d Opaque
Liquids (The Calculation of Dynamic Viscosity)
Density, Relative Density (Specific Gravity) or API
Gravity of Crude Petroleum and Liquid Petroleum
Products by Hydrometer Method
Smoke Point of Kerosine and Aviation Turbine Fuel
Luminometer Numbers of Aviation Turbine Fuels
Freezing Point of Aviation Fuels
Vapor-Liquid Ratio of Spark-Ignition Engine Fuels
Water Separation Characteristics of Aviation Turbine Fuels
Electrical Conductivity of Aviation and Distillate
Fuels Containing a Static Dissipator Additive
Thermal Oxidation Stability of Aviation Turbine
Fuels (JFTOT Procedure)
Estimation of Net Heat of Combustion of Aviation
Fuels
Dynamic Surface Tension by the Fast-Bubble Technique
Determining Water-Separating Characteristics of
Aviation Turbine Fuels by Portable Separometer
Filter Flow of Aviation Fuels at Low Temperatures
Electrical Conductivity of Liquid Hydrocarbons by
Precision Meter
Heat of Combustion of Liquid Hydrocarbon Fuels
by B o m b Calorimeter (Precision Method)
Measurement of Lubricity of Aviation Turbine Fuels by the Ball-On-Cylinder Lubricity Evaluator
(BOCLE)
Autoignition Temperature of Liquid Chemicals
SAE STANDARDS
ARP492
REFERENCES
[1] Goodger, E. M., Transport Fuels Technology, Landfall Press, Norwich, UK, October 2000.
SCIENCES
OF AEROSPACE
FUELS
749
BIBLIOGRAPHY
1] Schobert, H. H., The Chemistry of Hydrocarbon Fuels, Butterworths, London, UK, 1990.
2] Handbook of Chemistry and Physics, R. C. Weast, Ed., CRC Press,
Cleveland, OH, republished periodically.
3] Rogers, G. F. C. and Mayhew, Y. R., Engineering Thermodynamics Work and Heat Transfer, Longmans Group Ltd., Harlow, UK,
latest edition.
4] Rose, J. W. and Cooper, J. R., Technical Data on Fuel, The British
National Committee, World Energy Conference, London, 1977.
5] Datschefski, G., Lewis, C, and Walters, M. B., Jet Fuel Specification Requirements, Defense Evaluation and Research Agency,
London, 1997.
6] Fielding, D. and Topps, J. E. C, Thermodynamic Data for the Calculation of Gas Turbine Performance, Aeronautical Reseach
Council R & M 3099, 1959.
7] Breitwieser, B., Gordon, S., and Gammon, B., Summary Report
on Analytical Evaluation of Air and Fuel Specific-Impulse Characteristics of Several Non-hydrocarbon Jet Engine Fuels, NACA R M
E52L08, 1952.
8] Dukek, W. G., Selected Hydrocarbons as High Performance Fuels,
American Chemistry Society, Symposium on High Energy Fuels,
Philadelphia, 25 Feb. 1960.
9] Brewer, G. D., Hydrogen Aircraft Technology, CRC Press, London,
1991.
APPENDIX 1
T h e r m o d y n a m i c Properties a n d their Interrelationship in Static Gases
A collection of hot gases suited to act as a working fluid in a
heat-work conversion is known as a thermodynamic system.
At any instant, this system exists in a particular thermodynamic state as defined by its set of properties, which are consequently described as state functions. Such a property is recognizable by the fact that it exhibits no change when the
system goes through a complete cycle of events (as discussed
in Appendix 2).
In a thermodynamic system:
an extensive property is dependent on the mass of the system, e.g., volume V, internal energy U, enthalpy//, energy,
entropy S, etc.
a specific property is an extensive property expressed on a
basis of unit mass of the system, e.g., specific volume v.
0.5
1.5
Volume, Vm3
Process Name
0
1
>1 to<-)'
y
Cyclic
i -
-Cp{T, -To)'
CpiTs --T2)
Heat Transfer
Work Transfer
-CpiTj - T2)
CpiTs - T,)
Cp(T3 - T4)
-Cp{T, - T4)
{T4 - T,)
(T3 - T2)
Process
It is evident that reversible processes can be arranged sequentially in a variety of ways so that they return to the initial point and comprise complete cycles. Thus, as outlined
earlier, the properties do not change once the cycle is completed since the initial and final states coincide. Clearly this
cyclic process encompasses a fixed area (which represents
work transfer in the case of pressure-volume axes), and can
be repeated indefinitely. Each individual component process
is related to external transfers of energy (as heat and/or
work), which are all calculable from thermodynamic theory.
Consequently, suitable selection of component processes,
and of their relationship within the cycle, can result in overall transfers of heat and work. Traversing the cycle diagram
clockwise gives rise to the potential of the continuous conversion of heat input to work output (as in a heat engine),
provided the second law of thermodynamics is followed in
that such a conversion can never be complete, i.e., some of
the heat input must be rejected as heat output at a level of
temperature lower than the initial. The derivation of the effi-
Compression ratio r^
10
20
L
Typical S-l
Typical C-l
may r
maX i j .
60
OTTO
2
'o
40 ic
(U
.
"
-
maxrn
Cut-off ratio
Spark ignition piston engine
Compression ignition piston engine
Gas turtine engine
r
10
"T
20
Isothermal
r=k
Non Flow
Steady Flow
Cp (T2 - Ti)
R (T2 - Ti)
R T In (p,/p2)
= RTln(v2/v;)
RT\n{p,/p2)
= r i n (V2 /V,)
^ T ^ (Ti - T2)
n= 1
Pol3^ropic
pv = k
n = n
(7 - n) , ^
Cv j^ _ J {T,
^ ,
T2)
dD
SI
30
Heat Transfer
RT\n(p,/p2)
RT\n(v2/vt)
20
Pressure ratio Xp
Work Transfer
Isobaric
p = k
n = 0
75
E
)_
Typical GT
a
S-l
C-l
GT
30
(T, - T2)
Isentropic
p v"* = k
n = -y
Cv {Ti - T2)
Cp {T, - T2)
Isochoric
v = k
Cv {T2 - T,)
R {T, - T2)
n = 00
HANDBOOK
APPENDIX 3
Enthalpy
Bond
Enthalpy
AHa.H2(g)
AHa.02(g)
AH,.N2(g)
AHa.C2(gr)
D (HO)
E (H0)
435.4
498.2
946.2
717.2
428.7
463.1
D(HOH)
E(CH)
E(CC)
E(C=C)
E(C=C)
E(C0)
497.5
414.5
347.5
615.5
812.2
351.7
which is the mean value for a n u m b e r of such bonds in different molecules, and in different locations within them. A
simple physical analogy of the complete formation process is
given by a mass descending from a depression in a hilltop;
the overall change in potential energy is the net result of the
climb to the lip of the depression, and the subsequent descent
from it (Fig. A3.1). Representative values of AHa, D(X^Y)
and E(XY) are given in Table A3.1
Hence, in the methane example above, the net enthalpy released, which is described as the standcird enthalpy of formation, AHf, is given by:
A//f .CH4 = lAHa - l E ( X - Y ) approximately
= [AHa-Cigr) + 2 AHa-H2{g)] - 4 [ E ( C - H ) ]
[717.2 + 870.8] - 1658.0
70 kJ/mol
= E(n AHf\
I(A//;?)R
- Km
AHf\
XD (X-Y)p
(AHpP
AH?
Uj = moles of product j .
As an example, consider the stoichiometric oxidation of
methane to gaseous CO2 and H2O given the following vaJues;
A///-CH4(g) = - 7 4 . 9 0 kJ/mol
Product
molecules
FIG. A3.1Schematic of standard molar enthalpies of formation (A H,) and of reaction (AHr) [1].
CHAPTER
28: ENGINEERING
SCIENCES
OF AEROSPACE
FUELS
753
= - 3 9 3 , 5 2 - 483.66 + 74.90
APPENDIX 4
= - 8 0 2 . 2 8 kJ/mol
It is noteworthy that the enthalpy of formation of O2, N2,
C(gr) and other elemental molecules at their standard conditions is zero since AHa and D(X^Y) are equal and opposite
in sign. It is also of interest to note that the above value is a
net quemtity since the product water is in the vapor phase.
(See the section on Calorific Values.)
From the above discussion on enthalpies of formation, it
might appear that the full complement of the dissociation
bond energies would be required in order to dissociate a fuel
molecule into its component free gaseous atoms of carbon
and hydrogen. However, the chain nature of the ignition process implies that only one bond need be broken to start the
chain. Furthermore, some molecules will have more than the
average level of energy, and also both bond breaking and remaking are occurring together. All these factors result in an
"activation energy" of a considerably lower level t h a n
D(CC) or D(CH). The actual value can be determined experimentally by plotting ignition temperature (T) against delay (t) on the Arrhenius basis as follows:
combustion.
dissociation
Reaction rate
where
q
t
e
E
Ro
T
dt " ^
kR [C]'^
where
instantaneous molar
concentration of material X,
[X]
dq
Since --T- a t -\tae'^''^:
constant e
[Cf
It follows that
Int
In (ti/t2) =
Hence, E
_\_
J_
Rn
Ti
T2
Ro lniti/t2)
Ti
J_
T2
For n-octcine the calculations appear as follows:
8.3143 In (20/1.2)
598/
8.3143 In 16.67
0.001992 - 0.001672
8.3143 X 2.8135
0.00032
Furthermore,
^ = -n
r. where p = total pressure.
p
total mol
^
^
Thus in each case, p^ can be expressed in the following
manner:
Px = P, (
L\
^^502
Y + constant + constant
^ = K'
kR
[A]^ [Bf
PCO2
pCO {pOzT
,,
_
Kco,
"CO2
nr>_/n+^0.5
"C0(p"02/"t)'
Solution for the six unknown values of n requires six equations, four of which are provided by molar balances of C, H,
O, and N as for the simple non-dissociated case. The remaining two equations are then derived from the published values
of Kco2 and KHJO for the temperature in question, where
H2 + 0.5 O2 ^ H2O
PH2O
PH2 ip02)'
Hence,
"H2O
= K,
'' " " ' " "H2 (p"O2/"t)0-5
PCOPHIO
KcOj
Pco2 Pw.2
(Note: This equilibrium constant is used for solving the imaginary non-dissociated rich mixture case since, although n o
dissociation complications arise, the distribution of the limited oxygen available to the CO and H2 has to be determined).
Selected values of the partial pressure equilibrium constants are given in Table A4.1.
Although at the higher temperatures dissociation proceeds
further to promote radicals such as O, H, OH and NOx (that
is, NO + NO2), a first approximation to realistic conditions
can be made by considering dissociation restricted to CO, H2
and O2 only, giving the following combustion equation for
any general mixture strength;
CaHb + m (O2 + 3.76 N2)
300
500
1000
1500
2000
2100
2200
2300
2400
2500
2700
3000
KcOj
1.1641 X 10"^
575.44 X lO''^
10.593 X lO^''
16.634 X 10^
207.01 X 10^
765.60
345.94
168.27
87.097
47.753
27.543
10.351
3.0549
K,H20
ni
n j {p Us/Ut)"
and
n2
n4 {p ns/nt)"
Temperature, K
Kco2
KH20
KWGS
11.169 X 10^^
6.1094 X 10^'
76.913 X 10^'
11.535 X 10'
530.88 X 10^
3.4670 X 10^
1.6866 X 10'
874.98
480.84
277.43
167.49
68.077
22.029
9.5945 X 10"^
10.617 X 10"^
7.2607 X 10"'
0.6935
2.5645
4.5285
4.8754
5.1999
5.5207
5.8097
6.0810
6.5769
7.2110
APPENDIX 5
Calculation of M a x i m u m Reaction Temperature
The method of solution is based on the concept of equating
the enthalpy released by the reactants, in generating the dissociated products at the initial temperature, with that which
would have been required to heat those products from the
initial temperature to the final temperature J*. As in most
thermochemical work, the standard initial temperature is
taken as 25C (298.15 K). Hence,
[Chemical enthalpy released (negative) with reactants at
298.15 K oxidized to products at 298.15 K, that is, the standard enthalpy of reaction] is equal to
[Physical enthalpy absorbed (positive) by products in heating
from 298.15 K t o r * ]
that is,
- MIr = (//^*jp algebraically
But
\Hr = [{^H^)p - (^H^)B.'\
Thus,
(H^* + A//;)p - (AHf )R = 0
CHAPTER
28: ENGINEERING
SCIENCES
OF AEROSPACE
FUELS
755
(AH/)R = 0
where H[*
= total thermochemical enthalpy at temperature T* based
on initial 298.15 K
Expansion gives
(A///)fuel
5 ns
= 0.05468
6 ng = 7.52
^ 0.05468
ns
10.536
(assumed nj/ut)
0.00519
Suj = (10.52 + ns) = 10.575
7 n,
TABLE AS. 1Standard-based total thermochemical enthalpy levels for gases, kj/mol [9] [1],
H[= (H^ + AH})
for Compounds
Hi = H"for Elements
Temperature, K
CO2
H2O
CO
H2
O2
N2
298.15
300
500
1000
1500
2000
2100
2200
2300
2400
2500
2700
3000
-393.52
-393.46
-385.21
-360.12
-331.81
-302.07
-296.02
-289.95
-283.85
-277.73
-271.60
-259.27
-240.66
-241.83
-241.76
-234.91
-215.85
-193.73
-169.14
-164.00
-158.79
-153.53
-148.22
-142.86
-132.01
-115.47
-110.53
-110.47
-104.60
-88.843
-71.680
-53.790
-50.154
-46.509
-42.853
-39.183
-35.505
-28.121
-16.987
0
0.054
5.883
20.686
36.267
52.932
56.379
59.860
63.371
66.915
70.492
77.718
88.743
0
0.054
6.088
22.707
40.610
59.199
62.986
66.802
70.634
74.492
78.375
86.199
98.098
0
0.054
5.912
21.460
38.405
56.141
59.748
63.371
67.007
70.651
74.312
81.659
92.738
756
MANUAL
HANDBOOK
In the absence of the effects of gravity or motion, this energy change is located entirely within the internal energy of
the system material, hence:
n.f. (q w) =
and
Qout) " W = 0
(A6.1)
n.f. d q z - 1W2) = M2 - Ml
APPENDIX 6
AM
+ g (z2
^2
2^
(A6. 2)
MNL37-EB/Jun. 2003
S p e c i f i c a t i o n s a n d A p p l i c a t i o n s o f F u e l Oils
Fuel oils are burned to generate heat for different purposes
ranging from home heating to raising steam in utility boilers
to generate electricity. Different types of burners used in
these applications under various climatic and operating conditions dictate the need for different grades of fuel oils. A
standard specification by the ASTM International has divided fuel oils into five basic grades, designated as Nos. 1, 2,
4, 5, and 6 (ASTM D 396). Based on the production methods
used in petroleum refining, fuel oils fall into two broad classifications: distillates and residuals. The distillates comprise
overhead or distilled fractions, whereas the residuals consist
of bottoms remaining from the distillation, or blends of distillates with the bottoms from distillation, visbreaking, and
catalytic cracking processes [2-4]. The six grades of oils can
consist of different t5^es according to the refining processes
used in their production, as described in the section on
Petroleum Refining [5]:
For each material, production processes, product properties, and specifications are discussed in the context of respective industrial applications. Standard methods used for
characterization of these materials are identified with a focused discussion on the interpretation of the results obtained
from the standard tests. Literature references are provided
for further information on each topic.
1.
2.
3.
4.
FUEL OILS
Petroleum refining processes generate many product streams
that can be used as fuel oil either in single streams or in
blends to adjust the desired properties for specific applications. A broad definition of fuel oils does occasionally include
diesel fuels since they are closely related to distillate and
heavy fuel oils. In this section, however, diesel fuels are not
included for discussion, since they are covered separately in
this manual [1]. Industrial use of fuel oil for generating heat
is the principal focus in this section. Specifications and
applications of fuel oils are introduced with an overview of
straight-run distillate;
straight-run residual (i.e., reduced crude);
catalytically cracked distillate;
cracked residuals from thermal or catalytic cracking, or
hydrocracking;
5. blends of any of the streams listed above.
Cracked oils have rather different composition and properties from those of the straight-run oils, as discussed later.
In the ASTM specification. Grades No.l and No.2 are distillates and Grades No. 4-6 are usually residuals. Some heavy
distillates may, however, be sold as Grade No. 4 fuel oil.
Grade Nos. 4 and 5 are subdivided into light and heavy categories. Table 1 summarizes the common uses and some significant properties of the different grades of fuel oils [6].
Grades 1 and 2 are used in domestic and small industrial
burners. Grade 1 is a particularly light distillate for use in the
vaporizing type burners and under storage conditions that require low pour points. Grades 4-6 are used in pressure atomizing-type commercial/industrial b u r n e r s that can handle
high viscosity fuels. The viscosity of these residual fuels increase with the increasing number in the grade scale such
that Grade 6 fuel, also called Bunker C, requires preheating
for handling and burning [6].
In general, all grades of fuel oil should be homogeneous hydrocarbon oils, free from inorganic acid, and free from ex-
757
Copyright'
2003 by A S I M International
www.astm.org
758
MANUAL
HANDBOOK
TABLE 1Common uses and some significant properties of different grades of fuel oils.
Grade
Classification
No. 1
Distillate
No. 2
Distillate
No. 4 (Light)
Heavy Distillate
No.4
Heavy Distillate,
Distillate/Residual
blends
No. 5 (Light)
& No. 5 (Heavy)
Residual
No. 6 or Bunker C
Residual
I m p o r t a n t F u e l Oil P r o p e r t i e s
Fuel oils are burned to generate heat. The a m o u n t of heat captured in combustion systems is the principal concern for the
fuel user. Important properties of fuel oils must, therefore,
relate to their combustion characteristics and performance in
different types of burners and fuel handling systems. Understanding these properties helps the user to select a fuel best
suited for a specific application. It is also useful to discern the
relationships between different properties of fuel oils. All the
properties of fuel oils identified in Table 2 are discussed below, with reference to standard measurement methods, and
the significance of the measured properties.
Gravity
The density of petroleum oils is often expressed in terms of
API gravity, a scale devised by the American Petroleum
Institute and National Bureau of Standards (continued as
National Institute of Standards and Technology). The API
Application
Domestic and small
industrial burners of the
vaporizing type
Atomizing type domestic and
small industrial burners
Pressure-atomizing type
commercial/industrial
burners
Pressure-atomizing type
commercial/industrial
burners; preheating not
required for handling or
burning
Industrial burners; preheating
may be required for
handling and burning
Industrial burners;
preheating required for
handling and burning
Significant Properties
Volatility and pour point
Volatility and viscosity
Viscosity and pour point
Viscosity, flash point, and
sulfur content
759
No. 1
0.8499
35 min
38 (100)
18''(0)
1.4
2.2
1.3
2.1
No. 2
0.8762
30 min
38 (100)
- 6 " (20)
2.0"
3.6
1.9
3.4
(32.6)
(37.9)
No. 4
(Light)
No. 4
No. 5
(Light)
No. 5
No. 6
55 (130)
55 (130)
60 (140)
0.8762"
38 (100)
-6" (20)
2.0
5.8
(32.6)
(45)
55 (130)
- 6 " (20)
5.8
26.4^"
5.5
24.0'
(45)
(125)
>26.4
65^
>24
58^
(>125)
(300)
>65
194^^
>58
168^
(42)
(81)
>92
638^^
(>300)
(900)
(>900)
(9000)
(23)
(40)
(>45)
(300)
215(420)
0.5
3
282'^
(540)
338 (640)
0.5*
3
0.15
0.35
0.05
0.05
288 (550)
0.05
0.10
0.15
0.15
(0.50)"
(0.50)'
(1.00)'
(1.00)"
(2.00)"
"It is the intent of these classifications that failure to meet any requirement of a given grade does not automatically place an oil in the next grade unless in fact
it meets all the requirements of the lower grade.
''In countries outside the United States other sulfur limits may apply.
"Lower or higher pour points may be specified whenever required by conditions of storage or use. When pour point less than - 18C (0F) is specified, the mini m u m viscosity for grade No. 2 shall be L7 cSt (31 SUS) and the m i n i m u m 90% point shall be waived.
'^Viscosity values in parentheses are for information only and not necessarily limiting.
"The amount of water by distillation plus the sediment by extraction shall not exceed the value shown in the table. For Grade No. 6 fuel oil, the amount of sediment by extraction shall not exceed 0.5 weight %, and a deduction in quantity shall be made for all water and sediment in excess of I.O weight %.
^Where low su Ifur fuel oil is required, fuel oil falling in the viscosity range of a lowered numbered grade down to and including No. 4 may be supplied by agreement between purchaser and supplier. The viscosity range of the initial shipment shall be identified and advance notice shall be required when changing from one
viscosity range to another. This notice shall be in sufficient time to permit the user to make the necessary adjustments.
*This limit guarantees a m i n i m u m heating value and also prevents misrepresentation and misapplication of this product as Grade No. 2.
''Where low sulfur fuel is. Grade 6 fuel oil will be classified as low pour -H5C (60F) max or high pour (no max). Low pour fuel should be used unless all tanks
and lines are heated.
oils from a single refinery stream, the API gravity can indicate w h e t h e r they are straight-run, or cracked oils. For
blends, e.g., No. 4 oil, the concentration of different types of
oils present, would, therefore, determine the API gravity of
the blend in the corresponding range.
In general, the API gravity of fuel oils can be qualitatively
related to other properties of the oils as shown below [7]:
The higher the API gravity, the lower the viscosity and carbon residue.
The higher the API gravity, the lower the volumetric heating value (Btu/gal), and the higher the gravimetric heating
value (Btu/lb).
The higher the API gravity, the lower the C/H ratio.
The higher the API gravity, the higher the rate of combustion, and the shorter the flame length.
Heating
Value
Heating value is broadly defined as the amount of heat released by complete combustion of a unit quantity of fuel. Experimental measurements can be reported as total (or high).
or net (or low) heating values in Btu per gallon. The total
heating value includes the latent heat of evaporation of the
water vapor produced during the combustion. For determining the net heating value, the water from combustion is considered to remain in the gaseous state, and, therefore, the
latent heat of evaporation is not recovered. Although no direct reference is made to heating value measurement in the
ASTM classification of fuel oils (there is indirect reference
through limiting API gravity. See footnote g in Table 2), heating value is a n important specification requirement. The
heating value, or the heat of combustion of fuel oils, can be
measured by the ASTM D 240. The net heating values of fuel
oil samples can also be measured by the ASTM D 4529, D
3338, or D 4809.
Depending on the specific gravity and composition of fuel
oils, total heating value ranges typically between 130 000
and 160 000 Btu per gallon (36 400-44 800 kJ/liter). The
net hea-ting value is usually 8400-8500 Btu per gallon
(2350-2380 kJ/liter) lower t h a n the total heating value, depending on the hydrogen content of the fuel. Figure 1 shows
760
MANUAL
.5' 160000
..... ...-r-:.
5 155000 J^^^/^,':: :
.:v.;-::=:;.:.;V
" 150000
oT 145000 -^sPiRiet^/.f:^***
*^ii_
&
I 140000
^'-'iftKi^> 135000
^[^-T.':--^^^^
o) 130000
~ 125000
; ri^7^:;:\
S 120000 "\r^ ^ ^i ' ^ I r' f H I". ^ ' i.":' '1
r
"^^^^feu'
'
'
'
HANDBOOK
-Total Heating
Value
-Net Heating Value
'
0 4 8 1216202428323640
API Gravity
FIG. 1Total and net heating values of fuel oils versus API
gravity.
Viscosity
The viscosity of oil measures its resistance to flow [10]. It is
one of the most important properties of especially the residual fuel oils that affect handling, heating, pumping, and atomization of heavy residual fuels in combustion. The most
commonly used viscosity term, kinematic viscosity, is determined by measuring the time for a fixed volume of liquid to
flow under gravity through the capillary of a calibrated viscometer (ASTM D 445 with specifications given in ASTM D
446). The measurements must be m a d e under a reproducible
driving head and at a closely controlled and known tempera-
Softening point
Viscosity
Solvent Fractionation
Coking Value
Density
Ash
Sulfur Content
ASTM Designation
Point
Point
As fuel oils are heated, they evaporate, and the vapors flash at
a certain temperature when ignited by an external flame.
This temperature is called the flash point. There are two standard ASTM tests to measure the flash point: ASTM D 92
(Cleveland), a n d ASTM D 93 (Pensky-Martens), using an
open-cup, and a closed-cup flash tester, respectively. The
closed-cup tester gives lower flash points because of the more
effective retention of very light vapors that are blown away by
the air flow in the open-cup tester. Therefore, the closed-cup
test is more sensitive in detecting the small amounts of light
vapors in the fuel oil samples. As shown in Table 3, desirable
flash points of fuel oils range from 38C (Grades N o . l , 2) to
60C (Grade No.6) measured by closed-cup testers. Flash
points lower than the desired values may cause fire hazard,
whereas high flash points can lead to difficulties with starting, especially in a cold furnace.
Distillation
ASTM D 86 is used to determine the 10% and 90% points of
the distillate fuel oils (Grade No. 1 and No. 2) as specified in
Table 3. The distillation characteristics (volatility) of these
fuels are related to their ignition and combustion properties
and the tendency to form solid combustion deposits. The
lower and upper limits to volatility are set to ensure safety
and smooth operation in the use of these fuels.
Water and Sediment (BSW)The presence of water and
sediment, also called bottom sediment and water (BSW), in
761
Residue
The term carbon residue is used in several different connotations related to the use of fossil fuels, including carbonaceous
particles present in fuel, carbon formed on the burner tips
and furnace walls because of incomplete combustion, and
carbonaceous residue remaining after pjTolysis of fuels in
standard tests. Only the results from standard carbon residue
tests are used in fuel specifications. It is important to distinguish between the carbon deposition due to the high carbon
residue of the fuel oil, and coke or soot formation as a result
of poor combustion [15]. Understanding the difference between these two types of deposition helps identify the root
cause of any deposition problem: fuel composition or combustion conditions [16].
Three standard methods used to determine carbon residue
are ASTM D 189, Conradson Carbon Residue (CCR), ASTM
D 524, Ramsbottom Carbon Residue (RCR), and ASTM D
4530, Micro Method. Most specifications are based on CCR,
but correlations exist to convert between CCR and RCR test
results [ASTM D 189].
Table 3 shows that carbon residue is specified only for light
fuel oils, No. 1 and No. 2, because small vaporizing-pot and
sleeve-t3^e burners used in domestic applications have less
tolerance for carbon deposition. The carbon tests are conducted on 10% bottom residue of the fuel samples remaining
after distillation.
Ash
Ash results from the noncombustible organic and inorganic
species found in fuel oils. Most of the ash can be traced back
to the constitution of the crude oil from which the fuel oils
762
MANUAL
HANDBOOK
were derived. To a lesser extent, contamination during refining and handling may be responsible for the ash content.
Most of the ash-producing materials present in crude oil
(e.g., water soluble sodium and calcium chlorides, and oil
soluble organometallic compounds of nickel and vanadium)
tend to concentrate in the heavy products, such as residual
fuel oils. Ash contents of fuel oils can be determined by
weighing the n o n c o m b u s t i b l e residue after c o m b u s t i o n
using ASTM D 482.
Table 3 shows the permissible ash contents specified for
Grades No. 4 (0.05%, 0.10% for light and heavy, respectively),
and No.5 (0.15%). No specifications are given for No. 1 and 2
because ash is seldom found in distillate oils. Also, there is n o
ash specification for No. 6 oils (which may contain u p to
0.2% ash [17]) since the combustion equipment designed for
burning heavy residual fuels can handle relatively high ash
contents.
Problems encountered with high ash contents depend on
the application and type of combustion operation, including
contamination of products in direct firing applications (e.g.,
glass and ceramic industry), erosion of p u m p p a r t s and
burner tips, and accumulation of ash on boiler tubes. High
metal contents of heavy oils would also be responsible for
producing particulate emissions from combustion with potentially significant toxicity [18].
The removal of ash from fuel oils is not practical and very
costly because most ash-forming compounds are soluble in
the oil. Problems with high ash contents are usually addressed by blending with low ash oils and/or by reducing the
impact of ash in combustion operations with fuel additives
and combustion system treatments [17].
Sulfur
Content
and
Incompatibility
Conclusions
A standard classification of fuel oils according to selected
specifications facilitates the selection of the right fuel oil for
wide ranging applications in different combustion systems
that show significant variations in size, combustor design,
and process needs. A large number of ASTM methods exist to
characterize many properties of fuel oils that are of interest
for a particular application. Understanding the significance
of these tests and careful interpretation of the test results will
help troubleshoot m a n y performance problems in fuel oil
handling and combustion systems.
PETROLEUM PITCH
Petroleum pitch has become an important material for a
n u m b e r of industrial applications, in particular, for manufacturing high-performance c a r b o n fibers and carboncarbon composites. This section provides an overview of
p r o d u c t i o n processes, applications, and properties of
petroleum pitch.
Production Processes and Applications
Petroleum pitch is a term used for certain petroleum residues
due to their resemblance to other pitch materials, such as
coal tar pitch, that are thick, dark colored bituminous substances obtained from destructive distillation processes.
Generally, petroleum pitch is the nonvolatile product obtained from thermal or catalytic cracking of heavy petroleum
residua [4,21]. It may also be defined as the high boiling
point fraction (420-520C) obtained by vacuum distillation
(0.5-1.0 m m Hg) of catalytic cracking bottoms [22], or as solvent deasphalted bottoms [23]. Due to its resemblance to coal
tar pitch, the ASTM methods that are summarized in Table 3
are often used to test both materials. However, petroleum
and coal tar pitches are substantially different in origin,
structure, and behavior, and, therefore, a ccireful interpretation of the test results is necessary.
CoaJ tar pitch is obtained from the distillation of volatile
by-products, or tar, from coke ovens during the manufacture
of metallurgical coke from coal. The differences in the origin
and processes that lead to the production of petroleum and
coal tar pitch are apparent in their chemical composition and
respective industrial applications [24,25]. For instance, the
carbon content of petroleum pitch is around 85-90%, which
is somewhat lower than that of coal tar pitch (94-96%). This is
linked to the higher hydrogen content of 4-6% for petroleum
pitches, versus 2 - 3 % for coal tar pitches. Hence, petroleum
pitches contain a relatively high proportion of aliphatic carbons compared to coal tar pitches. Both petroleum and coal
tar pitches are predominantly aromatic, with the majority of
alkyl groups being methyl. However, while a tj^ical coal tar
pitch has an aromaticity of 98-99%, petroleum pitches have
around 10-20% aliphatic carbon. Coal tar pitches contain relatively more condensed aromatic ring structures with a
bridgehead aromatic carbon content (i.e., aromatic carbon
only bound to other aromatic carbons) of 0.45-0.50. Therefore, the volatile compounds in coal tar pitches, as detected by
GC-MS, are mainly three to six aromatic ring compounds,
such as phenanthrene, fluoranthene, pyrene, benzo[a]pyrene,
benzo[b]fluroanthene, and a n t h a n t h r e n e , while the nonvolatile compounds have a much higher condensed structure.
In contrast, petroleum pitches have a rather open structure,
with a bridgehead aromatic carbon content around 0.35-0.40
[26]. The volatile compounds are two-to four-ring compounds
that are heavily alkylated. The non-volatile compounds are
non-defined entities of larger a r o m a t i c ring structures
substituted with long-chain alkyl groups and possibly some
saturated rings. These differences in structure and composition explain the differences in softening points and
viscosity behavior, solubility, density, and coking yields from
the coal tar and petroleum pitches, as described in Properties
of Petroleum Pitch.
763
764
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
Description
D 3461
Softening point of asphaltene and pitch (Mettler cupand-ball method)The pitch is loaded in a small
metal cup with a bottom orifice and a ball is placed
on top of the solid pitch. The assembly is placed in a
furnace and a light beam is used to detect the
temperature when the ball is penetrating the pitch
(the softening point).
Softening point of bitumen (ring-and-bsdl apparatus)
The pitch is loaded in a small metal ring and a ball
placed on top of the pitch. The assembly is placed in
a bath and the temperature when the ball is
penetrating the pitch is manually detected (the
softening point).
Softening point of pitch (cube-in-air method): Molded
cubes of pitch with center holes are placed on hooks
and suspended in an oven. The temperature of the
hooks when the pitch is flowing is manually detected
(the softening point).
Softening point of pitch (cube-in-water method):
Molded cubes of pitch with center holes are placed
on hooks and suspended in water. The temperature
of the hooks when the pitch is flowing is manually
detected (the softening point).
Softening point of pitches (Mettler softening point
method): The pitch is loaded in a small metal cup
with a bottom orifice. The assembly is placed in a
furnace and a light beam is used to detect the
temperature when the pitch is flowing through the
orifice (the softening point).
D 36
Point
Petroleum pitches are mixtures of condensed aromatic compounds. As a result, petroleum pitches are eutectic, i.e.,
soften at a lower temperature than the individual melting
points of the different compounds that make u p the pitch.
At ambient temperatures, the pitch has an isotropic structure and is generally characterized as a glassy solid (hardpitch). When the pitch is heated in an inert atmosphere, it
has no defined melting point, but will pass through a glass
transition region before it becomes an isotropic liquid.
While a pure compound, e.g., anthracene, goes from a solid
to liquid at 217.5C, a mixture of similar aromatic compounds and their alkylated derivatives will exhibit a wide
temperature interval (4Tg can range from 10' to over 10^C)
from the end of the solid phase to a fully liquid state. The
transition from a glassy solid to a viscous substance gives
rise to a physico-chemical characteristic CcJled the glass
transition temperature, Tg [33]. Although there is no ASTM
method yet developed, both the Tg and the temperature interval, ZlTg can be determined by different methods [34]
such as ' H N M R , electron-nuclear double resonance (ENDOR) or differential scanning calorimetry (DSC). The enthalpy, /IH, and activation energy, Ea, for pitches can then
be derived from the above techniques, ft has been shown
that the Ea can be considered to be proportional to the
mean molecular size in pitch, and can give an estimate of
the degree of condensation [35].
During the transition from a glass to a liquid, the viscosity
of the pitch changes drastically (see Viscosity). However, it is
relatively tedious and labor intensive to determine the viscosity behavior for every single pitch. Therefore, several standard test methods, ASTM D 3461, D 36, D 2319, D 61, and D
3104, have been developed to establish when a pitch reaches
a viscosity of about 10^ Pa s, generally referred to as the
softening point of the pitch [36]. Table 4 lists the differences
between the five standard test methods given by ASTM. D
3104, Mettler Softening Point Method or D 61, Ring and Ball
Softening Point, are the most commonly used. D 3104, Mettler Softening Point Method, provides fast and accurate determination of the softening point but requires the purchase
of an instrument. D 61, Ring and Ball Softening Point, is fast
and inexpensive, and, therefore, it is also frequently used.
The softening points can be given both in C or F, and sometimes they give rise to pitch nomenclature, where Ashland
petroleum pitches A-170 and A-240 have softening points of
170 a n d 240F, respectively. Furthermore, it has been reported that pitches having similar softening point can have
different Tg, which can be associated to differences in viscosity as described below.
D 2319
D 61
D3104
Viscosity
The determination of changes in viscosity and other rheological properties during and after the glass transition region is
crucial for applications of pitch as a binder for electrodes and
road aggregate. ASTM D 5018, Standard Test Method for
Shear Viscosity of Coal-Tar and Petroleum Pitches, is a good
tool to follow the rheological properties of pitches at temperatures of 40-100C over its softening point, since it requires a
relatively simple setup. The setup consists of a hotplate, a
temperature controller, a thermometer, and a rotational viscometer. The pitch is melted into a cup on the hotplate where
the rotor from the viscometer is inserted, and at different
temperatures the viscosity is measured. The method is limited to 230C and 15 000 cps (15 Pa s).
Viscosity, 17, is defined as the ratio of the shear stress, T, to
the rate of change of shear strain, ySR, at constant temperature and pressure, TJ = r/ySR [37]. When the viscosity of a
system is only a function of temperature and pressure, and
independent of the shear rate at constant temperature and
pressure, the fluid can be classified as Newtonian. For nonNewtonian systems, such as polymers and most liquid crystals, the viscosity is dependent on the shear rate as well [34].
Isotropic pitches before thermal decomposition are mainly
Newtonian [38]. However, non-Newtonian flow, such as
Bingham behavior, has been detected where there is no flow
until the shear stress exceeds a critical value called the yield
stress [39]. The variations in viscosity with temperature for
the petroleum pitch Ashland A-240 is compared to a coal tar
pitch and its solvent fractions (see Solvent Fractionation in
Fig. 2 [40]. With increasing temperature, there is a rapid decrease in viscosity during softening of the pitch. In the tem-
765
TABLE 5Nomenclature and solvents used historically in the petroleum and coal tar pitch industries.
Petroleum Pitch
Carboids
Carbenes
Insoluble in CS2
Insoluble in CCI4, but
soluble in CS2
a-resin
/3-resin
Asphaltenes
Insoluble in n-pentane,
but soluble in CCI4
or CeHft
y-resin
Resinoid
Crystalloid
Fractionation
A drawback in pitch characterization is that the nomenclature used for solvent fractionation of petroleum pitch and
coal tar pitch has been different in the past [36]. The
766
HANDBOOK
D 2318
Description
Determination of quinoline insolubles (QI) in tar and
pitch by pressure fihration; The pitch is dissolved in
quinoHne at 75C and fihered through a porcelain
filtration crucible with a medium-porosity bottom at
a pressure in the range of 10-30 psig using nitrogen.
The sample is washed in hot quinoline until clear
followed by acetone and dried. The portion of the
pitch remaining in the crucible is defined as the QI
fraction.
Quinoline-insoluble (QI) content of tar smd pitch; The
pitch is dissolved in quinoline at 75C and digested
for 20 min. The solution is filtered through a
porcelain filtration crucible with a fine-porosity (7
yum) bottom using a suction filter apparatus. The
sample is washed in hot quinoline until clear,
followed by toluene, then acetone and dried. The
portion of the pitch remaining in the crucible is
defined as the QI fraction.
D 4312
D 2764
Description
Toluene-insoluble (TI) content of tar and pitch: The
pitch is dissolved in toluene at 95C for 25 min and
filtered through an extraction thimble using a
gravimetric filtration tube. The extraction thimble is
transferred to an extraction apparatus where it is
further extracted for 18 h using a toluene reflux rate
of 1 to 2 drops/s. The extraction thimble is dried at
105C for 30 min and the portion of the pitch
remaining in the thimble is defined as the TI fraction.
Toluene-insoluble (TI) content of tar and pitch (short
method): The pitch is dissolved in toluene at 95C for
25 min and filtered through an extraction thimble
using a gravimetric filtration tube. The extraction
thimble is transferred to an extraction apparatus
where it is further extracted for 3 h using a toluene
reflux rate of 120-150 drops/min. The extraction
thimble is dried at 110C for 30 min and the portion
of the pitch remaining in the thimble is defined as the
TI fraction.
Dimethylformamide-insoluble (DMF-I) content of tar
and pitch: The pitch is dissolved in dimethylformamide at 95-100C and digested for 30 min. The
solution is filtered through a porcelain filtration
crucible with a fine-porosity (7 /xm) bottom using a
suction filter apparatus. The sample is washed in hot
dimethylformamide until clear followed by acetone
and dried at 105-110C. The portion of the pitch
remaining in the crucible is defined as the DMF-I
fraction (mainly used as a rapid TI determination).
purities. The primary fraction consists of material that partially retards coalescence during carbonization of pitch. The
secondary fraction is in itself able to coalesce and is therefore
referred to as the mesophase QI. The impurities consist of
dirt and metal particles, and in the case of coal tar pitch,
c a n y over coke from the by-product furnace. Both the primary and the secondary QI consist of high molecular mass
species as reflected in low atomic H/C ratios (tjrpically 0.25
and 0.35, respectively). The effect of the QI on pitch carbonization is heavily dependent on the size and the distribution of primary and secondary QI in the a-resin.
Petroleum pitches are generally free of primary QI. On the
other hand, the j3-resin can be a substantial component of the
pitches produced from petroleum (ranging from 0-80%),
while coal tar pitches for binder purposes contain around
10-20% ;S-resin. Even though the H/C ratio of around 0.40 of
the 13-resin fraction is close to that of the secondary QI, the
first will undoubtedly have a lower molecular mass since
thermal treatment of the /3-resin could transform it partially
into secondary QI. This suggests that the structures of secondary QI and /3-resin are relatively similar and only differ by
some degree of condensation [26]. The y-resin, i.e., the
toluene-soluble fraction, has the highest H/C ratio and, due to
its high solubility, it can be readily investigated by chromatographic a n d other analytical techniques. Such techniques include high-pressure liquid chromatography (HPLC)
where different aromatic compounds can be identified by
their UV spectra following a separation by elution through a
packed column with different solvents, gel permeation
chromatography (GPC) to identify the molecular mass distributions, and nuclear magnetic resonance (NMR) for the determination of the average hydrogen and carbon skeletal
parameters [26,27].
The influence of primary QI on pitch carbonization has
been the subject of intensive research. Primary QI has sometimes been referred to as "carbon black-like" due to its smeJl
particle size. However, there are several differences between
the two forms. First of all, primary QI can reach a particle
size of about 1 /xm and secondary QI much higher, while carbon black particles have an average size of 20-30 n m [44].
Scanning electron microscopy (SEM) studies have shown
that primary QI particles are generally spherical, reaching an
average particle size of 0.1-1 fim. Figure 3 illustrates the particle size distribution of (a) typical primary QI of a coal tar
pitch and compares those to (b) the particle size of secondary
QI particle from a heat-treated petroleum pitch. The differences are clearly observed in Positions A, B, and C in Fig. 3
(a) and Position N in (b). The coal tar pitch has a range of particle sizes between 0.1-1 /xm in diameter, while the
petroleum pitch contains agglomerated secondary QI particles in the range of 2-10 /xm in diameter. Secondly, carbon
black particles have the ability to form chains, where hundreds of units are aggregated together, with some degree of
(a)
(b)
FIG. 3SEM micrographs comparing the particle size distribution of (a) typical primary QI of a coal tar pitch and (b) the
particle size of secondary QI particle from a petroleum pitch.
Position A, B and C: primary QI spheres ~ 0.1 /xm in dia., agglomerated, and ~1 fim in dia., respectively. Position N: Agglomerated secondary QI particles. Reprinted with permission
from Elsevier Science.
(a)
767
1 iMui, and an attempt has been made to quantify the secondary QI content by the difference in particle size. However,
secondary QI particles are frequently coating the infusible
particles of primary QI, which makes this technique inaccurate [45].
Coking
Value
(b)
768
MANUAL
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'^
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'
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Temperature / C
o'ju
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FIG. 5Comparison of TGA traces for a coal tar pitch and its
TS, beta-resin and Ql fractions.
Fig. 5. There is a good agreement between the whole pitch
and the added loss profile from its solvent fractions. From the
individual solvent fractions, it is clear that the QI loses very
little weight, which is also the case for the )3-resin. The main
weight loss occurs in the TS fraction, which indicates that the
weight loss is particularly dependent on the y-resin content.
Hence, a particular concern for the utilization of petroleum
pitch as a binder for carbon artifacts is its low content of
insolubles, in particuljir QI and to some extent also )3-resin.
Density
The density of pitch is a property closely watched by consumers, since low pitch density is generally related to low
coking value, increased costs, and reduced quality of the
resultcint carbon products. The ASTM standard methods differentiate between specific gravity (density) and relative
density, however, specific gravity is usually reported for
pitches. Due to the different appearance of pitch, three standard methods for specific gravity have been developed by
ASTM: D 2320 deals with sohd fragmented hard pitch, D 70
concerns soft pitch, and D 4892 applies to pulverized pitch.
All three methods involve the use of pycnometer. Since the
pitch density is dependent on temperature, ASTM has developed a standard test method, D 2962, for calculating a volume-temperature correction. However, this test method is
only developed for coal tar pitch and there is no equivalent
m e t h o d for p e t r o l e u m pitch. The d e p e n d e n c e of specific
gravity upon pressure is normally ignored. The standard test
method for relative density, D 71, utilizes water displacement, a n d is therefore a quick method. However, relative
density of pitch is rarely reported.
Petroleum pitches have densities spanning from 1.10-1.30
gcm^^ cind are somewhat lower than that of coal tar pitches,
which have specific gravity in the range 1.30-1.40 gcm~^.
Hence, increasing the density of petroleum pitches is a key issue in their competition with coal tcir pitches.
Sulfur
Content
The sulfur content in some oil crudes may be very high (3-5
wt%) and correspondingly can result in high sulfur levels in
the resultant petroleum pitch, where levels u p to 4 wt% have
been reported [23]. Since there is no specific ASTM method
for sulfur determination in pitch, it is typical to use a Leco sulfur analyzer. However, ASTM D 1552, Standard Test Method
Ash
Petroleum pitches have generally low ash contents below
0.1%. The standard test method for ash in pitch is described
in ASTM D 2415 and applies to both hard and soft petroleum
pitches. The m a i n elements in ash from petroleum pitch are
iron, nickel, and vanadium [23], and these heavy metals are
known to m a r the carbon products used in the aluminum and
steel industries [49].
Conclusions
The ASTM standard methods for pitch chetracterization Eire
i m p o r t a n t tools for the establishment of petroleum pitch
properties such as softening point a n d viscosity behavior, solubility, density and coking yield, and ash and sulfur levels, as
described in the above sections. The monitoring of pitch
quality through standardized methods is crucial for the future of the carbon industry, due to its dependence on high
performance pitches for purposes such as binders and for impregnation of carbon materials, and precursors for carbon
fibers and composites. Although coal tar pitch is presently
dominating the market, a decline in its availability is forecasted, especially in the U.S., due to the reduced numbers of
by-product coke ovens. Hence, petroleum pitch cam gain access to these markets through innovative manufacturing processes for tailored properties. The ASTM standard methods
will be important reference points for the development of
high performance petroleum pitches.
PETROLEUJVI COKE
Petroleum coke is a generic term used to describe a variety of
carbonaceous solid products intentionally produced by severe thermal cracking of p e t r o l e u m heavy fractions. The
composition, microstructure, and properties of petroleum
cokes depends on the nature of the feedstock and the coking
process. Specific chemical a n d physical properties a n d microtextural characteristics of petroleum cokes are critically
important for their industrial/commercial uses. Petroleum
coke production processes, the composition and properties
of coker feedstocks, and the formation of coke microtexture
in coking processes are described a n d discussed in this section along with classification, properties, and uses of
petroleum cokes.
Petroleum Coke Production Processes
Low-temperature carbonization (coking) at temperatures below 500C converts high-boiling petroleum fractions or
APPEARANSi
< -
769
OPTICAL
TEXTURE
NEEDLE COKE
OPTICAL MICROGRAPH
OF NEEDLE COKE
SPONGE COKE
OPTICAL MICROGRAPH
OF SPONGE COKE
SHOT COKE
OPTICAL MICROGRAPH
OF SHOT COKE
/"^^"N
NAPHTHA
SEPARATOR
770
MANUAL
HANDBOOK
Very different in design and operation from Delayed Coking, Fluid Coking is another commercial coking process commonly used in petroleum refining to convert VDR and other
heavy fractions into distillate liquids, gases, and fluid coke. In
contrast to the semi-continuous nature of Delayed Coking,
Fluid Coking is a continuous process (see Fig. 6). In Fluid Coking, the feed is sprayed onto fine size hot coke particles in the
coker where coke is deposited on these seed particles by thermal cracking of the feed at temperatures between 480-525C.
Some of the coke product is introduced into a combustor
where partial combustion of the coke particles with air takes
place. Partially combusted hot coke particles are returned to
the coker to provide the heat necessary for thermal cracking/coking to complete the cycle. The resulting coke product,
fluid coke, has a different structure and different properties
compared to those of the delayed cokes, as discussed in the
following sections. Fluid coke is used principally as fuel with
some limited use in the manufacture of carbon materials.
Flexicoking process is a variation of Fluid Coking where the
fluid coke product is partially or completely gasified with air
and steam to produce fuel gas in the refinery [50,52].
Table 9 s u m m a r i z e s the coking processes, coker feedstocks, different kinds of petroleum cokes and their principal
industrial applications. Petroleum cokes produced by delayed or fluid coking are generically called green cokes because of their relatively high volatile matter content (5-15%).
Fluid cokes have generally lower volatile matter contents
than delayed cokes (typically around 5%) because of the relatively high temperatures used in fluid coking.
Formation of Coke Microtexture in Coking
Processes
Delayed cokes produced from VDR (sponge, fuel, and shot
coke) show substantial differences in microtexture, including
variations in the degree of structural anisotropy, the size
of anisotropic domains, and porosity. Sponge cokes are more
anisotropic, i.e., with a higher degree of microstructural
order, and more porous than shot cokes. Fuel cokes have
an intermediate degree of anisotropy and porosity between
those of sponge and shot cokes. Differences in the degree of
structural anisotropy of delayed cokes (illustrated in Fig. 7)
can be traced to the development of an intermediate liquidcrystalline phase, carbonaceous mesophase, during liquidphase carbonization in the delayed coker. Carbonaceous
mesophase is a unique, ordered fluid consisting of essentially
planar molecules. The prevailing molecular order, which exhibits an intermediate state between isotropic liquids and
Process
Delayed Coking
Fluid Coking
Flexi-coking
CCB
CCB
771
CCB
ETR
FIG. 8Stages of mesophase formation during carbonization of a decant oil (CCB)
and ethylene tar residue (ETR) sample, nucleation, growth, and coalescence of
mesophase spheres to form anisotropic coke texture.
Isotropic
Anisotropic
Fine mosaics
Medium mosaics
Coarse mosaics
Small domains
Domains
Flow domains
Description
produced by carbonization of a decant oil and a vacuum distillation residue in a laboratory batch reactor.
Figure 7 shows the optical textures of the samples of needle,
sponge, and shot coke particles, in addition to their external
morphologies, as described before. Commonly, the optical
texture of delayed cokes is heterogeneous, comprising a mixture of structures with different levels of anisotropy from mosaics to flow domains. A preponderance of a given texture, or
a mixture of textures, characterizes the principal optical texture of delayed cokes. The optical texture of needle cokes, for
example, consists mostly of straight flow domains. Sponge
cokes, on the other hand, display a predominance of acicular,
or twisted flow domains and large domains, while shot coke
texture consists mostly of mosaics and some small domains.
In other words, on the two extremes of optical texture scale,
needle cokes result from a high degree of mesophase development, whereas shot cokes display an inhibited mesophase
development. Distinct differences in the optical texture of delayed cokes explain many differences in physical and chemical properties of needle, sponge, and shot cokes, as further discussed in the Classification of Petroleum Cokes section.
Fluid cokes have very different microtextures from those of
the delayed cokes because of the substantial differences in
the operation and conditions of the two coking processes, as
MOSAICS
FIG. 9Flow domains and mosaics textures
as viewed by polarized-light microscopy.
described in Petroleum Coke Production Processes. Characteristically, fluid cokes have layered structures resembling
onions, because coke deposition tcikes place in layers on the
seed coke particles. Figure 10 shows the optical texture of a
fluid coke sample. In contrast to liquid-phase carbonization
in delayed coking, vapor phase cracking and polymerization
772
MANUAL
HANDBOOK
FIG. 10Optical texture of fluid coke (Petrographic Atlas, Prepared by Ralph Gray and Jack
Crelling, http://mccoy.lib.slu.edu/cgi-bin/projects/crelling/pageBuilder.pl?find=P36).
reactions on coke surfaces is primarily responsible for coke
formation in fluid coking. The opticcil texture of fluid cokes
is, therefore, very different from those of the delayed cokes.
Parallel orientation of concentric layers of coke creates more
isotropic structures in contrast to large anisotropic domains
present in sponge and needle cokes.
Coker Feedstocks
Commonly used coker feedstocks are vacuum distillation
residua (VDR), FCC U decant oils (DO), and thermal tars (TT).
Table 11 summarizes coker feedstock properties, presented
either as average values, or ranges of variation for typical
properties. The important differences between VDR and DO
include typically lower API gravity and higher aromaticity of
DO. VDR contains a large fraction of sulfur and metals (particularly Ni and V) found in crude oil because of their close association with asphaltene structures. VDR can contain u p to
40% wt asphaltenes (defined here as toluene solubles and pentane insolubles), whereas the maximum asphaltene content of
DO is usually not greater than 10% wt [54]. Further, the aromatic molecules in the asphaltenes of VDR, consisting of polycyclic aromatic ring systems connected with alkyl bridges, are
much larger than those in DO. Heteroatoms (S, N, and metals) tend to concentrate in these large molecules of VDR asphaltenes. The aromatic compounds in DO consist of much
simpler structures, containing mainly two- to six-ring fused
polycyclic aromatic hydrocarbons (PAH) [54,58]
Table 11 shows that despite their high API gravity (or low
specific gravity), VDR has a m u c h higher Conradson Carbon
value than DO, mainly because of the high asphaltene contents of VDR. In general, Conradson Carbon value is directly
proportional to coke yield from the delayed coking, or fluid
coking processes [50]. Generally higher sulfur contents of
VDR compared to those of DO should also be noted. Thermal
tars are similar in overall properties to DO; although TT tends
to be more aromatic than DO, and contain much less naphthenes. These differences in feedstock properties combined
with differences in coking conditions control the structure
and important properties of petroleum cokes, such as the optical texture, heteroatom contents, strength, and reactivity.
Chemical composition of coker feedstocks strongly affects
the mesophase development through the carbonization chem-
istry and the rate of coke formation [59]. In general, feedstocks with high aromaticity produce a high degree of
mesophase development, as explained by the planarity and
lower thermal reactivitity of aromatic c o m p o u n d s . Coker
feedstocks, particularly VDR, with a high asphaltene content
produce inferior cokes with a low degree of anisotropy, and
high heteroatom a n d metals contents. It has been shown,
however, that the molecular nature of the asphaltene fractions
is as important as, if not more important than, the asphaltene
contents of the feedstocks for controlling the mesophase development [60]. Hydrogen aromaticity, rather than carbon
aromaticity of the asphaltene fractions, appears to be an important structural parameter that relates to the carbonization
behavior of the coker feedstocks, such as carbonization reactivity, and hydrogen shuttling ability of the molecular constituents during carbonization. High hydrogen aromaticity,
which indicates small aromatic ring systems and low degree
of alkyl substitution on the aromatic rings, gives rise to a high
degree of mesophase development through controlling the
rate of molecular growth and fluidity (or viscosity) during carbonization. Heavily alkyl substituted, large aromatic ring systems, as found in the asphaltene fractions of VDR, lead to
rapid growth of n o n p l a n a r intermediates, and a rapid increase in the viscosity of the carbonization medium, thus impairing the mesophase development. In extreme cases, these
conditions lead to severe inhibition of mesophase development and to the formation of shot coke in delayed coking [53].
A good understanding of the chemistry of mesophase formation from complex petroleum feedstocks still remains a
current challenge, especially in terms of predicting the quality of needle cokes produced by delayed coking. Differences
in molecular constitution of DO, in terms of the distribution
of two- to four-ring aromatic compounds, have been shown
to affect the mesophase development in laboratory reactors.
An abundance of pyrene and alkylpyrenes in the DO, for example, leads to a high degree mesophase development. In
contrast, high concentrations of biphenyl, fluorene, and alkylated phenanthrenes produce inferior optical textures in the
resulting cokes [58]. Figure 11 shows a two-dimensional
high-pressure liquid chromatography trace of a decant oil
sample obtained with a photodiode array detector from normal phase separation using n-hexane and methylene chloride
as solvents. The HPLC chromatogram (x-axis:time, y-axis:ulraviolet light wavelength, and z-axis: intensity of ultraviolet
light absorption) with some indicates the complexity of the
molecular structure of the decant oils with a few peaks labeled (pyrene, methylpyrenes, and methylbenzopyrenes) for
demonstration purposes. However, individual compounds in
Vacuum
Distillation
Residue
Decant Oil
Thermal Tar
API Gravity
Sulfur, wt%
Conradson Carbon, wt%
Molecular Weight
C/H Ratio, Atomic
Aromatics, % wt
Paraffins, % wt
Naphthenes, %wt
7-15
0.5-3.0
10-20
850
0.65
35
10
55
1-8
0.5-0.8
5-10
300
0.8
62
0
38
-1-4
0.5
8-9
380
0.9
68
7
25
Graphitization Heat Treatment is a process of heat treatm e n t of nongraphitic carbon, industrially performed at
t e m p e r a t u r e s in the range between 2500-3300 K, to
achieve transformation into graphitic carbon.
Green Coke (raw coke) is the primary solid carbonization
product from high boiling hydrocarbon fractions obtained
at temperatures below 900 K. It contains a fraction of matter that can be released as volatiles during subsequent heat
treatment to approximately 1600 K. This mass fraction, the
so-called volatile matter constitutes 4 and 15wt% of green
cokes.
Needle Coke is a special t5rpe of coke with extremely high
graphitizability resulting from a strong preferred parallel
orientation of its layered structure and a particular physical shape of the grains.
Premium Coke is a n extremely well graphitizing carbon
with a high degree of optical anisotropy and is characterized by the combination of the following properties: high
real density, low reversible thermal expansion, and low ash
content combined, in most cases, with low sulfur content.
Puffing is an irreversible expansion of some carbon artifacts during graphitization heat treatment between 1650 K
and 2700 K.
Petroleum Coke Properties
Green cokes with relatively low sulfur, metal, emd ash contents are calcined-heat treated to 1600 K-to remove volatile
matter. Polarized-light m i c r o g r a p h s in Fig. 12 show the
shrinkage cracks and pores developed upon calcination of a
needle coke and a sponge coke. Calcined coke has a mass
fraction of hydrogen less than 0.1%. Calcined cokes are used
as fillers for carbon anodes, graphite electrodes, or specialty
carbons. Table 12 lists the specifications of calcinable green
0.030
0.025
0.020
'immnm^KMSm
^375.00
0.00
5.00
10.00
15.00
20.00
Hinutes
773
25.00
30.00
35.00
774
HANDBOOK
sis, p r o v i d e s u s e f u l g u i d e l i n e s f o r s a m p l e p r e p a r a t i o n f o r a
v a r i e t y of l a b o r a t o r y a n a l y s e s .
Volatile
Matter
V o l a t i l e m a t t e r c o n t e n t of g r e e n c o k e s is d e t e r m i n e d b y m e a s u r i n g t h e loss i n w e i g h t r e s u l t i n g f r o m h e a t i n g u n d e r r i g i d l y
controlled c o n d i t i o n s (ASTM D 4 4 2 1 , Volatile M a t t e r in
P e t r o l e u m Coke a n d ASTM D 6374, Volatile Matter in Green
P e t r o l e u m Coke, Q u a r t z Crucible P r o c e d u r e ) . T h e volatile
m a t t e r c o n t e n t is p a r t i c u l a r l y i m p o r t a n t for t h e i g n i t i o n c h a r a c t e r i s t i c s of t h e fuel c o k e s ; t h e h i g h e r t h e v o l a t i l e m a t t e r
0.1-1.0%
25-500 p p m
87-97%
3.0^.5%
50-2000 p p m
2-100 p p m
10-250
0.5-2.0%
10-100 p p m
0.1-0.5%
1.6-1.8 g/cc
50-300 p p m
0.2-2.5%
2-60 p p m
5-500 p p m
5-15%
Calcined Coke
0.2-1.5%
25-500 p p m
97-99%
<0.1%
50-2000 p p m
2-100 p p m
10-250 p p m
Negligible
10-100 p p m
<0.1%
2.08-2.13 g/cc
50-300 p p m
0.2-2.5%
2-60 p p m
5-500 p p m
<0.5%
Water Content
Oil Content
Granulometry
>8 mm
8-4
4-2
2-1
1-0.5
0.5-0.25
<0.25
Vibrated Bulk Density
8-4 m m
4-2
2-1
1-0.5
0.5-0.25
Grain Stability
8 ^ mm
Reactivity in CO2 at lOOOX
Ignition Temperature
Reactivity in Air at 600C
Elements
S
V
Ni
Si
Fe
Al
Na
Ca
K
Mg
CI
Crystallite Size, Lc
Density in Xylene
Specific Electrical Resistance
Total Porosity
Typical Value
0-0.2%
0.1-0.3%
10-20%
15-25%
15-25%
10-20%
5-15%
5-15%
0
0.64-0.70 kg/dm^
0.73-0.79
0.80-0.86
0.86-0.92
0.88-0.93
75-85%
5-10%
615-630C
0.1-0.20%/min
1-3%
80-300 p p m
80-160
50-250
50-250
50-250
30-120
20-100
5-15
10-30
0.1-0.2%
26-30 A
2.05-2.09 kg/dm^
480-520 Micro O h m m
15-20%
Method
ISO 2325
DIN 51 916
ASTM 5003-89
ISO 8723
ASTM 5004-89, ISO 8004
ASTM D 4422-89, DIN 51 903
DIN 51 911
Thermal Gravimetric Analysis
(TGA)
TGA
Elemental Analysis, X-Ray
Methods, Atomic Absorption
Spectroscopy
content, the easier the ignition. Emission of PAH from combustion of fuel grade cokes is an important environmental
concern that requires strict monitoring and control of emissions from the combustors. Fluid cokes have lower volatile
matter contents than the cokes produced by delayed coking,
because of higher coking temperatures used in Fluid Coking.
Among the cokes produced by delayed coking, needle cokes
have lower volatile matter contents (5-8%) than sponge and
shot cokes (10-15%). Green cokes with high volatile matter
content are not suitable for calcination. High volatile matter
content result from i m p r o p e r coking conditions, such as
short residence time and low coking temperatures, or feedstock properties. Calcination reduces the volatile matter content of the green cokes to less than 0.5% in the calcined cokes
used for carbon anode, or graphite electrode manufacture.
Ash
Ash content of petroleum coke can be determined by reducing the sample to an ash by heating in a muffle furnace according to the standard method ASTM D4422, Standard Test
Method for Ash in Analysis of Petroleum Coke. For fuel
cokes, high ash contents create operational a n d disposal
problems. Green cokes with high ash contents are not suitable for calcination mainly because of the detrimental effects
of inorganic impurities on calcined coke properties, e.g., reactivity, as explained below. Ash contents of less than 0.5
wt% are required for sponge cokes used for carbon anode
manufacture [52].
Sulfur
Sulfur content of petroleum cokes can be measured using
several ASTM standard methods including D 1552, Sulfur in
Petroleum Products (High-Temperature Method), D 3177,
Total Sulfur in the Analysis Sample of Coal and Coke, and D
4239, Sulfur in the Analysis Sample of Coal and Coke Using
High-Temperature Tube Furnace Combustion Methods. Sulfur content of petroleum cokes is important for both fuel
cokes, a n d green cokes calcined for c a r b o n anode and
graphite electrode applications. For fuel coke and sponge
coke applications, concerns related to SO2 emission and
equipment corrosion are the main considerations for limiting the sulfur content. Sulfur content in fuel grade petroleum
cokes and sponge cokes vary in the range 3-6 wt%, and < 3
wt%, respectively. Needle coke has a more strict specification
on the sulfur content (<0.5wt%), because sulfur causes puffing during the graphitization heat t r e a t m e n t resulting in
lower density and lower strength of graphite electrodes.
Nickel,
Vanadium,
and Other
Metals
775
sponge cokes used for anodes are related to the contamination of aluminum, or other produced metals with the heavy
metal impurities. Heavy metal contamination requires further treatment for purification, or limits the use of the produced metal in certain applications.
High alkali metal contents, e.g., Ca and Na, are also not
desired in sponge cokes, since these metals act as strong oxidation catalysts a n d increase anode c o n s u m p t i o n during
electrolysis.
Density
Several ASTM standard methods can be used to measure the
apparent and real densities of petroleum cokes, including D
167, Apparent and True Specific Gravity and Porosity of
Lump Coke; D 2638, Standard Test Method for Real Density
of Calcined Petroleum Coke by Helium Pycnometer; D 5004,
Real Density of Calcined Petroleum Coke by Xylene Displacement; and D 4292, Determination of Vibrated Bulk Density of
Calcined Petroleum Coke. Both apparent and real densities of
petroleum cokes depend on their thermal history and operating variables in the production processes. For many applications of petroleum cokes, apparent, or real density of the cokes
are closely monitored, since many industrial properties of
cokes, such as strength, thermal and electrical conductivity,
and reactivity of cokes can be related to coke density. Porosity of the petroleum cokes can be calculated from the apparent and true density measurements by the following formula:
Porosity = 100 - 100(apparent density/true density)
For true density measurements, helium pycnometry is commonly used to obtain meiximum penetration of the pores by
helium gas. For petroleum cokes, helium density is usually
5% below the theoretical density. This difference is attributed
to "closed porosity" in cokes that is not accessible to helium.
Porosity of cokes is particularly important for applications
where petroleum coke is used as filler in mixed formulations
with a binder (e.g., carbon anode, and graphite electrode
manufacture), usually coal tar pitch. Desired pitch/coke
ratios and the resulting properties of the baked, and graphitized carbons, therefore, depend strongly on the porosity, or
apparent density of the cokes. Strong correlations were reported between the bulk density of the filler cokes and the
electrical resistivity, strength, and coefficient of thermal expansion of the resulting graphite electrodes [62].
The real density of petroleum cokes increases with the increasing heat treatment temperature, and depending on the
graphitizability of the cokes, approaches the real density of
graphite u p o n graphitization heat treatment. Apparent density, on the other hand, can go through a m i n i m u m with the
increasing heat treatment temperature during calcination of
green cokes, because of porosity formation by devolatilization. F u r t h e r increase in h e a t t r e a t m e n t t e m p e r a t u r e increases the apparent density because of collapsing porosity
upon increasing the microstructural order.
Optical Texture
and Crystalline
Structure
776
HANDBOOK
Description
OTI [57]
OTI [58]
Isotropic
Anisotropic
Fine mosaics
Medium mosaics
Coarse mosaics
Small domains
Domains
Flow domains
No optical activity
Isochromatic areas (lA)
lA, 0.5-1.5;u,ni in diameter
lA, 1.5-5.O^m in diameter
lA, 5.0-lO.Ojixm in diameter
lA, 10-60/!Am in diameter
lA, > 6 0 ^ m in diameter
lA, >60/Ltm in length, >10/xm in width
1
3
7
20
30
30
1
1
1
5
50
100
Description
I
A
S
F
Isometrics
Acicular
Stringy
Fibrous
Size
<100 ij.m
100-300 ixm
300-1000 fj.m
> 1000 length,
> 6 0 /iim width
OTI [58]
1
5
50
100
Expansion
The coefficient of linear thermal expansion (CTE) is a critically important property for many applications of graphitic
carbons, particularly graphite electrodes used in electric-arc
furnaces. CTE is defined as the increase in length per unit
length per degree rise in t e m p e r a t u r e [71]. A low CTE is
essential for high thermal shock resistance, one of the most
important properties of graphite electrodes, defined as the
ability to resist weakening, or fracture when subjected to sudden heating, or cooling [72,73]. Compared to other materials,
graphite stands out in resistance to thermal stress and high
t e m p e r a t u r e s above 1300 K. As the m a i n c o m p o n e n t s in
graphite electrodes, the needle coke fillers exert the most important influence on thermal expeuision behavior of graphite
electrodes. Strongly anisotropic crystals, such as graphite,
have layered crystalline structure, in which the bonding is
highly directional. Graphite has a m u c h lower thermal
expansion in the layer planes (a-direction) that contain covalently bonded carbon atoms, than in the direction perpendicular to the layer planes (c-direction) that are held together by
van der Waals forces [74], as shown in Fig. 13.
The major factors that influence CTE of cokes and graphites
are texture and the orientation of crystallites. Pores and cracks
777
a-direction
Stacking height:
c-direction
FIG. 13A diagram of section of microcrystals of pregrahipitic order indicating covalent bonding in basal planes
(a-direction) and planes held together by van der Walls forces
(c-direction) responsible for anisotropic structure and
anisotropic properties.
778
MANUAL
HANDBOOK
Reactivity
Reactivity of cokes in oxidizing atmospheres constitutes another important industrial property of cokes. For fuel cokes,
high reactivity is desired for ease of ignition and combustion.
Relatively high volatile m a t t e r contents are, therefore,
desirable for fuel cokes. For calcined cokes used in material
applications, either intermediate or low reactivity is desired
depending on whether carbon needs to be consumed, or not
in the particular application.
Carbon anodes used for electrochemical reduction of AI2O3
are, for example, consumed in the reaction to liberate alum i n u m metal. Four major carbon-consuming reactions are
identified during electrolysis for aluminum production [25]:
1) 2Al203(diss) +2C(anode) > 4Al + SCOa - desired reduction
reaction
2) Al203(diss) +2C(anode) ^ 2Al + 3CO - generation of primary
CO, low C efficiency
3) CO2 + 2C(anode) > 2CO - uudesired consumption of carbon
4) O2 + C(anode) ^ 2C02 ; O2 + 2C(anode) ^ 2 C 0 - uudesircd
consumption of carbon by a i r b u m
Obviously, the first reaction is the desired reaction,
whereas third and fourth reactions lead to undesired consumption of anode carbon by Boudouard and a i r b u m reactions, respectively [25]. The second reaction also produces Al
but only with half of the yield obtained from the first reaction. An intermediate reactivity of carbon anodes (sponge
coke and pitch coke) is, therefore, desirable to promote the
desired reduction reaction and to inhibit the undesired anode
consumption.
In contrast to the electrochemical production of aluminum
by the consumption of carbon anodes, the consumption of
graphite electrodes in electrical-eirc production of steel takes
place only due to the uncontrolled b u m - u p of the electrodes
in air [88]. Consequently, extremely low reactivities of
graphite electrodes (made u p of needle coke filler and coal tar
pitch binder derived carbons subjected to graphitization heat
treatment) are desired to minimize electrode consumption
by a i r b u m .
The reactivity of cokes in oxidizing atmospheres depends
primarily on the degree of microcrystalline order (i.e., optical
texture), accessible surface eirea (related to the porosity), and
catalysis by inorganic impurities, such as Ni, V, Fe, K, Na,
and Ca. Oxidation, or gasification of cokes is a surface reaction that occurs at active sites at elevated temperatures. Carbon atoms at the edges of graphene layers (or basal planes)
or at defects on graphene layers such as vacancies and dislocations, are m u c h more reactive than the carbon atoms in
basal planes. The high reactivities of edge atoms result from
the dangling bonds, or unpaired sp^ electrons, at these sites
that readily chemisorb oxygen. Highly anisotropic cokes,
such as needle cokes, with relatively large microcrystallites
found in well-developed flow domains or domain textures
have low concentrations of these active edge sites, and, therefore, exhibit low reactivities. Sponge cokes, in comparison,
have a lower degree of anisotropy, and higher porosity, and,
therefore, have higher reactivities than needle cokes. High
porosity, or high accessible surface area, increases the ease of
diffusion of oxidant molecules to the active sites. Inorganic
impurities, on the other hand, promote the dissociation of
molecular oxygen to produce more active oxygen species that
readily react with carbon atoms even in the basal planes,
Conclusions
Petroleum cokes have many industrial applications, ranging
from generating heat (fuel coke) to manufacturing carbon
products such as carbon anodes and graphite electrodes. Produced from various petroleum heavy residua or fractions
from petroleum refining operations, petroleum cokes are
classified into different types on the basis of feedstocks (e.g.,
vacuum distillation residua or FCC decant oil), coke production processes (e.g., delayed coking or fluid coking), or their
appearance (e.g., sponge coke, shot coke, or needle coke).
Feedstock composition, the coking process used, and coking
conditions determine the structure a n d properties of
petroleum cokes that are important in various applications.
Among the important properties of petroleum cokes are
volatile matter content, density, sulfur and metal contents,
optical texture, coefficient of thermal expansion, and reactivity. Standard methods have been developed to quantitatively
determine many of these properties for selecting, or producing the most desirable cokes for a given application. A fundamental understanding of the relationships between feedstock
constitution and the structure and composition of petroleum
cokes, and those between coke properties and coke structure
is critically important for controlling the coking processes
and subsequent thermal treatment operations to manufacture carbon materials with the desired properties.
needle coke, respectively. Manufacturing processes, properties, and applications of these four carbon materials will be
reviewed briefly with reference to their respective precursors
as discussed before in this chapter.
Carbon Blacks
Classification,
Manufacturing
and
Applications
Processes,
Carbon black is defined as "an industrially manufactured colloidal carbon material in the form of spheres and of their
fused aggregates with sizes below 1 /u-m" [61]. They are produced by gas phase thermal decomposition of hydrocarbons
using various feedstocks and processes [90-93]. Of the five
major processes, Lampblack Process, The Cheinnel Process,
Acetylene Process, Thermal Process, and Oil Furnace Process, the last one is the most widely used process to produce
most of the carbon blacks available today [90]. These processes yield products t h a t are identified by the process
names, such as lamp black, channel black, acetylene black,
themiEj black, and furnace black. Each carbon black has a
unique structure and a set of properties that are determined
by the different manufacturing processes. Except for the
Channel (or Impingement) and Acetylene processes that convert natural gas and acetylene to carbon blacks, respectively,
a r o m a t i c oils are used as principal feedstocks for carbon
black production. Most commonly used oils are residual fuel
oils, or FCC decant oils. Carbon black oils, a distillate fraction of coal tar produced in by-product coke ovens, are also
used as feedstocks in some processes. Thermal Black and
Furnace Black processes that use aromatic oils as feedstocks
are described below, along with the major applications of
carbon blacks manufactured by these processes.
Thermal blacks are produced by thermal decomposition of
oils in the absence of air using a cyclic process that consists
of heating and production cycles that rotate in a pair of furnaces (generators) in 2.5 min intervals [90]. The furnaces are
lined with open checker brickwork that is preheated before
the introduction of oil feed. Production of carbon black takes
place in a heated furnace followed by a steam purge to remove the products (carbon black and byproducts including
hydrogen gas). The products are sprayed with water for cooling and passed through a collection filter to separate the carbon black particles. Following the steam purge, air is passed
through the furnace to bum-off the carbon black remaining
in the furnace (supplemented by burning oil, if necessary) to
produce heat for the next production cycle. Pairs of furnaces
are used for continuous operation using S3rnchronous heating and production cycles in separate furnaces.
Thermal blacks consist of larger particles (250 to 500 n m
average particle diameter) with lower degree of aggregation
compared to other types of carbon black. They are used in applications that require very high volume fractions of fillers,
including the production of r u b b e r a n d cross-linked
polyethylene, as well as some specialty pol5rmers [90].
As opposed to intermittent production in the Thermal Black
process, carbon black is produced continuously from highly
aromatic oils in a combustion gas environment at high temperatures in a Furnace Process [90]. Production of furnace
black takes place in a fraction of a second when the feed is injected into a flame that is established in the reactor with oil or
779
780
MANUAL
HANDBOOK
of Carbon
Blacks
Four fundamental properties of carbon blacks that are important for industrial applications are particle size, structure
(aggregate size and shape), porosity, and surface activity.
These fundamental properties determine, to varying extents,
a n u m b e r of functional properties, such as surface area, tint
strength, and oil absorption, which are measured by well-established ASTM m e t h o d s to characterize carbon blacks.
Table 17 lists ASTM methods used for characterization of
carbon blacks.
The particle d i a m e t e r (fineness) is the most i m p o r t a n t
property of carbon blacks that relates to the level of elastomer reinforcement and color. Both the level of elastomer
reinforcement and the degree of blackness increases with the
decreasing particle size. The measurement of carbon particle
size is very difficult and highly dependent on the measurement technique used. The most dependable method involves
direct m e a s u r e m e n t of particle sizes a n d aggregate sizes
using standard transmission electron microscopy (TEM) procedures (ASTM D 3849). Surface area measurements are also
used (ASTM D 6556, D 3765, and D 1510) as indications of average particle size. All these surface area measurements are
also affected by the pore size distribution, and in some instances, by surface properties of the particles. The results obtained by a commonly used standard method (ASTM D 1765)
adopted in 1965 for characterization of rubber grade carbons
are often inconsistent with those obtained by TEM procedures (ASTM D 3849). Because of difficulties in replicating
particle size measurements even using ASTM D 3849 in different laboratories, particle size ranges reported by ASTM D
1765 have been abandoned in the ASTM designation of carbon blacks since 1996. Average nitrogen surface areas are re-
Particle Size
Structure
Measured Property
ASTM
Method
N2 surface area
CTAB adsorption
Iodine number
Particle and
aggregate sizes
Particle size range,
N2 surface area
D4820
D3765
D1510
D3849
Tint strength
Dibutylphthalate
(DBTA) absorption
Sulfur content
Extractable
organics
Ash
D3265
D2414
Sieve residue
D1765
D1619
D4527
D1506
D1514
Remarks
Tensile
Modulus, GPa
Tensile
Strength, GPa
Density,
g/cm^
159
379
724
724
241
517
724
1.38
1.72
2.24
2.24
2.83
3.10
3.31
1.90
2.00
2.15
2.15
2.10
2.16
2.17
231
172
231
290
345
3.24
2.24
3.64
3.25
2.21
1.79
1.80
1.78
1.83
781
increase upon pyrolysis/polymerization reactions with the attendant formation of mesophase (see Formation of Coke Microtexture in Coking Process). Strictly controlled heating is
necessary to control the kinetics of mesophase formation to
produce a mesophase pitch that is suitable for melt spinning
process. A complete conversion of isotropic pitch to
mesophase is necessary, but the resulting mesophase pitch
must have a sufficiently low melting point and low viscosity
to allow melt spinning. This becomes a challenge for treating
pitches with a complex composition containing a wide distribution of molecular constituents with different reactivities
towards mesophase formation. A pre-fractionation of such
pitches may be necessary to obtain a more homogenous mixture of molecular species with comparable propensities for
mesophase formation [96]. These pretreatment processes increase the cost of producing mesophase pitches suitable for
carbon fiber production. Mesophase pitches produced from
single compounds such as acenaphthylene, naphthalene, or
methylnaphthalene by thermal, or catalytic procesess
[97-99] are ideal, but expensive precursors to anisotropic
carbon fibers.
Continuous c a r b o n fibers are p r o d u c e d in a three-step
process: spinning, stabilization (oxidation), and carbonization. To produce anisotropic carbon fibers using a melt-spin
process, powdered mesophase is heated above its melting
point and forced through a spinneret and wound onto a rotating reel. The m i c r o d o m a i n s of mesophase are aligned
along the fiber axis as the melt passes through the spinneret.
The fibers are drawn to approximately 10-/xm diameter from
100 /Am diameter at the exit of the spinneret, producing a
fiber with a high degree of molecular orientation. The spun
fibers need to be stabilized by oxidation to prevent melting
and loss of structure during carbonization. For stabilization,
fibers are oxidized at temperatures below their melting point,
typically at 275-325C, depending on the composition and dia m e t e r of the fibers [100]. The stabilized fibers are carbonized to increase their carbon content by heating to
1000-1600C in an inert atmosphere. Carbonized fibers can
be subjected to graphitization heat t r e a t m e n t to produce
graphitic fibers.
Mesophase carbon fibers have high modulus (>520 Gpa),
high thermal and electric conductivity, and low thermal expansion coefficients. These properties cannot be achieved by
PAN-based isotropic carbon fibers. In addition to being a precursor to mesophase carbon fibers, petroleum pitch is also
used to produce a carbonaceous matrix in C-C composites
with PAN fibers and as impregnating pitch for densification
of C-C composites [100,101].
782
MANUAL
HANDBOOK
tion/baking stage. The "green" Soderberg anode paste is carbonized/baked by the heat generated by the electrolysis cell,
whereas the prebaked anode, as the n a m e suggests, is carbonized and baked in a separate furnace to produce the finished anode.
Manufacture of prebaked anode involves three stages:
green paste production
paste compaction
anode baking
For grain paste production, grains of anode grade calcined
sponge coke (55-65%) is mixed with butts (material from
used anodes) a n d coke fines (15-30%) and coal-tar pitch
binder (14-17%). The mixing is carried out at a temperature
50-60C higher than the melting point of the binder pitch to
ensure a sufficiently low viscosity of the binder to flow into
pores and voids of the aggregates. Particle size distribution of
the aggregates plays an i m p o r t a n t role in controlling the
properties and the performance of the anode.
Paste compaction, i.e., forming of the green paste into anode blocks, is achieved either by hot pressing, or vibratory
compacting. Vibratory compacting is a preferred process for
large anode blocks heavier than 700 kg [27].
The final stage of anode production is carbonization/baking
to convert the thermoplastic binder pitch into coke by heat
treatment. In this stage both expansion and shrinkage take
place, respectively, during carbonization of the pitch binder
at temperatures between 200 and 600C, and upon subsequent
heating to temperatures of 100-1250C over several weeks.
Cores (usually 2-inch diameter) taken from commercial
anodes are tested for some or all of the following properties:
green apparent density, baked apparent density, conversion
of pitch to coke, volume change during baking, electrical resistivity, carbon dioxide/air reactivity, consumption during
electrolysis, thermal expansion, thermal conductivity, compressive and flexural strength. Young's modulus, gas permeability, porosity, microstructure, and cracking resistance.
Among these properties, baked apparent density and electrical resistivity are the primary characterization parameters
that correlate well with many of the other variables. ASTM
Section D2.5E is developing standard methods for testing
laboratory anodes and cores taken from commercial anodes.
The following methods are in development: sampling, electrical resistivity, C02/air reactivity, thermal conductivity, cind
thermal expansion.
Graphite E l e c t r o d e s for Electric-Arc F u r n a c e s
High-performance graphite electrodes are required for electric-arc steel production because of extremely high temperatures, u p to 4000C, and large temperature gradients involved
in the process [102]. The function of the graphite electrodes
in electric-arc furnaces is to provide high electrical current
density to produce an arc between two- or three-electrodes to
generate sufficient heat to melt the furnace charge of scrap
iron and steel. In contrast to the use of carbon anodes in the
aluminum industry, carbon consumption is not necessary in
the operation, but is unavoidable under the extreme conditions present in the furnace. As in carbon anode production,
graphite electrodes for the steel industry are manufactured
from a green mix of petroleum coke filler and coal-tar pitch
binder. There are, however, substantial differences in preparation of the green mix and subsequent processing steps com-
CHAPTER 29: PROPERTIES OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS 783
Conclusions
A glimpse of the fascinating diversity and versatility in structure and properties of different materials made up, essentially, of a single element, carbon, should be apparent in the
four examples discussed in this section: carbon black, carbon
fibers, carbon anodes, and graphite electrodes. Carbon
blacks, particulate aggregates of carbon produced by vapor
phase decomposition of aromatic oils, provides elastomer reinforcement and color pigments used in many industrial operations. Pitch-based carbon fibers offer very high modulus
and impressive strengths that find applications in the manufacture of Carbon-Carbon composites. Carbon Carbon
anodes are used for electrochemical reduction of cJuminum
oxide to produce metallic aluminum. Graphite electrodes,
with their excellent thermal properties along with high electrical conductivity, high strength, and low chemical reactivity, find applications in electric-arc furnaces for recycling
scrap iron and steel.
These materials are manufactured from petroleum- and
coal-based feedstocks in well-established processes under
carefully controlled conditions. Although the detailed mechanisms of how the feedstocks are converted into the final
products are not well known, critical properties of these carbon materials are effectively controlled by the right selection
of feedstocks and the operating conditions. Many established
standard methods are used for the characterization of feedstocks and the finaJ products, and several ASTM standard
methods are currently under development.
D 70
D 71
D 86
D 92
D 93
D 95
D 97
D 129
D 130
D 167
D 189
D 240
D 287
D 346
CONCLUSION
Covering a vast area of petroleum-derived products ranging
from fuel oils, highly aromatic feedstocks from catalytic and
thermal cracking, petroleum pitch, and petroleum coke to industrial carbons and graphites, within the bounds of one
chapter presents a great intellectual challenge. The coverage
in this chapter has been necessarily limited to highlighting
the interconnectivity between the end products in this wide
array of materials in reference to production processes,
property characterization using standard methods, and the
significance of measured properties in relation to specific industrial applications. It is important to recognize that despite
the great diversity in the nature and applications of the materials covered in this chapter, there are common threads
that constitute the complex web of converting petroleum
feedstocks to fuels and materials. A careful use of standard
methods for classification of materieJs and quantification of
important properties has contributed to the technology of
converting petroleum feedstocks into desired fuels, hydrocarbons, and carbon materials, as discussed in this chapter
and others.
D 396
D 445
D 446
D 473
D 482
D 524
D 1266
D 1298
D 1510
D1552
D 1756
ASTM STANDARDS
D 1765
No.
D 36
D 1796
D 61
Title
Standard Test Method for Softening Point of Bitumen (Ring-and-Ball Apparatus)
Standard Test Method for Softening Point of
Pitches (Cube-in-Water Method)
D2318
784
MANUAL
D2319
D 2320
D 2414
D 2415
D 2416
D 2492
D 2569
D 2622
D 2638
D 2764
D 2962
D 3104
D 3177
D 3245
D 3279
D 3338
D 3461
D 3765
D 3849
D 3997
D 4045
D 4057
D 4072
D 4239
D 4292
D 4294
D 4296
D 4312
D4421
D 4422
HANDBOOK
D 4529
D 4530
D 4616
D 4715
D 4740
D 4746
D 4809
D 4892
D 5003
D 5004
D 5061
D 5056
D 5018
D 5600
D 5341
D 5187
D 6374
D 6376
D 6556
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Doped Graphitizable Carbons of Increasing Heat Treatment
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[88] Marsh, H. and Kuo, K, Introduction
to Carbon Science, H.
Marsh, Ed., Butterworths, London, 1989, p. 108.
[89] Gregg, S. J. and Tyson, R. F. S., "The Kinetics of Oxidation of
Carbon and Graphite by Oxygen at 500-600," Carbon, Vol. 3,
1965, p. 39.
[90] Taylor, R., Ch. 4, Introduction to Carbon Technologies, H. Marsh,
E. A. Heintz, and F. Rodriguez-Reinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain, 1997.
[91] Donnet, J. B., Bansal, R. C , and Wang, M.-J., Carbon Black Science and Technology, Second Edition, Marcel Dekker, NY, 1993.
[92] Schwob, Y., "Acetylene Black: Manufacture, Properties, and
Applications," Chemistry and Physics of Carbon, P. L. Walker
and P. A. Thrower, Eds., 1982, p. 109.
[93] Donnet, J. B. and Bansal, R. C , Carbon Fibers, Marcel Dekker,
NY, 1984.
[94] Murdie, N., Ch. 14, Introduction
to Carbon
Technologies,
H. Marsh, E. A. Heintz, and F. Rodriguez-Reinoso, Eds., Universidad de Alicante, Secretariado de Publicaciones, Spain,
1997.
[95] Johnson, D. J., Introduction to Carbon Science, H. Marsh, Ed.,
Butterworths, London, 1989, p. 197.
[96] Edie, D. D. and Diefendorf, R. J., Ch. 2, Carbon-Carbon Materials and Composites, NASA 1254, Park Ridge, NJ, 1992.
[97] Singer, L. S., "The Mesophase a n d High Modulus Carbon
Fibers from Pitch," Carbon, Vol. 16, 1978, pp. 409-415.
[98] Yoon, S.-H., Korai, Y., Mochida, I, and Kato, I., "The Flow
Properties of Mesophase Pitches Derived from Methylnapthalene and Napthalene in the Temperature-Range of Their Spinning," Carbon, Vol. 32, 1994, pp. 273-280.
[99] Mochida, I., Yoon, S.-H., Korai, Y., Kanno, K., Sakai, Y., and
Komatsu, M., 'Carbon-Fibers from Aromatic-Hydrocarbons,"
Chemtech, Vol. 25, No. 2, 1995, p p . 29-36.
[100] Cranmer, J. H., Plotzken, I. G., Peebles, L. H., and Uhlmann, D.
R., "Carbon Mesophase-Substrate Interactions," Carbon, Vol.
21, 1983, pp. 201-207.
[101] Meyer, R. A. and Gyetvay, S. R., Petroleum Derived Carbons,
ACS Symposium Series No. 303, J. D. Bacha, J. W. Newman,
and J. L. White, Eds., American Chemical Society, Washington, D.C., 1986, pp. 380-394.
[102] Vohler, O., von Sturm, F., and Wege, E., Vlhnann's Encyclopedia of Industrial Chemistry, A5, VCH, Heidelberg, 1986, p . 98.
[103] Heinz, E. A., "The Characterization of Petroleum Coke," Carbon, Vol. 34, 1996, p. 699.
MNL37-EB/Jun. 2003
787
Copyright'
2003 by A S I M International
www.astm.org
Alkenes
AROMATICS
VEGETABLE OIL
)c-0CHj
.R
R=
HCOC
R.
X-0CH,
ESTERS
CH20C^
O
O
II
II
RO C ~ ( C H 2 ) n C O R
R=C5TOCio
CH3CH2CCH2OC ^
O
CH2OC //
R=C8 TO Ci3
Polyol Ester
Allylic
Benzylic-
AJIylic
I I
H
C'
Aflylic
I l"x/H
/\
H
- Allylic
Y"-
Allylic
I
H
BenzylicAriylic
Secondary
Tertiary
LJ
'
/\
H H
tt
'*"
\
/
HjCCH,
Primary
H,
HjC
CH,
H2
"2 H H2
-2 HI, H2
. . 2 HI, Hj H CH3H2 A_
HsC" I CH3
H
t t
Tertiary
'
Tertiary
irtiarv
tt
Secondary
I
I
Tertiary
789
INITIATION
activation
RH + O2 + RH
*-
R- + H'
(1)
R- + H2O + R'
(2)
PROPAGATION
(3)
R' + O,
-^
RO,' + RH
ROOH + R'
(4)
(5)
(6)
Various Products
(7)
Nonradical Products
(8)
Decomposition of Peroxide:
ROOH
2 ROOH
RO- + ROOH
ROz'
ROOH
+
+
+
+
ROOH
ROOH
ROOH
ROOH
Free Radicals
(9)
ROH + YO
(10)
Inactive Prodcts + Z
(11)
Free Radicals
(12)
TERMINATION
Self Termination:
ROa' + RO2-
Inactive Products
(13)
Chain-Breaking Termination:
ROz + IH
ROOH + r
(14)
RO- + IH
ROH + |-
(15)
RH + |-
(16)
R-
+ IH
RH = Organic substrate
ROOH = Hydroperoxide
stage, oxygen reacts with the fuel and the lubricant to form
alkyl radicals (Eqs 1 and 2; Fig. 3). During the propagation
stage, these radicals react with oxygen and the lubricant to
form peroxy radicals and hydroperoxides (Eqs 3 and 4). As
indicated by the oxygen uptake in Fig. 4 [2], hydroperoxides
are accumulated during the induction period, after which
the autoacceleration of oxidation occurs. Hydroperoxides,
either thermally or in the presence of metal, decompose to
a variety of additional radicals and oxygen-containing
compounds (Eqs 5-12, Fig. 3). The oxygen-containing compounds include alcohols, aldehydes, ketones, and carboxylic
acids. The detailed mechanism of thermal decomposition of
790
HANDBOOK
J ^
"1
OH
"^
=^
OH
HO
/
HO
R2
.^
Ri
O x y g e n a t e d Polymer
HO
R2
-*-
N2 + O2
2NO2
Induction Period
F I G . 4 E f f e c t of h y d r o p e r o x i d e c o n c e n t r a t i o n o n t h e rate of
4 - ^
HN03 +
H,0
s + o.
Time
2 NO
--
SO2
-1^
2N02
(22)
HN02
(23)
S03
(24)
(25)
12S04
H,0
oxidation.
F I G . 7 F o r m a t i o n of a c i d s .
R0-0
H-O-O-R
(17)
6 R C O O H + 2 Fe
2 (RCOO)3Fe + 3 H2
(26)
4 R C O O H + 2 Cu
*-
2 ( R C 0 0 ) 2 C u + 2 H2
(27)
2 ( R C 0 0 ) 2 P b + 2 H2
(28)
R,.
CHOO-
/^
4 R C O O H + 2 Pb
F I G . 8 F o r m a t i o n of metal c a r b o x y l a t e s .
C=0
,CHOH +
O2
(18)
Carbonyl
Compound
RiCH2\
c=o
Carbonyl
Compound
-fe
3
u
Hydrocarbon Containing
500 ppm Iron Octanoate
2 6
X
o
u
u s
Q.
O
X
O 3-
Rl-Cs
(19)
OH
Aldehyde
Carboxylic Acid
Polymeric Materials
(20)
/ Pure Hydroarfeop
<1
/L
RCHO
c
3 2
'
_t>
cr-
10
Time (days)
RCOOH + Metal
--
Metal Salts
F I G . 5 M e c h a n i s m of h y d r o p e r o x i d e d e c o m p o s i t i o n .
(21)
F I G . 9 C a t a l y t i c e f f e c t of Iron c a r b o x y l a t e o n t h e rate of
oxidation.
CHAPTER
Oil thickening occurs mainly due to polymerization or association of certain oxidation products. A model showing oxidative and thermal degradation of lubricants is shown in
Fig. 11 [2].
During the t e r m i n a t i o n stage, t h e radicals either selft e r m i n a t e or t e r m i n a t e by reacting with oxidation inhibitors (Eqs 13-16, Fig. 3). The m e c h a n i s m involving
self-termination leading to the formation of harmful carbonyl
compounds is shown in Eq 18 of Figs 5. Oxidation inhibitors
circumvent the radical chain mechanism of the oxidation process (Eqs 9-11 and 14-16, Fig. 3). Oxidation inhibitors can be
Sulfur
F u e L ^ H2SO4
(29)
(30)
R,C=0
-*-
Resins
(31)
*"
Sludge
(32)
- Deposits
(33)
30: OXIDATION
OF LUBRICANTS
AND FUELS
791
classified as hydroperoxide decomposers and radical scavengers, depending upon the mode of their controlling action.
Sulfur and phosphorus-containing inhibitors, such as sulfides, dithiocarbamates, phosphites, and dithiophosphates,
structures shown in Fig. 12, act as hydroperoxide decomposers. Nitrogen and oxygen-containing inhibitors, such as
arylamines and phenols, structures shown in Fig. 13, act as
radical scavengers. Hydroperoxide decomposers convert
chain-propagating hydroperoxides to alcohols while they
themselves become oxidized to higher oxidation levels. Sulfur compounds, represented by alkylsulfides, react with hydroperoxides and are converted into sulfoxides or sulfones.
Sulfoxides can decompose thermally to form other sulfurcontaining products, such as sulfonic and sulfuric acids,
which themselves are hydroperoxide decomposers. Nonhindered phenols also act as hydroperoxide decomposers and, in
the process, are converted to polyhydroxy compounds [1].
See Parts 1 and 2 of Fig. 14 for the mechanism.
Phosphorus compounds also act as hydroperoxide decomposers. Phosphines, rarely used as inhibitors because of their
toxicity, are not as effective as other phosphorus derivatives.
This is because they react stoichiometrically with hydroperoxides to form phosphine oxides that lack further oxidationinhibiting ability. Alkyl phosphites are better because during
HANDBOOK
Sulfides
R-S-(s)-S-R
R-S-R
Monosulfide
R = Olefin or fatty
ester derived
Polysulfide
DIthlocarbamates
R.
-N-C,
R = Alkyl
Zn
CH,
S
-12
Ashless Dithiocarbamate
Zinc Dithiocarbamate
RO^ /^S
R0-.
RO
R0"%
R = Alkyl
Zn
N-Phenyl-1 -naphthylamine
(PANA)
Diall^yldiphenyiamine
2,6-DI-f-butyl-4-niethylphenol
(BHT)
Arylamines
FIG. 13Radical scavengers.
hydroperoxide decomposition they are converted into phosphates, which continue inhibiting oxidation by forming
acidic materials via thermal decomposition [3]. The hydroperoxide decomposing mechanism by phosphorus additives is shown in Part 3 of Fig. 14.
Dithiophosphoric acid derivatives are the most potent of
the phosphorus compounds, primarily because they can
inhibit oxidation both by hydroperoxide decomposition and
by radical scavenging [7]. They decompose hydroperoxides
catalytically as well as by reacting with them to form compounds that are peroxide decomposers in their own right [3].
Initially, dithiophosphoric acid derivatives are converted into
dialkyl dithiophosphoryl disulfide, which is the key intermediate in the oxidation-inhibiting process. The disulfide oxidizes to thiosulfenate, followed by the sulfur-sulfur bond
cleavage to form sulfenyl and dithiophosphoryl radicals.
These radicals react with hydroperoxides and other radiccJs
II
3R0H
RiSR2
II
Dialkyl Sulfide
Dialkyl Sulfone
Dialkyl Sulfoxide
O
II
RlSR2
-*~
-^
H2SO4
Dialkyl Sulfoxide
2. Phenols
ROOH
ROH
3. Phosphorus C o m p o u n d s
ROOH
(Ri)3P
ROH
Trialkylphosphlne
ROOH
(RiO)3P
(R0)2P\
{Ri)3P0
Trialkylphosphlne
Oxide
ROH
(RiOJaPO
H3PO4
TrialkyI
phosphate
TrialkyI
phosphite
RC-OOH +
793
1. Sulfur C o m p o u n d s
3 ROOM + R 1 S R 2 -
AND FUELS
Zn
ROH
Alcohol
Zinc Dithiophosphate
;c=o
^Ketone
Zinc
Dithiophosphate
Zn
(RO)2P^
+ 2R00-
{R0)2P\
/P(0R)2
SS
Zinc Dithiophosphate
(RO)2P\
I!
o
/P(0R)2
Thiosulfenate
\
S-
2 ROOH
//
//o
^SH
II
Thiosulfonic Acid
Thiosulfenyl Radical
/o
{ R 0 ) 2 P C ^ + SO2
"^QQ"*.
On
S03(H2S04)
Oxidation-inhibiting
Species
RO-
ROH +
^1
Arylamine
~^
ROO- +
t^;
Diphenylamino Radical
ROOH
^
R-i
R2
Arylamine
ROOH or ROO-
?
^
f^
ROH
Nitroxy Radical
^J
Resonance Stabilized/
Delocalized Radical
OH
I
N
OR
I
N
R-
P-elimination
or liydrolysis
i^
Ri
ROH + Olefin
FIG. 16Oxidation inhibition by hindered phenols.
CHAPTER
30: OXIDATION
OH
RO-
OF LUBRICANTS
AND FUELS
795
O-
f-Bu r T ^ t-Bii
II
I
ROH +
2,6-Di-t-butyl-4methylphenol
CHj-
CH2
Quinone Methide
Benzylic Radical
HO
t-Bu
t-Bu
t-Bu
OH
t-Bu
Cn^^n2
Diphenoxyethane
FIG. 17Oxidation inhibition by arylamine.
Fe"^** + ROOH
++
Fe +
+
H + ROO
Hydroperoxide
Fe
ROOH -
Peroxy Radical
+++
Fe + OH
+ RO'
Alkoxy Radical
plexes with the metal ions and taking t h e m out of the chain
reaction. These additives have a synergistic effect with oxidation inhibitor types discussed above. Ethylenediaminetetraacetic acid derivatives, N-ScJicyhdene-ethylamine, and N,
N-disahcyhdene-1, 2-propanediamine represent the most
popular members of this class. However, their use is limited
to fuels. Other derivatives, which are used in this application, include lecithin, derivatives of heterocycles, such as
thiadiazole, imidazole, and pyrazole, and citric and gluconic
acid derivatives [10]. Figure 19 shows the structures of
some of these materials.
Copper ions promote oxidation just like other transition
metal ions. They do this by forming radicals both directly and
by delivering molecular oxygen in a more reactive state. In addition, they catalyze hydroperoxide decomposition to free radicals. Copper ions also exhibit excellent oxidation-inhibiting
ability [11]. They remove radicals by converting them into
ions, which do not have the ability to take part in the oxidation
process. Oxidation promoting and the oxidation inhibiting reactions by copper ions are presented in Fig. 20. Their oxidation-inhibiting activity is concentration dependent. They act
as inhibitors when used at low levels, i.e. at 250 p p m or below,
above which they become oxidation promoters.
In some instances, compounds that intercept oxidation by
different m e c h a n i s m s reflect synergism w h e n present together. Synergism is an effect greater than the additive effect
of the two or more compounds [12,13]. A combination of a
sulfur compound with an arylamine or a hindered phenol is
a c o m m o n way to benefit from this phenomenon.
Oxidation inhibitors are used in almost all lubricants, with
gasoline and diesel engine oils, and with automatic transmission fluids, which account for 60% of the total use. High
operating temperature and high air exposure applications
require a high level of oxidation protection. Zinc dialkyl
dithiophosphates are the primary inhibitor type, followed by
aromatic amines, sulfurized olefins, and phenols. This order
is based on effectiveness, cost considerations, and supplemental benefits.
A n u m b e r of tests are used to assess a lubricant's oxidation
stability u n d e r conditions of accelerated oxidation. A
reasonably comprehensive list of such tests is provided at the
conclusion of the chapter. Some of the tests are described in
detail in the following section.
^CHzCOOH
CH=N-C,H=
H3C.
^ N
CH2COOH
^CHjCOOH
OH
CH2COOH
N-Salicylidene'ethylamine
Ethylenediaminetetraacetic Acid
N,N-DrsalJcyfidene-1,2propanediamine
CH,C-OH
H2C-O-C-R
HO-C-
R=C16-18
Hc-o-c;
OH
CH,C-OH
HoC-O
COOH
I
H-C-OH
HO-C-H
H-C-OH
op
II
P\
+
1^ OCH2CH2N(CH3)3
Citric Acid
HS
Lecithin
Gluconic Acid
SH
A //
N-N
Dlmercaptotliiadiazole
H-C-OH
I
CH2OH
H
N
,N
N
N
Imidazole
Pyrazole
Benzotriazole
^ Cu* + R + H *
*- Cu**(02)- + RH
-*- Cu* + R 0 2 + H *
-*- Cu** + R O + O H -
Purpose of Testing
Cu**+RO+OH-
RO2+CU**
R*+02+Cu*
RO" + Cu**
CHAPTER
Petroleum; DIN: Deutsches Institute for N o r m u r s ; ISO:
International Standards Organization, and other organizations. These tests are designed to evaluate performance of
additives and lubricant systems including industrial lubricants, greases, gear oils, engine oils, and fuels. Outlines of
these various methods and procedures follow.
Antiwear
Hydraulic,
Oils
30: OXIDATION
OF LUBRICANTS
AND FUELS
797
Rere fined
Group I
Group II
Group III
Synthetic
2000+"
2,000+"
2500+"
8000+ "
6000+"
12 000+"
10 000+
12 000+
10 0 0 0 + "
15 000+ "
I I
tOWM^K SftMMe M l
oun&ricM ciu
M * M Cki
798
MANUAL
HANDBOOK
The test apparatus consists of a pressurized vessel axially
rotating at 100 rpm, at an angle of 30 from the horizontal, in
a bath maintained at 150C (302F). Fifty grams of test oil, 5
g of distilled water, and a freshly polished copper coil are
placed into a glass liner, and inserted into the vessel. The
vessel is initieJly pressurized to 90 psi (600 kPa) at room temperature. The 150C bath temperature causes the pressure in
the vessel to increase to approximately 200 psi (1400 k Pa). As
oxidation occurs, the pressure drops, and the usual failure
point is taken at 25 psi (175 k Pa) from the maximum pressure obtained at 150C. The results are reported as the number of minutes to 25 psi (175 k Pa) loss.
AWH
R&O
100 max.
200 max.
100 max.
D 4310: Determination of the Sludging and Corrosion Tendencies of Inhibited Mineral OilsThis method is a modified
alternate to the ASTM D 943 test method, and is used to
determine the tendencies of inhibited mineral oils, especially
turbine oils, to form sludge during oxidation (see Table 2),
The test conditions described under ASTM D 943 are used.
After 1000 h, the test is stopped. The oil and water layers are
separated and filtered. The weight of insoluble material is determined gravimetrically by filtration of the contents of the
oxidation test tube through a 5 micron pore size filter. The
a m o u n t of copper in the oil, water, and sludge phases is also
determined according to any suitable method, such as atomic
absorption (AA), direct current plasma (DCP), inductively
coupled plasma (ICP), or x-ray fluorescence (XRF). It should
be noted that there is n o requirement for the amount of iron
present.
This method is used primarily for specification purposes. It
is widely accepted that the presence of sludge and insoluble
material is due to oxidation. Formation of oil insolubles or
metal corrosion products during this test may indicate that
oil will form insolubles or corrode metals, or both, during
field service. However, correlation with field service has not
been established.
D 2272: Oxidation Stability of Steam Turbine Oils by Rotating
Pressure Vessel (formerly Rotary Bomb)The Rotaiy Pressure
Vessel Oxidation Test (RPVOT) is a rapid method of comparing the oxidation life of lubricants in similar formulations, in
the presence of water and a copper catalyst. This method can
be used to evaluate the oxidation characteristics of turbine
oils, hydraulic oils, and transformer oils.
System
IP-280: Determination of Oxidation Stability of Inhibited Mineral Turbine OilsThis method comes u n d e r the jurisdiction
of the Institute of Petroleum (IP) and is commonly used for
E u r o p e a n specifications relating to turbine oils and other
hydraulic fluids. This method is technically identical to the
CIGRE method "Turbine Oil Oxidation Stability Test."
The test apparatus consists of a suitable size test tube containing 30 g of test oil, plus copper naphthenate and iron
n a p h t h e n a t e as soluble catalysts. The sample test tube is
placed in a heated bath, 120C for 164 h. During the test period, oxygen is bubbled through the oil sample at a rate of 1.0
1/h. Both the test temperature and the oxygen flow rate must
be carefully m a i n t a i n e d t h r o u g h o u t the test period. The
volatile acids are trapped in a tube containing distilled water
and alkali blue solution. At the conclusion of the test period
the oxidized oil sample is filtered and the sludge is determined. The water in the absorption tube is titrated with alcoholic potassium hydroxide (KOH) to determine the volatile
AND FUELS
799
C.
-624 JOIMT
;S5-2fr5 Qg WAUI-2-W
4<-5<OgWAL(.0-7-M
-OIL SAMPLE
r-J
WSTiaEO WATER
+ INDICATOR
m^
100-200
OXIDATION TUBE
ABSORPTION TUBE
acids. The oxidized oil is mixed with heptane, and this solution is titrated with alcoholic KOH to determine the soluble
acids. The volatile acids, soluble acids, and the sludge are
used to calculate the "Total Oxidation Products" (TOP).
Because of the relatively short test time, this method is
sometimes used as a replacement for the longer running
ASTM D 943. However, no correlation between this test and
the D 943 exists. Formation of acids and oxidation products
during this test may indicate that the oil will form sludges
and acids that might corrode metals during field service
(Figs. 25 and 26).
IP-306: Determination of Oxidation Stability of Straight Mineral OilsThis method is designed to give an indication of
the oxidation stability of straight, unadditized, mineral oil
based lubricants under specific conditions.
This test method employs the same apparatus and a similar procedure to those used in IP-280. IP-306 differs from the
IP-280 procedure in (a) the time test time is reduced to 48 h,
(b) two conditions, namely no catalyst and solid copper catalyst, are used and (c) the degree of oxidation is expressed as
"total oxidation products" (TOP) percent.
IP-307: Determination of Oxidation Stability of Mineral Insulating OilsThis method is designed to give an indication
of the oxidation stability of insulating oils under specific
conditions. Insulating oils are nonelectric conducting oils
used in various electrical applications, for example, electric
transformers.
This test method employs the same apparatus and a similar procedure to those used in IP-280. IP-307 differs from the
IP-280 procedure in (a) the test temperature is reduced to
100C (212F), (b) a solid copper catalyst is used, and (c) the
degree of oxidation is expressed as sludge and acidity.
D 2070: Standard Test Method for Thermal Stability of Hydraulic OilsAt elevated temperatures, the long hydrocarbon chains in mineral oils may break apart into shorter
800
MANUAL
HANDBOOK
Acceptable
Unacceptable
Unacceptable
Acceptable
(0.2Acm)
AND FUELS
801
DRILL 2 HOLES
j ^ WAMETER
(0.16cin)
MAGNESIUM
STEEL
ALUMINUM
CADMIUM
COPPER
FIG. 29ASTM D 4636, Oxidation of Hydraulic Fluids. Metal
square dimensions and arrangement.
HANDBOOK
CSimensions in m m
Vent lube
Insert
NS 29/32
conical ground
joint
a$ specified
in DIM 122^2
Part I
Ageing vessel
Gear Oils
D 2893: Oxidation Characteristics of Extreme Pressure Lubricating OilsThis test was developed to measure the high
temperature oxidation stability of industrial gear oils. It is
important to note that D 2893 was designed to run at 95C.
However, to meet the requirements of U.S. Steel requirement, #224, and AGMA 9005 (American Gear Manufactures
Association), the temperature is elevated to 121C (250F).
The other test conditions remain unchanged.
The test method is designed to measure resistance to oxidation by determining the change in viscosity.
In this test, the same glassware required by the D 943 T.O.
Oxidation test is used. Three hundred milliliters of the test lubricant is measured into the tube. The glass inlet tube from D
943 is used to introduce the air into the test lubricant. The entire assembly is placed in an oil bath at 95C, (121C for the
USX S-200 procedure (U.S. Steel)). Dry air is bubbled
through the sample at 10 1/h for a period of 312 h. At the end
of the test the final viscosity and precipitation number are determined. The appearance of the test tube and oil may be inspected for evidence of oxidation.
Qualifying industrial gear oils give 0-6% viscosity increase
in test. Though unspecified, cleanliness of the glassware is
very important for today's industrial gear oils. It is felt that
glassware cleanliness is an indication of the lubricant's thermal stability (see Figs. 33 and 34).
D 5763: Oxidation and Thermal Stability Characteristics of
Gear Oils Using Universal GlasswareThis test method is a
modification of D 2893. Of significant value is the determination of sludge in this method, which is not done in D 2893.
This method can be used to evaluate both extreme pressure
and nonextreme pressure gear oils.
This test method is run using universal glassware apparatus. A 100 g sample of gear oil is weighed into the test tube.
The test assembly is placed in a heated bath at 120C for 312
h. Dry air is bubbled through the sample at a rate of 3 1/h. At
the end of the test period the apparatus is cooled to room
temperature and reweighed to determine any oil loss. The
Ring mark
at 4 0 ml
*25,S--o.s
FIG. 32DIN 51352, Pneurop Oxidation. Test apparatus for determining the aging characteristics of
lubricating oils.
AND FUELS
803
Thermometer
Flowmeter
Measures Air
Liters per Hour
Air Inlet
KJ
Thermally
Stable Oil
i fi
Borderline
Thermally
Stable Oil
Non-Thermally
Stable Oil
Mineral
Mineral
Mineral
Mineral
o
o
o
O O C#
o o o o
Minimum
Standard
Premium
Top Tier
Psi loss
@ 100 hours
Additive
B
C
10.0
Additive
Additive
D
No
Additive
1.8
1.9
14.2
0.6
Aluminum
Complex
Calcium
Complex
Lithium
Lithium
Complex
Psi loss
@ 100 h o u r s
14.2
2.6
1.4
3.6
s i SOX
160C
170C
Equivalent
A more severe
thanB
Only B is
evaluated
Current Type
E x : R L 181
High Temperature
Resistant Gear Box
OilEx:RL 184
Equivalent
B more severe
than A
Equivalent
Equivalent
Test Apparatus
Duration, h
Temperature, (C)
Oil Volume (1)
Air Flow, (1/h)
Agitation
Metal Catalysts
Air/Oil Volume Ratio
Steel Case
50
163
0.12
1.1
Gears at 1725 min~*
Iron and Copper
458
Viscosity A%
A AN
Insolubles
Carbon/Varnish
Sludge
Blotter Test
100% max
CEC
L-48-08 (DKA)
Glass Tube
192
160
0.1
5.0
Air
None
9600
Evaluation Criteria
< 2 cSt.
<2.0 cSt. mg KOH/gm
2% max.
7.5 large gear
9.4
100% (no sludge)
ISOT
JIS-K2514
Glass Beaker
96
135
0.25
None
Impeller at 1300 m i n . " '
Iron and Copper
IT-1
Fluids
DKA Oxidation
Test (192 h, 170C)
AN Increase
% Viscosity
Increase at 40C
% Viscosity
Increase at 100C
Tube Rating
Blotter Spot Rating
Industrial
Traction
Fluid
Commercial
Automotive
Traction
Fluid 1
PAT-2
PAT-3
PAT-4
Commercial
Automotive
Traction
Fluid 2
Prototype
Automotive
Traction
Fluid 1
Prototype
Automotive
Traction
Fluid 2
Prototype
Automotive
Traction
Fluid 3
Prototype
Automotive
Traction
Fluid 4
4.0
10.5
1.1
7.2
7.6
53.4
0.9
10.6
1.3
13.7
0.7
8.8
0.2
5.0
4.7
3.4
26.2
5.9
4.8
0.2
1.3
light
100
light
100
light
100
light
100
light
100
light
100
heavy
48.5
04.2.1
04.2.2
04.2.3
04.2.5
04.2.10
Special Erlenmeyer
Oil bath
Flowmeter enabling to control 101/h + 0.5 1/h
Clean and dry air supply
Silicone hosepipe
\\\\\\\\v\\\\A\\\\\\\\\^:\T
FIG. 37CEC L-48-08, Gear Oil Oxidation. Sample storage container.
HANDBOOK
Afe^^'^
^ ^ . . : i ^ ^
te:iJ
Aspects
Aspect 2
Aspect 1
Several factors, including type and quantity of the oxidation inhibitor, influence the performance of a grease in this
test. Most grease specifications require no more than a 5 psi
loss after 100 h, or 10 psi after 500 h (see Figs. 41 and 42).
D 5483: Oxidation Induction Time of Lubricating Greases by
Pressure Differential Scanning Calorimetry (PDSC)This
method covers the determination of oxidation induction time
of lubricating greases subjected to oxygen at 500 psig (3.45
mPa) and temperatures between 155C (SITF) and 210C
(410F). Oxidation Induction Time (OIT) is the period of time
from the first exposure to an oxidizing atmosphere until the
extrapolated onset time.
A small quantity of grease is weighed into a sample pan and
placed in a test cell. The cell is heated to a specified temperature and then pressurized with oxygen. The cell is held at a
regulated temperature and pressure until an exothermic reaction occurs. The extrapolated onset time is measured and
Dimensions in mm
Air inlet tube
DIN 1 2 2 4 2 - V 2 9 / 3 2
conical ground joint
DIIM 1 2 2 1 5 - D 1 1 adapter
DIN 1 2 2 1 5 - D T I adapter
FIG. 40CEC L-48-08 Gear Oil Oxidation. Assembled apparatus for Part B.
-DIN 1 2 2 4 2 - V 2 9 / 3 2
conical ground joint
Lead Gasket
0 = diameter
Oxygen Atmosphere
s
Supplier
0'i
FIG. 39CEC L-48-08 Gear Oil Oxidation. Dimensions of glassware for Part B.
Grease
Sample
Oxygen Bomb
Oil Bath
210F-rF
FIG. 41ASTM D 942, Grease Vessel Oxidation. Oxygen
vessel apparatus.
807
Oils
Thermal Analyzer
PDSC
Cell
rc^
0
4>*\A I 8 B
Flowmeter
mm
0000000 i
00000001
ill
ooooooo j
>-/
'fgJMvDSC
Oxygen
Cylinder
FIG. 43aASTM D 5483, Grease Oxidation by PDSC. Test
unit.
200
180
120
80
40
Sample: Grease A
Size: 2.00 mg
Temperature: 210C
Oxygen Flow: 100 mUminutes
Induction Time: 42.4 minutes
EXO
ENDO
42.4
-40
209.8C
-80 J
0.0 4.0 8.0 12.0 16.0 20.0 24.0 28.0 32.0 38.0 40.0 44.0
Time (min)
FIG. 43bASTM D 5483, Grease Oxidation by PDSC. Onset
temperature.
808
HANDBOOK
tdclfontc pick up
Inboard 8arlng
LM&704e Cone
LM&7CI0 Cup
OulboTd Baannq-
LM11949 Cone
LMII9I0 Cup
CHAPTER
is under consideration within an ASTM technical committee,
but has not received all of the approvals required to become
an ASTM standard.
Savant Laboratories originally developed this test in the
1980s. In 1989, Savant, with cooperation of the Chrysler Corporation, developed a procedure that correlated with turbocharger deposits. The e q u i p m e n t b e c a m e k n o w n as the
Chrysler/Tannas TEOST apparatus.
This test method describes the general oxidation and depositforming characteristics of engine oils at moderately high temperatures (MHT) of 285C, using the TEOST apparatus.
Using a TEOST test apparatus, a 10-gram sample of the engine oil containing an organo-metallic catalyst (lead, iron,
manganese, tin and copper naphthenates) is forced to flow
past a tarred, wire-wound depositor rod held in a glass mantled casing. The rod is resistively heated to obtain a constant
30: OXIDATION
OF LUBRICANTS
Drive Unit
FIG. 45ASTM D 4742, Thin Film Oxygen Uptake Test (TFOUT). Test apparatus.
To Pressure
Recorder
Ctosure
0.64 cm
^'-^"^ ti
Sample Container
O-Ring Seal
TFE Cover
Sample Container
Aluminum Insert
7.46 cm
6.03 cm Diameter
Aluminum Insert
809
Bomb Stem
AND FUELS
FIG. 46ASTIM D 4742, Thin Film Oxygen Uptal<e Test (TFOUT). Assembled
vessel, aluminum insert, and glass sample container.
810
MANUAL
HANDBOOK
Orig cSt
at 40C
Final cSt
at 40"'C
% Vis increase
39.6
56.2
41.9
33.3
63.1
89.5
46.5
79.6
71.2
39.3
40.7
3.5
33.4
38.7
15.8
46.1
46.8
1.5
41.5
42.0
1.2
FIG. 47Thermal Oxidation Engine Oil Simulation Test (TEOST). Chrysler/Tannas apparatus.
Gas
Outlet
ControIUnj
Tharmocaupla L
N,0-
Vdve
ThrTnocoupls
P0I-I11.S<S
(a)
FIG. 48a) Thermal Oxidation Engine Oil Simulation Test (TEOST). Configuration of TEOST
layout for Test Protocol #33; b) Depositor rod ratings.
Eight test cells are used concurrently and the test is a representation of insoluble development in 10-minute intervals;
i.e., 40, 50, 60, 70, 80, 90, 100, and 110 min. If the induction
time is not reached in the first test series, a second series
stcirting at 80 min and continuing u p to 150 min is conducted. The air blowing is continued for a one-minute mini m u m after completion of the test period. The test coupon
is rinsed in tetrahydrofuran (THF) and the total weight gain
of coupon plus the weight of the THF insolubles is converted to a percentage of the initial sample weight versus
the test time and are plotted to determine the sample induction time.
The results of the CMOT have been correlated to piston
deposit levels measured on Caterpilleir oil evaluation tests.
Engine oils having an induction time less than 90 min have
generally produced excessive levels of piston deposits in laboratory test engines and in actual field operations.
The CMOT is only one part of the oil selection criteria. A
high.CMOT induction time does not assure adequate oil performance in the 3600 series diesel engine. Caterpillar will
only recognize CMOT results from tests performed at certified laboratories. Presently only Caterpillar offers this service^ (see Figs. 51a and b and 52a and b)
BT-10: International Harvester Oxidation
CorrosionInternational Harvester developed this m e t h o d during the early
and
Fuels
TEOST MHT4-GF3
NEW
'
.'
VERY GOOD
PASS
BORDERLINE PASS
FAIL
TEOST D6335-GF2
NEW
VERY GOOD
PASS
BORDERLINE PASS
lUK^l
FAIL
(b)
FIG. 16(Continued)
CHAPTER
30: OXIDATION
OF LUBRICANTS
AND FUELS
813
33 R e f e r e n c e O i l
T E O S T 33
W t/M g
-TotalDeposits
80 -
60
40
20
CRO-l
m
CRO-2
CRO-3
CRO-4
hn
o
^ ^
^^
^^
N O IR O N
WITH
IRON
Races and
Bearing
Set Screw
Shaft
Bearing
Pump Housing
Teflon
Gasl<et
Cu and Pb
Plates
beakers are cooled a n d reweighed to determine the unwashed gum, for aviation gasohne and aircraft turbine fuel.
For motor gasolines, the residue is washed with n-heptane.
The heptane washed residue is reported as existent g u m
content.
The gums contained in gasolines and fuels can be harmful,
causing sticking of the intake valves, and plug carburetor jets.
It may interfere with the action of moving parts and, in general, obstruct the flow of fuel through the lines and p u m p .
Existent gum is related to the quantity of gum already present in gasoline and fuel (see Fig. 53).
Marinite Board
Insulation
Cover Plate
Test Block
Fiber Frax
Loose Insulatiai
Case
1-5/32" Dia
Hole Typical
2" Dia Hole
Marinite Board
Insulation
(a)
(b)
FIG. 51a) Caterpillar Micro-Oxidation Test (CiVIOT). Test apparatus side view of cover plate, b) Blotter spots showing acceptable versus unacceptable sludge deposits.
Inlet Tube
Inlet/Outlet Cap
27 cm
Outlet Tube
4 mm ID
24/40 Ground Glass Joint
Glass Vessel
(a)
(b)
FIG. 52a) CMOT glass test vessel; b) Test coupon.
814
CHAPTER
30: OXIDATION
OF LUBRICANTS
AND FUELS
815
Removoble
Adopter
if-in, 0.0.
816
HANDBOOK
^mn
II
Hi
sential data derived are the amount of deposits on the aJuminum heater tube and the rate of plugging of a 17-micron
nominal porosity precision filter located just downstream of
the heater tube.
The test results are indicative of fuel performance during
gas turbine operation and can be used to assess the level of
deposits that form when liquid fuel contacts a heated surface.
The test is rejected if the amount of spent fluid pumped
during the test is less than 405 mL. The final result from this
test method is a tube color rating based on an arbitrary scale,
established for the method, plus two additional yes/no crite-
CHAPTER
COVER
PORCeUMN OR OLASS
-Z BUSTS OR
DEPRESSIONS
SAMPLE
30: OXIDATION
OF LUBRICANTS
AND FUELS
817
Because the storage periods are long (4-24 weeks), the test
method is not suitable for quality control testing, b u t does
provide a tool for research on storage properties of fuels, ft
should be noted that the results obtained by this test are not
necessarily the same as those obtained during storage in a
specific storage situation (see Figs. 58 and 59).
D 6468: High Temperature Stability of Distillate FuelsThis
test method covers relative stability of middle distillate fuels
CONTAINER
OLASS
CLASS CONDENSER
MM O.D.
FILTER
FUNNEL
MEMBRANE
FILTER
SUPPORT
818
HANDBOOK
GLASS S T O P P E R
tive relationship exists between the pad rating and the gravametric mass of filterable insolubles.
Lubricants
500 ML S E P A R A T C
FUNMEL
*4 PORCELAIN CRUCIBLE
OOOCH HOLDER
TO VACUUM
500 M L P V R E X
SUCTION FLASK
under high temperature aging conditions with limited air exposure. A summary of the method is as follows:
Two 50-mL volumes of filtered middle distillate fuel are
aged for 90 or 180 min at 150C in open glass tubes with air
exposure. After aging and cooling, the fuel samples are filtered through a Whatman No. 1 filter. The average amount of
filterable insolubles is estimated by measuring the light reflectance of the filter pads. The 100 and 0% extremes of the
reflectance rating range are defined by an unused filter pad
and a commercial black standard, respectively.
This test method provides an indication of thermal
oxidative stability of distillate fuels when heated to high temperatures that simulate those that may occur in some types of
recirculating engine or burner fuel delivery systems. Results
have not been substantially correlated to engine or burner
operation. The test method can be useful for investigation of
operational problems related to fuel thermal stability.
When this method is used to monitor manufacture or storage of fuels, changes in filter rating values can indicate a
relative change in inherent stability.
The test method uses a filter paper with a nominal porosity of 11 microns, which will not capture all of the sediment
formed during aging, but allows differentiation over a broad
range. Reflectance ratings eire also affected by the color of filterable insolubles, which may not correlate to the mass of the
material filtered from the aged fuel. Therefore, no quantita-
D 6186: Oxidation Induction Time of Lubricating Oik by Pressure Differential Scanning Calorimetry (PDSC)This method
covers the determination of oxidation induction time of
lubricating oils subjected to oxygen at 3.5 MPa (500 psig) and
temperatures between 130C and 210C (265^10F). Oxidation Induction Time (OIT) is the period of time from the first
exposure to an oxidizing atmosphere until the extrapolated
on-set time. A summary of the test procedure follows:
A small quantity of oil is weighted into a sample pan and
placed into a test cell. The cell is heated to a specified temperature and at a regulated temperature and pressure until
an exothermic reaction occurs. The extrapolated on-set time
is measured and reported as the oxidation induction time for
the lubricating oil at the specified test temperature.
Oxidation Induction Time (OIT) may be used as an indication of oxidation stability. This test method is faster than other
oil oxidation tests and requires a very small amount of sample. This method may be used for research and development,
as a quality control, and for specification purposes. However,
no correlation has been established between the results of this
method and actual service performance.
Panel Coker TestThe Panel Coker Test is a method for determining the relative stability of lubricants in contact with
hot metal surfaces.
The test apparatus consists of a rectangular stainless steel
reservoir, inclined 25 from horizontal. The reservoir is fitted
with a machined steel piece fitting integrally into the top of
the reservoir, and framing a 95 mm by 45 mm aluminum
panel. The test panel is held in place by a heating element,
which is fitted with thermocouple probes to control the
temperature of the aluminum test panel. A horizontal shaft,
BOROSILICATE GLASS BEND
FIG. 59ASTM D 4625, Distillate Fuel Storage Stability at 43C (110F). Sample storage
container.
CHAPTER
fitted with a series of tines, is positioned above tlie oil and is
rotated at 1000 rpm. During rotating of tlie shaft, the tines
sweep through the test lubricant and lubricant droplets are
thrown onto the heated aluminum test panel. A summary of
the procedure follows:
The apparatus is assembled forming a closed system and
the test panel is heated to the specified test temperature, usually 260-325C. The shaft is rotated at 1000 r p m and the test
lubricant is splashed onto the heated, weighted test panel.
The splashing heating cycle is continued for normally 2-6 h,
from the time the splasher is started. Some other variables in
the p r o c e d u r e w o u l d b e the i n t r o d u c t i o n of air, a n d the
splash/bake cycle. At the end of the specified time period, the
heat is removed, the splasher is stopped, and the test panel is
allowed to cool. The test panel is reweighed and the a m o u n t
of deposit is determined.
Weight gain of the aluminum test panel and the amount of
test lubricant consumed during the test are an indication of
the lubricant's performance under high temperature conditions. Examples of accepted performance are as follows:
Gear Oils: leaded type give deposits in the range of
700-1000 mg, in contrast to sulfur/phosphorus t5T3es which
give 150-220 mg.
S/P Lub*
174 mg Wt Cain
30: OXIDATION
OF LUBRICANTS
AND FUELS
819
820
HANDBOOK
used for sjTithetic materials and highly refined petroleum fluids if desired. Circulation of the sample from the sump to the
heated surface and back to the pump is accomplished by
means of a peristaltic pump. After the prescribed test period,
normally 5 h, the steel test specimen is removed from the
apparatus and evaluated. The masses of deposits remaining
after washing with pentane, after washing with chloroform,
and after wiping with a tissue, are reported. An optional procedure provides a method for the determination of the tendency of sample vapors to form deposits on heated surfaces.
A second test specimen is placed in the vapor space over a
thin flowing film of the liquid in the constant temperature
chamber. After circulation of the test liquid, the deposits on
the test specimen exposed to the liquid and vapor phases, cire
measured as above.
The test method shall measure the deposit formation tendencies of liquid petroleum products on heated steel surfaces, in air, at 101.3 kPa (10 atm) pressure. Other surfaces
and other atmospheric media may be substituted for steel
and air at 1 atm, provided the substitution is noted in the test
report.
RULER (Remaining Useful Life Evaluation Rig)This
method is not an ASTM standard. It is under evaluation
within an ASTM technical committee, but it has not received
the approvals required to become an ASTM standard.
The RULER was originally designed for use by the U.S. Air
Force to determine the remaining useful life of lubricants.
The remaining useful life of a lubricant is the length of time
from the original lubricant sampling, until large changes in
the lubricant's physico-chemical properties occur. This test
can be performed with any lubricant containing at least one
antioxidant species. The test is conducted as follows:
The test vial (electrolytic cell) is prepared by mixing an oil
sample with a solvent and a solid substrate. The solvent separates the antioxidant from the oil as the vial is shaken. When
C/)
Q.
the substrate settles to the bottom of the vial, the oil and
other debris common to used oil adheres to the substrate
particles.
An electrode is inserted into the vial and a controlled voltage ramp is applied to the electrode inserted into the diluted
oil sample. As the voltage potential increases, the antioxidants become more chemically active, causing the increasing
oxidation current to reach a peak, and then decrease as voltage potential continues to increase.
Through time-series testing, the remaining useful life of a
lubricant can be tracked from test to test, enabling the user
to identify "normal" trends for a given lubricant. Variations
from this trend can be indicative of changes in operating conditions causing accelerated oxidation. Determinations can be
made to predict when rapid changes in the lubricant are
likely to occur and decisions can be made regarding oil
changes of additive reinforcement.
This method can be used to determine the remaining useful life of automotive engine oils, diesel oils, hydraulic fluids,
turbine engine lubricants, transmission fluids, and greases
(See Figs. 61 and 62).
Biodegradable
Lubricants
Compound "B"
Phenyl - a - naphylamine
E
CO
CD
o
Voltage increases with time
FIG. 61RULER test. Oxidation curve for the RULER test.
CHAPTER
30: OXIDATION
OF LUBRICANTS
AND FUELS
821
Hours: 25
Sample ID: GO 1
Sample Date: 5/06/98
Standard:
60&
/Sample
/Additive
10
11 12 13 14 15 16
17
Seconds (V lUlode)
Ruler Numbers
Standard: 552
Sample: 441
RUL: 80%
Ruler Areas
Standard: 7451
Sample: 6294
RUL: 84%
Additive RULs
#1:85%
#2: 77%
pie reaches a peroxide value of 100 milliequivalents. The peroxide value is determined by method AOCS official method
Cd 8-53.
The length of this period of time is assumed to be an index of resistance to rancidity. The exact relationship
between peroxide value and such queJities as shelf-life, actual rancidity, and oxidative stability has not been firmly
established.
AOCS Official Method Cd 126-92: Oil Stability Index (OSI)
This method measures the oxidation resistance of oils and
fats. Initially the oxidation proceeds slowly until the oxidation resistance is overcome, at which point the oxidation
rate accelerates a n d becomes very rapid. The length of
time before this rapid oxidation occurs is commonly referred to as the "induction period." The test is conducted as
follows:
A sample of oil or fat is heated at the specified test temperature, and a stream of purified air is bubbled through the
sample at a rate of 2.5 mL/s. The effluent air from the sample
is then bubbled through a test tube containing 50 mL of
deionized water. The conductivity of the water is continually
monitored. The effluent air contains volatile organic acids
that increase the conductivity of the water as the oxidation
proceeds. The conductivity of the water is monitored by computer or strip chart recorder. The Oil Stability Index (OSI) is
defined as the point of m a x i m u m change of the rate of
oxidation. The test time is normally a m i n i m u m of 4 h or a
maximum of 15 h. The OSI may be r u n at temperatures of
100, 110, 120, 130, and 140C.
Fluids
ABOT Test
(300 h, 155C)
(requirement*)
TAN Increase
(3.5 mix)
IR Carbonyl
Increase (30 max)
% Viscosity Increase
at 40C
(25 max)
% Pentane Insolubles
Increase
(0.35 max)
IT-1
CAT-1
CAT-2
PAT-1
PAT-2
Industrial
Traction
Fluid
Commercial
Automotive
Traction
Fluid 1
Commercial
Automotive
Traction
Fluid 2
Prototype
Automotive
Traction
Fluid 1
Prototype
Automotive
Traction
Fluid 2
0.50
0.9
20
14.4
9.2
0.20
1.4
0.6
13
7.5
13
22
16.4
13.1
0.09
4C, flaking
Copper Strip
2.4
3B
Prototype
Automotive
Traction
Fluid 4
1.2
2.4
12
8.7
0.07
3A
3B
3B
PAT-4
PAT-3
Prototype
Automotive
Traction
Fluid 3
3B
35
19.7
1.73
3B
are for biodegradable fluids and require less than a 20% increase in viscosity to be considered acceptable.
Table 8 represents the relative oxidative stability of various
biodegradable fluids as measured by their change in viscosity before and after being subjected to the Baader test (see
Fig. 63).
<P5T
TEST METHODS
Hydraulics, R & O, and Turbine Oils
D943
Olive DIN
12215-08
D4310
D2272
Ground taper
NS 45127
in accordance
witfi DIN 12242
IP-280
IP-306
IP-307
D2070
D4636
D5846
D6514
DIN 51352
Gear Oils
D2893
D5763
D5704
nS-K2514
L-48-08
D3527
Engine Oils
D4742
D6335
BT-10
General Lubricants
D6186
D3711
VW1302 Test
VW Diesel intercooler test
VW DI engine test
Peugeot XUDl lATE and XUDUBTE
M-B OM 364A and M-B OM 441LA
MAN 5305 tests
IP
131
40
138
142
157
DIN
51780
51575
51808
51587
ISO
6246
4263
388
51586
280
306
307
51352
51554
15380
Biodegradable Lubricants
AOCS Cd 12-57
AOCS Cd 12b-92
DIN 51554
The following listing of engine tests is included for reference only and outlines of these methods are not included in
this chapter.
REFERENCES
[1] Ingold, K. U., "Inhibition of Autoxidation of Organic Substances
in Liquid Phase," Chemical Reviews, Vol. 61, 1961, pp. 563-589.
[2] Rasberger, M., "Oxidative Degradation and Stabilization of
Mineral Oil Based Lubricants," Ch. 4, Chemistry and Technology
of Lubricants, R. M. Mortier and S. T. Orszulik, Eds., VCH Publishers, Inc., NY, 1992, pp. 83-123.
[3] Rizvi, S. 0. A., "Lubricant Additives and Their Functions," ASM
Handbook, Friction, Lubrication and Wear Technology, Vol. 18,
1992, pp. 98-112.
[4] Abou El Naga, H. H. and Salem, A. E. M., "Effect of Worn Metals on the Oxidation of Lubricating Oils," Wear, Vol. 96, 1984,
pp. 267-283.
[5] Lachowicz, D. R. and Kreuz, K. L., "Peroxynitrates. The Unstable Products of Olefin Nitration with Dinitrogen Tetroxide in the
Presence of Oxygen. A New Route to a-Nitroketones," Journal of
Organic Chemistry, Vol. 32, 1967, pp. 3885-3888.
[6] Kreuz, K. L., "Gasoline Engine Chemistry as Applied to Lubricant Problems," Lubrication, Vol. 55,1969, pp. 53-64. (b) Kreuz,
BIBLIOGRAPHY
[1] Aspects of Lubricant Oxidation, ASTM STP 916, Stadmiller and
Smith, Eds., ASTM International, West Conshohocken, PA,
1986.
[2] Significance of Tests for Petroleum Products, ASTM STP 7C (now
ASTM Manual 1), Boldt and Hall, Eds., ASTM International,
West Conshohocken, PA, 1934.
[3] American Society of Metals (ASM) Handbook, Volume 18,
P. J. Blau, Volume Chairman, American Society of Metals, Materials Park, OH, 1992.
[4] Lubrication Engineers Manual, Association of Iron and Steel Engineers (AISE), Pittsburgh, PA, 1996.
MNL37-EB/Jun. 2003
Corrosion
Maureen E. Hunter^ and Robert F. Baker^
BACKGROUND
Corrosion becomes a problem when the appearance or functionality of metal is impaired. To some extent, corrosion is inevitable and may not be prevented, only delayed or retarded.
Chemical "inhibitors" are added to fuels and lubricants to
protect metal surfaces. The metcJs requiring protection are
typically iron and its alloys (steel) and copper and its alloys
(primarily brass and bronze). Other metals, including aluminum, lead, tin, zinc and cadmium, come in contact with
fuels and lubricants and are subject to veirious forms of corrosion, but most fuel and lubricant testing focuses on the corrosion of copper and the oxidative corrosion of iron, commonly called "rust."
of
Rust
(3)
(4)
(5)
(6)
(2)
Copyright'
(1)
www.astm.org
826
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
External Circuit
Surface
MX+
N
MX+
MX+
_ electron
flow
Cathode
Anode
H,0
H,o
Cathodic Site
Cathodic Site
0,
^o
^
X
0
o
OH
HjO
Fe++
electrons
Fe
Fe/
^
Fe++
Fe++
Fe
Fe Fe
Activity
Inhibitors
electrons
<
Anodic Site
Iron oxide layer is porous and non-passivating
FIG. 2Mechanism of rust formation.
that once a corrosion cell has been established, the formation
of rust is maintained without the further addition of water.
Only oxygen is required for rust to propagate.
The rusting of iron and steel is destructive to engines, machinery, equipment, and containers contacting fuels and lubricants. Additionally, in a lubricated system, ferrous ions
are recognized to have a catalytic pro-oxidant effect on the
degradation of the lubricant [2], so the rust inhibitor also assists in prolonging the life of a lubricant by the inhibition of
oxidation.
Copper
of Corrosion
HjO
O,
O,
O,
Corrosion
Carboxylic Acid
-CO2-H+
-CO2R
Carboxylate
-CO2M+
Sulfonate
-SO3-M+
Imidazoline
Amine
,N ->__/
-NH2
HS^S
SH
\\ //
HS^^S
SSR
\\ //
N-N
N-N
Dimercaptothiadiazole
(DMTD)
DMTD Derivative
827
CORROSION TESTS
The test methods and practices most commonly used to measure performance and/or specify the requirements for lubriCcints to resist rust emd corrosion will be covered in this section. The significemce of each test will be discussed and a brief
summary of the test procedure will be given. The rust and corrosion methods and procedures eire outlined in Tables 1 and 2.
Generally the procedures fall into four categories: fuels, automotive lubricants (including engine and gear oils), industrial (non-automotive) lubricants, and greases. Greases are
separated because they have unique tests and they do not distinguish between automotive and non-automotive applications. The ability to resist rust and corrosion is an important
lubricant characteristic; however, fuels are generally not
evaluated for anti-rust. In some fuel specifications, copper
corrosion testing is required.
Fuels and Lubricants
H,C
H,C
Tolyitriazoie
Tolyitriazoie
Derivative
TABLE 1Corrosion specifications and test methods for fuels and lubricants.
ASTM
D 130
Common Name
Copper Strip Corrosion
Fuels
D910
Description
Copper corrosion test widely
used for fuels and lubricants
Related Procedures"
DIN 51 759
IP 154
D975
Automotive Engine OUs
D4485
D5844
Sequence IID
D6557
Gear Oils
CRC L-33 Gear Oil
Corrosion Test
Industrial Fluid Lubricants
FTMS791B(M5326.1)
B 117
DIN 50 021
D665
Spindle Test
D 1748
Humidity Cabinet
D2070
D3603
D4310
Cincinnati Milacron
Thermal Stability Test
Horizontal Disk Test
1000 Hours Sludge Test
D4627
D4636
Oxidation-Corrosion Test
' Test procedures may not be identical but evaluate similar characteristics.
DIN 51 585
IP 135
DIN 51 359
IP 366
828
MANUAL
HANDBOOK
D4048
D5969
D6138
Description
Related Procedures"
DIN 51 802
IP 220
Common Name
" Test procedures may not be identical but evaluate similar characteristics.
TABLE 3 --Copper strip
Classification
Appearance
Designation
Color Descripti on
Slight tamish
Moderate tamish
Dark tamish
Corrosion
for
for
classifications.
of
ASTM D 4485 is not a procedure, but the "specification covers engine oils for light-duty and heavy-duty internal com-
CHAPTER
ASTM D 6557, Standard Test Method
of Rust Preventive Characteristics
of
Engine Oils
for
Evaluation
Automotive
Evaluation
The ASTM D 5968 test method is used to determine the tendency of diesel engine lubricants to corrode various metals,
specifically alloys of lead and copper commonly used in cam
followers and bearings. This test method is similar to the
Cummins Bench Corrosion Test and is based on Federal Test
Method Standard 791, Method 5308.
Four clean, polished, pre-weighed metal coupons of copper, lead, tin, and phosphor bronze are tied together and
placed in a test tube containing 100 ml of test oil. The test
tube is heated in a bath to 121C and air is delivered to the
system at a rate of 5 L/h. The test is r u n for 168 h. An industrial reference oil is evaluated with each group of tests to verify test acceptability. Upon completion of the test, the following results are reported:
the raw data of the calibration and the analysis of the reference oil
concentrations of copper, lead and tin in the oil before and
after adjustment based on the internal standard
corrected change in lead concentration
the tarnish rating of the copper coupon
the change in weight of each of the coupons
31: CORROSION
Operating
Gear Oils
CRC L-33, Gear Oil Corrosion
Test
829
830
MANUAL
HANDBOOK
in nature, can contribute to wear, particularly of p u m p s . Additionally, particles of rust in the oil can act as catalysts to increase the rate of oil oxidation.
A polished steel rod (spindle) is suspended in a 400 ml
beaker containing 300 ml of the test oil, which is stirred at
60C. After 30 min, 30 ml of water are added to the oil. It is
customary to run the test for 24 h; however, other times may
be specified. The 10% water addition to the oil can be either
distilled water (Procedure A) or a defined synthetic sea water
(Procedure B). The test is normally r u n in duplicate and any
visible rust on both rods indicates failure. Results are reported as a pass or fail. Because of the greater severity, the
synthetic sea water (Procedure B) is frequently used as a
screening test [salt makes water a better electrolyte and accelerates the corrosion process]. Results should always specify which procedure (A or B) was used a n d the amount of
time the test was run. Figure 7 shows a passing (rust-free)
spindle on the left and a failing spindle on the right.
ASTM D 1748, Standard Test Method
Rust Protection by Metal Preservatives
Humidity
Cabinet
for
in the
for
evaluate the thermal stability of h y d r o c a r b o n based hydraulic oils in the presence of copper a n d steel at 135C.
However, oxidation of the oil may also occur during the test.
Clean, polished, pre-weighed copper a n d steel rods are
placed in a 250 ml beaker, which contains 200 ml of the test
oil. The bcciker is placed in an aluminum block in an oven
for 168 h at a test temperature of 135C. At the completion of
the test, the copper and steel rods are rated visually for discoloration and the oil is analyzed for the quantity of sludge
formation.
ASTM D 3603, Standard Test Method for
Rust-Preventing
Characteristics
of Steam Turbine Oil
in the Presence of Water (Horizontal Disk
Method)
The ASTM D 3603 test method is used to eveJuate the ability
of steam-turbine oils (under full flow and quasi-static conditions) to prevent the rusting of horizontjil and vertical ferrous
surfaces w h e n water becomes mixed with oil. Horizontal
metal surfaces, on which water droplets tend to be retained,
are more prone to corrosion than vertical or sloping surfaces.
This test m e t h o d is therefore more discriminating t h a n
method ASTM D 665 Procedure A, since it gives a separate
evaluation of the oil on a horizontal emd a vertical surface.
A horizontal steel disk and vertical steel cylinder assembly
is placed in a bath of 275 ml of oil, which is stirted at 60C.
After 30 min, 25 ml of distilled water are added to the oil. The
test is r u n for 6 h. The test is r u n in duplicate and any visible
rust on b o t h assemblies indicates failure. Results are reported as a pass or fail.
ASTM D 4310, Standard Test Method for
of the Sludging and Corrosion Tendencies
Inhibited Mineral Oils
Determination
of
CHAPTER
This test utilizes a special piece of glassware known as a n
oxidation cell. A 300 ml sample of the test oil, 60 ml of water,
and a catalyst (a 225 m m braided low carbon steel-copper
coil) are placed in the oxidation cell, which is heated in a bath
to 95C. Oxygen is delivered to the system at a rate of 3 L/h.
The test is run for 1000 h. Upon completion of the test, the
weight of the insoluble material (sludge) that is formed and
the total a m o u n t of copper in the oil, water, a n d sludge
phases is reported.
ASTM D 4627, Standard Test Method for Iron Chip
Corrosion for Water-Dilutable
Metalworking
Fluids
Also known as the Cast Iron Chip Test, the ASTM D 4627 test
method evaluates the ferrous corrosion control characteristics of water-dilutable metalworking fluids. The results obtained by this test are useful in determining the ability of water-diluted metalworking fluids to prevent or minimize rust
under specific conditions. This procedure is typically used
for screening and comparative purposes.
Cast iron chips are placed in a petri dish containing a filter
paper and a water-diluted metalworking fluid. The dish is
covered and allowed to stand for 20-24 h. At the end of the
test period, the filter paper is rinsed with water and the percent of the filter paper area that was stained by the rusting
chips is estimated. The amount of rust stain on the filter paper is an indication of the corrosion control provided by the
fluid. The "breakpoint" is defined as the weakest concentration tested that left no stain on the filter paper.
ASTM D 4636, Standard Test Method for
Corrosiveness
and Oxidation Stability of Hydraulic
Oils, Aircraft Turbine Engine Lubricants,
and Other
Highly Refined Oils
The ASTM D 4636 test method is used to test hydraulic oils,
aircraft turbine engine lubricants, and other highly refined
oils to determine their resistance to oxidation and corrosion
degradation and their tendency to corrode various metaJs.
Petroleum and synthetic fluids may be evaluated using moist
or dry air with or without metal test specimens. (This test
method is basically Federal Test Method 5307.2 expanded to
include Federal Test Method 5308.7.)
This test method consists of a standard test procedure and
two alternative procedures. In the test procedure, a large
glass tube containing the test oil and pre-weighed metal specimens is placed in a constant temperature bath and heated
for a specified n u m b e r of hours while air is passed through
the oil. The different test procedures allow for various oil
sample sizes (200 ml, 165 ml and 100 ml), various bath temperatures (typically 100C to 360C) and different shaped
(washer-shaped and square) specimens of various metals (titanium, magnesium, steel, bronze, silver, aluminum, copper,
cadmium and others).
At desired test times, oil samples are withdrawn from the
test oil and checked for changes in viscosity cind acid number. At the end of the test, the amount of sludge present in the
oil remaining in the tube and the quantity of oil lost (evaporated) during the test are determined. The corrosiveness of
the oil is determined by loss of mass of the metal specimens
and microscopic examination of the metal surfaces. Also, the
presence of liquid or solid material o n the inside of the
condenser and the appearance of deposit on the sample tube
are reported.
31: CORROSION
831
Greases
ASTM D 1743, Standard Test Method for
Determining
Corrosion Preventive Properties of Lubricating
Greases
Since the early 1960s, the most popular grease rust test in the
United States has been ASTM D 1743. This method determines the rust preventive properties of greases using tapered
roller bearings stored under static conditions in the presence
of distilled water.
Tapered roller bearings, as shown in Fig. 9, are packed with
grease and r u n under a light load to distribute the grease
evenly. The bearings are exposed to distilled water and then
stored at 52C and 100% relative humidity for 48 h. After
cleaning, the bearing races are examined for rust. Since 1987,
the ASTM D 1743 procedure has specified a pass or fail rating on the basis of a single corrosion spot of 1.0 m m or larger
in the longest dimension on two of three bearings tested simultaneously.
ASTM D 4048, Standard Test Method for Detection
Copper Corrosion from Lubricating
Grease
of
832
MANUAL
HANDBOOK
Description
No evidence of corrosion
No more than three spots of a size just sufficient to
be visible
Up to 1% surface corrosion
Between 1% and 5% surface corrosion
Between 5% and 10% surface corrosion
More than 10% surface corrosion
REFERENCES
MNL37-EB/Jun. 2003
USE OF MATERIALS Cannot be over emphasized. The flow properties of materials ranging from gasses, such as oxygen, to
hquids, such as water, paints and lubricants, to semi-solid
and solid materials such as asphalt cements, glass, and steel
aire important in both the manufacture and use of these materials. In the manufacturing of materials, flow properties
can affect the manner in which materials are handled and
packaged. For example, p u m p s , mixing equipment, and
packaging equipment must be correctly selected and sized to
handle the material being processed. Likewise, flow properties are important in the use of materials. Paints must be
designed to flow when brushed, but remain on the painted
surface, even when the surface is vertical. Lubricants must
have flow properties allowing them to be distributed to the
required location and then remain to provide appropriate
lubrication. As can be seen from these few examples,
m e a s u r e m e n t and characterization of flow properties are
essential.
There is a long history of the measurement of flow properties of materials. Isaac Newton laid the groundwork for the
m a t h e m a t i c a l t r e a t m e n t of the flow of materials in his
Philosophiae Naturalis Principia Mathematica, 1687, Book 2,
Section IX,
HYPOTHESIS: The resistance arising from the want of
lubricity in the parts of a fluid is, other things being
equal, proportional to the velocity with which the parts
of the fluid are separated from o n e another.
In 1823 Navier stated the general equations for fluids in
motion [1]. Hagen [2] and Poiseuille [3] both studied the viscosity of water flowing in capillaries in the mid 1840s, and
they determined the relationship between the quantity of
flow and the pressure drop, diameter, and length of the capillary tube. In 1890 Couette developed the rotating concentric
cylinder apparatus [4]. In the early 1900s A. Pochettino noted
a n u m b e r of types of apparatus for the measurement of viscosity of semi-solid materials such as asphalts and tars [5].
Bingham and Jackson [6] reviewed viscosity data attributed
to water, and selected a value (1.005 mPa-s at 20C) for the
primary viscosity standard, a value that was unchanged for
nearly 40 years. Ubbelohde [7] and Cannon and Fenske [8]
developed glass capillary viscometers in the mid-1930s,
which were responsible for the adoption and wide use of
kinematic viscosity measurements in the petroleum industry.
833
Copyright'
2003 by A S I M International
www.astm.org
834
MANUAL
HANDBOOK
Viscoelastic Materialsmaterials
that exhibit both elastic
and viscous properties. Under an oscillatory mode of applying the stress to Newtonian liquids, stress a n d the
resulting strain are in p h a s e with each other. For viscoelastic liquids, the stress and strain are out of phase. The
phase angle between stress and strain is a measure of the
elasticity of the liquid. Certain automotive engine oils
contain polymers that cause the oil to be viscoelastic.
Shear Stressthe motivating force per unit area for fluid
flow.
Shear Ratethe velocity gradient in fluid flow.
Newtonian Liquida fluid that exhibits a constant viscosity at all shear rates. If the viscosity is not constant, the
liquid is non-Newtonian.
Simple liquids such as water,
hexane, and refined oils without polymeric additives are
Newtonian.
Fluiditythe reciprocal of viscosity.
Consistencythe resistance of a non-Newtonian material
to deformation or flow. Consistency is not a fundamental
property but is m a d e u p of viscosity, plasticity, and other
rheological phenomena. These are not normally found in
petroleum jargon.
Shear Thinning (pseudoplastic)the
property of a nonNewtonian material exhibiting r e d u c e d viscosity at increasing shear rates. Lubricating Oils with high molecular
weight polymeric additives are t3^ically shear thinning.
Shear Thickening
(dilatancy)the
property of a nonNewtonian material exhibiting increased viscosity at increasing shear rates. Suspended particles emd slurries can
be examples of dilatant materiEils.
Yield Stressthe stress required to initiate flow. For all
Newtonian fluids and some non-Newtonian fluids, yield
stress is zero. Automotive oils when cooled slowly to low
temperature can form a partial, interconnecting wax structure; this structure can cause a yield stress sufficient to
prevent pumping of the oil.
Plastic (Bingham) Bodya liquid having a yield stress, TQ,
to be overcome before flow results, and thereafter the flow
is Newtonian.
riy
(1)
Symbol
SI Units
cgs Units
Shear stress
Shear rate
Viscosity
JCinematic viscosity
Viscosity of Solution
Relative viscosity, % = {riJ^i)
Specific viscosity, (% 1)
Intrinsic viscosity,
[rj] = lim(rjsp/c ), c ^ 0
First normal stress.
Weissenberg effect
T or <T
y
f]
V
rjs
Pa (Pascal)
s~'
Pa-s
m'^/s
Pas
dyn/cm^
s->
P (Poise)
St (Stokes)
P
7)r
%p
[ij]
m^/kg
mL/g
Ni(y)
V = (T-
Kinematic Viscosity:
1 Pa-s
1 mPa-s
1 Pas
1 m^/s
1 mm^/s
1 m^/s
=
=
=
=
=
=
V = Tj/p = r / p y
10 P
IcP
1000 m P a s
lO^'St
IcSt
IC* mm^/s
To)ly
(2)
(3)
Thixotropythat
p r o p e r t y of a material to thin u p o n
isothermal agitation, and to thicken upon subsequent rest.
Some paints are m a d e to be thixotropic, such that the energy needed to b r u s h the paint at high shear is reduced, but
when the brushing is stopped the structure reforms and the
paint stays in place.
(4)
when n = 1
Newtonian liquid
n< 1
Shear thinning liquid
First Normal Stress, Weissenberg EffectThe vector normal
to the direction of the applied shear stress. The first normal
stress is a measure of the elastic component of viscoelastic
materials. This elastic component can cause viscoelastic
materials to "climb" a rotating shaft or push the cone away
from the plate in a cone-plate instrument. Automotive engine oils with some polymeric additive packages can exhibit the Weissenberg Effect. See the Annex to ASTM D 5293
for a discussion of the Weissenberg Effect as related to the
Cold-Cranking Simulator. Note that all referenced ASTM
methods are included in a table at the conclusion of the
chapter.
Shear StrainThe quotient of shear deflection divided by
the thickness of the test piece.
ModulusThe ratio of stress to strain; that property of a
material which, together with the geometry of a specimen,
determines the stiffness of the specimen; may be static or
dynamic, and if dynamic, is mathematically a vector quantity, the phase of which is determined by the phase of the
complex force relative to that of deflection (ASTM D 5992).
Elasticas a modifier of dynamic force, descriptive of that
component of complex force in phase with dynamic deflection, that does not convert mechanical energy to heat,
and that can return energy to an oscillating mass-spring
system; denoted by the single prime (') as a superscript
symbol, as F' (ASTM D 5992).
(5)
drive
mechanism
torque
spring
cone
''.:.",] t e s t sample
plate
FIG. 2Cone-and-plate viscometer.
drive
mechanism
spring
THICKNESS OF
FLUID FILM = h
835
836
MANUAL
HANDBOOK
drive
flow through
capillary
Newtonian Liquid
driving head
piow Patte
Bingham Liquid
mechanism
torque
spring
Falling Ball viscometer
rotor
cup
drive
mecinanism
torque spring
paddle
cup
FIG. 5Paddle type rotational viscometer.
837
Method No.
D88
D445
D 1092
D2162
D2532
D2669
D2983
D3236
D3245
D3829
D4486
D4624
D4683
D4684
D4741
D5018
D5133
D5293
D5481
D5967
D6080
Type of Viscometer/Geometry
short capillary
capillary low shear
capillary high shear
capillary low shear
capillary low shear
rotational coaxial cylinder
rotational coaxial cylinder
rotational coaxial cylinder
rotational coaxial cylinder
rotational coaxial cylinder
capillary low shear
capillary high shear
rotational tapered cylinder
rotational coaxial cylinder
rotational tapered cylinder
rotational coaxial cylinder
rotational tapered cylinder
rotational coaxial cylinder
high shear capillary
capillary low shesir
capillary low shear
Kinematic Viscosity
(6)
g
D
L
H
=
=
=
=
(7)
V = Tj/p = C t
where
(8)
(9)
C = viscometer constant
t = measured flow time between two timing meirks
(10)
(n)
L
V
C
D
E
=
=
=
=
=
Viscometers
Standard
(BS)
Types
Volume
Types
Ostwald
Viscometers
Certain modified Ostwald viscometer designs have the precise volume of charge at test temperature adjusted so as to
have the calibration constant independent of the test temperature. Several of the Modified Ostwald designs have a precise
volume of chcirge (generally at ambient temperature) initially
introduced, with a small temperature correction required if
the test temperature is not the same as that of the initial
charge temperature (Figs. 8-10).
Some liquids are either very reactive to the surrounding atmosphere (they could explode in the presence of oxygen) or
too volatile (at the temperature of test, the pressure is near or
above that of the atmosphere) to be measured in the normeil
kinematic viscometers. Such liquids may be able to be run in
specially designed "tilting" viscometers, in which the test
o
CZ3
i
o
O
i
2
I
CO
B
in
C5
UJ
U.
nil
'I
I
I r
_Ll
I^1
o
u
o
U
839
^T7^
u
!Z!
U
, .
'
I
o
ti
E
o
O
(B
E
0)
00
>
a
0)
o
c
a
(0
3
(A
w
00
i^-Ni
1
^r
;5-^j^^^i_
-I
; ^
y
'
>
- *
*-%
00
Be
Caimon-Fenske Opaque
Zeitftichs Cross-Arm
841
Lantz-Zeitfiichs Reverse-Flow
CONNECTOR
KOVAfl TO
GLASS SEAL
I8ml VOL.
o
o
CAPILLARY
TUBING
e
(O
E
lOmm 0.0.
ARM ROTATED
9 0 * TO REAR
HEAVY WALL
CONSTRUCTION
THROUGHOUT
12mm O.D.
8
4SmfflO.O.
842
MANUAL
HANDBOOK
of water flowing in glass capillaries of 0.013-0.65 m m in diameter and u p to 1 m in length so as to better understand the
flow of blood through h u m a n capillaries [14,15]. The following equation was developed:
Q = k P D^'/L
(12)
where:
Q
L
D
P
k
ZAHN
GARDCO EZ
GARDCO Fisher
=
=
=
=
=
GARDCO FORD
FIG. 12Dip-cup viscometers. Viscosity cup drawings provided by the Paul N. Gardner Company, Inc.
32.5 0.5
LEVEL OF LIQUID
IN BATH-
OVERFLOW
RIM
1.7650.015
(0.0695t 0.0006)
12.25tO.10
(0.48210.004)
IOl
^ 3.0 + 0.2
(0.12t 0.01)
UNIVERSAL TIP
12511.0
(4.92t0.04)
3 MIN
3 MIN. _,;.
. 3 . 1 5 0 0.020
'^.i24otaoooe
I 12.25*0.1 0
r(0.482t0jl
0X)04)
BOTTOM OF BATH
CORK
STOPPER
;^ 4.3+0.2
1(0.17 10,01)
FUROL TIP
I.D. AT GRADUATION
MARK
(13)
Having obtained the values of the constants A and B by calibrating the viscometer with liquids of known viscosity it appears possible to calculate the kinematic viscosity -q/p, but if
absolute viscosities are desired it is necessary to make a supplementary determination of the density p. Thus, elaborate
tables and charts have been devised for converting Engler
"Degrees" (cf. Ubbelohde (1907)), and Redwood (cf. Higgins
(1913), Herschel (1918) o r Saybolt "Seconds") into true
viscosities.
ASTM D 88 - 21 T, Standard Test Method for SayboU Viscosity was originally published in 1921, and it is still cited in
a few specifications, although none for petroleum products.
Glass capillary viscometers appear to have been used little
if at all in ASTM specifications until the late 1930s, when
ASTM D 445 made its appearance in 1937. This delay is probably due to the overwhelming use of the viscometers (in particular the Saybolt viscometer), as described by Bingham.
However, the Saybolt, Engler, and Redwood viscometers all
have a problem in the measurement of kinematic viscosities
less than about 2.0 mm^/s. This problem may not have been
realized in the petroleum industry until the late 1930s. The
problem is illustrated by the Saybolt Universal kinematic viscosity scale at very low kinematic viscosities, where the efflux
time becomes essentially constant regardless of the kinematic viscosity of the liquid. Thus, the Saybolt Universal
scale is limited to a m i n i m u m kinematic viscosity of 32.0 SUS
(about 1.8 mm^/s).
843
high
- shear
Newtonian
A
\ ^ B
F
(n
o
u
Base Stock
3
10
High-Temperature High-Shear
4
10
5
10
1
6
10
1
7
10
1
Rote of shear y
844
HANDBOOK
gap between the rotor and stator in the rotational instruments and in measuring the precise diameter of the capillary in the capillary instrument.
Because of the very close tolerances required to achieve the
very high shear rates in the rotational viscometers, the designs have used a slight, matching taper to allow precise adjustment of the gap between the stator and rotor (Figs. 15 and
16). This adjustment ensures that the proper shear rate will
be maintained during the running of the test.
As described in the test method,
A motor drives a tapered rotor that is closely fitted inside a
matched stator. The rotor exhibits a reactive torque re-
FILTER
SCREEN
w
(
>
^-
PLUG
VALVE
PRESS./EXH,
" CDNNECTDR
ALUMINUM
SHELL
HEATED
-ALUMINUM
CYLINDER
^CAPILLARY
FIXTURE
FiSei- HoWi
FIG. 16Rotor, stator and stator housing of the tapered bearing simulator viscometer.
Viscometer Cell
FIG.
17Capillary
high-temperature highshear viscometer.
CHAPTER
inserted into the test cell and allowed time to reach test temperature. The excess sample is withdrawn, and a controlled
pressure applied to the sample, forcing it through the working capillary. With automatic timing (approximately 10-30
s), the viscosity and shear rate are ceJculated. If necessary, a
second measurement is made with a revised applied pressure
to ensure a shear rate at the wall of the working capillary of
1.4 X 10* s " ^ This apparatus can also be used from 35-175C
[20,21] (see Fig. 17).
For automotive gasoline engines, the m i n i m u m HTHS SAE
specifications at 150C are 2.6 mPa-s (SAE 20 grade), 2.9
mPa-s (SAE 30, OW-40, 5W-40 and lOW-40 grades), and 3.7
mPa-s (SAE 15W-40, 20W-40, 25W-40, 40, 50 and 60 grades)
as of December 1999 [22]. However, as the SAE Fuels and Lubricants Committee continues their studies of the best specifications, the HTHS specifications can be expected to be
continuously u p d a t e d in the future. There is significant
interest for measurements at other temperatures (100-200C)
and shear rates u p to at least 1 X 10^ s~'.
Much research in automotive lubricants also is related to
rheological studies, even though there may not be a n ASTM
test or SAE specification. One example of this research relates to the study of dynamically loaded journal bearings, the
m i n i m u m oil film thickness (MOFT) and the load bearing
capacity of engine oil lubricants. Many engine lubricants are
polymeric solutions, and as such many are also viscoelastic.
The research requires a n u m b e r of rheological studies, such
as the slit die rheometer (Lodge Stressmeter [23]) to study
the first normal stress difference [24], studies of the MOFT
[25,26], and cavitation [27].
(14)
AND SHEAR
STABILITY
845
between
846
HANDBOOK
Oils
REO-174-63
REO-151-61
REO-152-61
REO-153-61
REO-154-61
REO-155-63
REO-156-63
REO-157-63
REO-15 8-61
REO-159-61
REO-160-61
REO-161-63
REO-162-63
REO-171-63
REO-172-63
REO-173-63
REO-175-63
(730)
(1390)
(2340)
(3500)
(8400)
1470
1830
2700
1800
2590
3110
1000
2760
1700
600
890
5040
670
1320
2320
3410
8050
1970
1710
1900
1910
1990
1900
1080
3190
1710
790
730
5850
aiO/lOO-FExtrap.
REO-174-65
REO-151-65
REO-152-65
REO-153-65
REO-155-63
REO-156-63
REO-158-63
REO-159-63
REO-172-65
REO-173-65
REO-183-65
REO-184-65
(3000)
(6320)
(11500)
(19800)
6920
11400
6480
14360
2260
4040
3600
9440
2700
5760
10600
18900
6590
5280
5630
5880
2180
1800
2570
6750
Instrument
Slope
0.817
0.908
0.999
0.979
0.572
0.962
0.881
1.08
0.824
0.923
1.65
0.985
447
-105
-54
-284
442
-86
79
-284
-23
139
-1340
-300
534
138
147
355
1400
153
257
358
381
193
390
582
Corr Coef
0.908
0.994
0.997 (gel-corrected)
0.984 (Uncorrected)
0.705
0.992
0.991
0.983
0.981
0.989
0.984
0.958
CHAPTER
AND SHEAR
STABILITY
847
the SOD viscometer, and the Cannon-Manning Pressure viscometers were ehminated iirom additional consideration, as
the shear rate was too low. The Mason Torsion Crystal and
Texaco High Rate of Shear viscometers were both very complex and of a limited availability. However, all of the data
from laboratory instruments indicated that a higher shear
would correlate better with the engine cranking data.
About the time the above data became available, there was
a progress report on the development of low temperature viscometric techniques by ASTM Section B on Flow Properties
of Non-Newtonian Fluids. The GMR Forced Ball viscometer
consisted of a thermostatted, closed-end cylinder filled with
the test sample. A ball with a heavy weight was forced
through the test sample, and the time of fall automatically
measured (Fig. 18).
Manning reported that the GRM Forced Ball viscometer,
even with the Gel correction, would give inadequate correlation with the engine data [39].
At this same symposium two specially designed instruments showed promise. The reciprocating action of a single
cylinder model airplane engine [40] (later made m u c h more
sophisticated) by Stewart and Spohn gave much promise. At
the same time, a single Couette rotational viscometric cell
AIR BEARINGS
PUTFORM
REUASE CABLE
WEIGHTS
COUNTERWEIGHT
CONTACT SWITCHES
AIR BEARING
OIL CYLINDER
FIG. 1 8 G M R f o r c e d ball viscometer. Reprinted with permission f r o m t h e C a n n o n Instrument C o m p a n y , State College, PA.
ow
5W
low
15W
20W
25W
6200 at - 3 5 C
6600at-30C
7000 at - 2 5 C
7000 at - 2 0 C
9500at-15C
13000 a t - 1 0 C
lapse fast enough into the hole, the p u m p will become "airbound" and not continue to p u m p oil to the bearings of the
engine (Fig. 6).
Moyer [49] reported that ASTM pour points, channel tests
and the 17.8C extrapolated kinematic viscosities were poor
predictors of oil pumpability. Stewart and Smith [50]
and Stewart and Spohn [51] reported that high shear ColdCranking Simulator viscosities, Brookfield viscosities, GM
pour times, and ASTM pour points all failed to predict the oil
gallery pump-up time in their test engine. "One test oil, which
had a pour point of 15F and appeared to be solid at 20F,
p u m p e d satisfactorily in a test engine at 20F." It was quite
evident t h a t a cooperative study of the factors regarding
pumpability of engine oils at low temperatures must be performed, a n d a reliable bench test m u s t be developed for
predicting this low-temperature pumpability. Many benchtest procedures were proposed, including (a) pour point (see
ASTM D 97), vacuum viscometer (along the lines of ASTM D
2171), (c) Brookfield viscometer (see ASTM D 2983), (d) GM
Pour Time, (e) pressure glass capillary viscometer, (f) cylinder with a hole in the bottom, (g) and several specially modified low-temperature, high-shear instruments including the
Cold-Cranking Simulator (see ASTM D 2602), and Haake
Rotovisco viscometers. Engine gallery pump-up times gave
a temperature at which the oil failed to p u m p . The ability of
each of the several bench tests to predict the temperature at
which full scale engines noted pumpability failure served as
the criteria for a successful bench test. As a result of these
works and those of many other investigators, the SAE Fuels
and Lubricants Subcommittee 2 and the ASTM Subcommittee D02.07 on Flow Properties defined pumpability characteristics of reference oils in engines and developed a bench
test method to predict satisfactory pumpability for use in
lubricant specifications.
In 1973, a large cooperative p r o g r a m was initiated by
ASTM subcommittee D02/07, as described by Shaub, Smith
and Murphy [55] by the following:
A joint ASTM/SAE symposium, the first of several, was
held in 1973 to better define the mechanisms of oil pumpability failures. A number of studies [48,50,52,53] were beneficial in this respect and provided a basis for formulating
an ASTM program. The ASTM program established an
engine test procedure and determined the pumpability performance of thirteen Pumpability Reference Oils (PROs) in
seven full-scale engines. This program was begun in 1973,
PUMP OUTtET
'PUMP
AVAILABtE HEAD
J
Olt INLET SCREEN
CHAPTER
completed in 1974, and summarized in an ASTM report
and an SAE Paper in 1975 [33,54]. The engine pumpability program included a degree of complexity that earlier
engine cranking programs did not: in the engine pumpability program, oils were run at successively lower temperatures until the oil actually failed to pump. The data and
mechanisms from the ASTM Engine Oil Pumpability Program have served as a basis to develop bench tests and to
assess their ability to predict engine pumpability.
There were 13 fully formulated engine oils r u n in 7 engines,
according to the prescribed procedures, at successively lower
cold room temperatures until pumping failure occurred. The
temperature at which failure occurred was defined as the
Borderline Pumping Temperature (BPT) and the mechanism
of p u m p i n g failure recordedair binding (AB) or flow
limited (FL). See Table 11 [55].
Note that the several engines show as m u c h as 17C differences in the FL BPT temperatures. Thus the design of the
pumping assembly in the engine as well as the lubricant is
very important.
With the results of the ASTM Pumpability Program as a
guide, a n u m b e r of instruments were evaluated to assess
their ability to predict pumpability. These i n s t r u m e n t s
included the Philippoff Rotary Viscometer (Fig. 21), a vacu u m capillary viscometer, the Haake rotary viscometer, the
Texaco orifice viscometer, the Brookfield rotciry viscometer,
and others.
In order to narrow down the selection relative to possible
round-robin studies, the Pumpability Data Analysis Panel
(acting on a motion passed at the December 1975 ASTM
meeting) visited the sites of the various pumpability test
methods. Based upon the (1) degree of correlation with
pumpability engine data, (2) cost, (3) ease of operation,
and (4) number of samples which could be run at one
time, the Data Analysis Panel recommended (at the June,
1976 ASTM meeting) that two teststhe mini-rotary viscometer (a miniaturized version of the (Phillippoffj rotary
viscometer) and the vacuum pipettebe considered for
round-robin studies. The panel also suggested that other
tests be considered if their sponsors could provide a set of
data showing correlation with the engine data [55].
The bench test resulting from this work was based on a simplified Couette-type rotary viscometer (mini-rotary viscometer or MRV) (Fig. 22).
'/////////////
AIR BEARING
OIL
WEIGHT
STATOR
Total
AB
FL
01
03
05
06
07
08
09
10
11
12
13
15
16
7
4
7
7
4
4
4
7
7
7
7
7
7
3
0
5
0
0
0
3
5
0
0
2
0
0
4
4
2
7
4
4
1
2
7
7
5
7
7
849
Flow Limited
Avg (Min/Max)
Avg (Min/Max)
- 3 5 (-38.5/-30)
- 2 9 (-33.5/-24.5)
-25(-32.5/-17)
-23.5(-33/-15.5)
-28(-31/-24)
-28.5 (-31.5/-24.5)
- 3 7 (-39.5/-35.5)
-24
-28.5 (-30/-27)
- 3 3 (-33.5/-32.5)
- 3 1 (-31.5/-30.5)
-30.5 (-34.5/-25)
-28.5 (-34.5/-23.5)
- 3 1 (-33.5/-29.5)
-33 (-38.5/-24.5)
-23 (-29.8/-15)
-14.5(-22/-12)
-34.5
low
000 m P a s at - 4 0 C
000 mPa-s at - 3 5 C
000 mPa-s at - S C C
000 mPa-s at - 2 5 C
000 m P a s at - 2 0 C
000mPa-sat-15C
15W
20W
25W
" Tlie presence of any yield stress detectable by this method constitutes a
failure regardless of viscosity.
NOTE: Reprinted with permission from SAE J300_19912 1999 SAE International.
Operating
" fluid level
leve
Glass Stator
(Inner dianrefer 22.07 mm)
Rotor
(Length: 65.5 mm;
Diameter 18.42 mm)
Fill line
(marked on Sfator)
SHEAR STABILITY OF
POLYMER-CONTAINING OILS
With the advent of polymer-containing lubricating oils in the
1960s, there was concern that the polymeric additives may
degrade under the influence of the high-shear and high-temp e r a t u r e environment found in a n operating engine. A
n u m b e r of devices, including mechanical shear devices, a
sonic oscillator and nuclear irradiation, were examined as
possible bench-test apparatus. This research resulted in the
development of a sonic oscillator device (Fig. 24) specified in
851
852
MANUAL
HANDBOOK
V) Motor
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(TO)
(11)
(12)
(73)
(14)
Pump
Filter
Nozzle holder
Nozzle
Upper reservoir
Solenoid drain valve
Lower reservoir
Solenoid drain valve
Sample-collection bottle
Pump control rack
Rack adjustment screw
Rack spring
Filling funnel
D 3945, ASTM D 5275, ASTM D 5621) [64]. See Fig. 25. Both
procedures:
. . . evaluate the percent viscosity loss for polymer-containing fluids resulting from polymer degradation in the high
shear nozzle device. Minimum interference from thermal
or oxidative effects are anticipated. . . . This test method is
not intended to predict viscosity loss in field service for different polymer classes or for different field
equipment.
Some correlation for a specific polymer type in specific
field equipment can be possible.
The a p p a r a t u s consists of two fluid reservoirs, a singleplunger diesel fuel injection p u m p with a n electric motor
drive, a pintle-tjqDe fuel injection nozzle and control instrumentation. The shearing severity of the apparatus is verified
by a standard reference oil and measurements of the kinematic viscosity at 100C. Test specifications in Europe also
refer to the Coordination European Council (CEC) standards
(ASTM D 6278) [65-67].
According to test method D 3945:
[T]he polymer-containing fluid is passed through a diesel
injector nozzle at a shear rate that causes the less shear stable molecules to degrade. The resultant
degradation
reduces the kinematic viscosity of the fluid under test.
This loss of kinematic viscosity is a measure of the shear
stability of the fluid. It is important in the use of these
polymer-containing lubricating oils that the viscosity of the
oils remain stable and not decrease as a result of degradation of the polymer, especially in the high shear and high
t e m p e r a t u r e conditions of m o d e r n gasoline and diesel
engines.
CHAPTER
The permanent shear stabUity index (PSSI, see ASTM D
6022) is a m e a s u r e of the change due to shearing in an
additive's contribution to the lubricant's viscosity.
PSSI= 100X(Vo-Vs)/(Vo-Vb)
where:
PSSI
Vo
Vs
Vb
=
=
=
=
(15)
consensus process
In the ASTM system, a specific API
designation is assigned to each category. The system is
open-ended, that is, new designations are assigned for use
with new categories as each new set of oil performance
characteristics are defined.... Other service categories not
shown in this document have historically been used to
describe engine oil performance (SA, SB, SC, SD, SE, SF,
SG, CA, CB, CC, CD, CD-II, CE).
The Society for Automotive Engineers, Inc. (SAE) has specified engine oil performance categories and classifications for
many years. The SAE defines engine oil performance categories for gasoline and diesel engines. SAE J183, Engine Oil
Performance and Engine Service Classifications [68],
outlines the engine oil performance categories and classifications developed t h r o u g h the efforts of the American
Petroleum Institute (API), ASTM International (ASTM), the
American Automobile Manufacturers Association (AAMA),
the Engine Manufacturers Association (EMA), the International Lubricant Standardization and Approval Committee
(ILSAC), and SAE.
These specifications for engine oils incorporate a great
many ASTM methods such as sequence tests, volatility, chemicals, flash point, foaming tendency, etc. in addition to those
for flow-properties. Included in this specification is a discussion as to the background for each category, the dates the category was in use and the reasons why the category became
technically obsolete. The several categories are included in
Table 13. The reader is encouraged to refer to SAE J183.
Current flow-property specifications for gasoline engines
are included in SAE J300 [22], making reference to II ASTM
flow-property methods. This specification states that "the
limits specified are intended for use by engine manufacturers
in determining the engine oil viscosity grades to be used in
their engines, and by oil marketers in formulating,
manufacturing, and labeling their products."
The OW, 5W, lOW, 15W, 20W a n d 25W SAE viscosity
grades for engine oils specifications at low-temperatures
from 35 to 10C refer to the high shear Cold-Cranking
Simulator (CCS ASTM D 5293) tests. Pumpability specifications include temperatures from 40 to 15C and reference the Cannon Mini-Rotary Viscometer (MRV ASTM D
4684). Each of the "W" grade oils has a m i n i m u m kinematic
viscosity limit at 100C. From SAE J300,
. . . because engine pumping, cranking, and starting are all
important at low temperatures, the selection of an oil for
winter operation should consider both the viscosity required for successful oil flow, as well as that for cranking
and starting, at the lowest ambient temperature expected.
853
Description
No additives. Not suitable for use in gasoline automotive engines built after 1930.
Minimum level of performance additives. Oil considered non-detergent.
Additives improved to meet multicylinder engines sequence tests.
Enhanced additive treatment to meet performance requirements for current engines.
Emission control, high speed driving. CAFE advances required improved oils.
Reduced oil consumption, oxygenated fuels, longer drain intervals requuired new oils
Sequence HIE and VE to evaluate oxidation and sludge, CAFE and fuel injection.
Phosphorus and volatility control tests added. Reduced oil consumption.
Continuous improvements in motor oils as required for modem engines.
NOTE: reprinted with permission from the Society of Automotive Engineers, Warrendale, PA. The reader is encouraged to refer to SAE J183.
854
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
Each of the five SAE grades 20, 30, 40, 50, cind 60 reference
the low-shear-rate kinematic viscosity test range (ASTM D
445). The same grades also reference high shear (10* s"')>
150C tests (ASTM D 4683, or D 4741, or D 5481) to ensure a
m i n i m u m high-shear viscosity for each of the five SAE
grades.
KINEMATIC VISCOSITY/TEMPERATURE
RELATIONSHIP
In 1921, Neil MacCoulI created a viscosity - t e m p e r a t u r e
chart (Fig. 26) for sale by The Texas Company [69]. The ordinate of the chart was the double logio of the kinematic viscosity plus a constant and the abscissa was the logio of the absolute temperature. This chart was used to graphically show
the relationship between viscosity a n d t e m p e r a t u r e for
mineral oils. It was stated that
A close study of the various values of viscosity at different
temperatures reveals the fact that temperature-viscosity relations can be so expressed by a simple formula that when
plotted to the proper coordinates a straight line relationship is shown ... It has been found that there is no curvature to the line for any mineral oil so far tested, until the
temperature has been reduced to the point where paraffine
begins to precipitate . . . [69].
The equation used in the graph was
logio (logio {v + constant)) = A - B logio T
where,
pears that Walther may not have been aware of the prior
work by MacCouU until 1929 when advised by Herschel [73].
The constant in the above equation is required for the hightemperature, low-kinematic-viscosity part of the chart. The
constant was the subject of study in the 1930s, and various
values from 0.6 to 0.8 have been used. However, as reported
by W. Andrew Wright [74],
. . . a constant of 0.6 was used down to viscosities of 1.5
cSt. Below this viscosity, the constant was changed to 0.65
for the range from 1.5 to l.OcSt, 0.70for l.Oto 0.7 cSt, and
0.75 for 0.7 to 0.4 cSt.
This problem was the subject of an intensive study by Wright
resulting in the development of an improved chart at very low
kinematic viscosities and high temperatures. The equation
for the new charts is listed in the appendix to ASTM D 341 93. In 1974, Manning suggested a modification of the equations by Wright. These equations, shown below, are also
listed in the appendix to ASTM D 341 - 93, and have been
widely used, especially in the computational fitting of kinematic viscosity-temperature data by computers [75]. This
relationship is expressed as follows:
logio logio Z = A - B logio T
(17)
(18)
^^^^
(16)
(20)
(21)
The SUS/F charts were abandoned many years ago with the
worldwide emphasis on the use of the System Internationale
(SI) units in the specifications for petroleum products.
For many years a segment of these viscosity-temperature
charts has been used for blending two-component stocks.
The constant-temperature method of blending requires the
kinematic viscosity of each component at a given temperature. Using the chart from 0-100F as if these temperatures
represented 0 and 100% of the two components respectively,
the kinematic viscosity is plotted on the charts, drawing a
straight line between 0 and 100% of the components. Thus,
the approximate kinematic viscosity of blends could be estimated from the straight line connecting the two components
855
LI 3UIDFUE LS
TE M P ERj
20
1
0
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>o.oao
!
'
0.000
. 1
as
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= 5
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iO
o
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r '
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100
inml
i.OCDt
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40
SO
60
70
80
90
100
110
128
130
MU
TEMPERATURE CENTIGRADE
VISCOSITY-TEMPERATURE CHART
FIG. 26Neil MacCoull 1927 chart. Reprinted with permission from Texaco, Inc., White Plains, NY.
t.
ISO
<
"
at blends from 0-100% of the one component. This constanttemperature blending method is not very accurate, and mention of this process (as well as a special chart) was withdrawn
from ASTM D 341 many years ago. The constant-viscosity
method reported by W. A. Wright [81] is more accurate and
is described in the appendix to ASTM D 341-93 as follows:
Plot the known data for each component on an ASTM Viscosity-Temperature Chart and carefully draw straight lines
through the points. The lines should extend beyond the
blend kinematic viscosity required. Locate, or draw, the desired blend kinematic viscosity horizontal line on the chart
through both of the component oil lines. Lay a centimeter
scale along this line and carefully measure the distance between the lines for the two oils where they cross the line of
the desired blend kinematic viscosity. Without moving the
scale, on the same horizontal kinematic viscosity line read
the distance from the low viscosity oil line to the temperature desired. Dividing the latter by the first measurement
between the two oils gives the volume fraction needed for
the high viscosity oil.
VISCOSITY INDEX
As described in the Significance and Use section of ASTM D
2270 (originally published by ASTM as D 567 - 40T, and
revised and renumbered in 1964),
The viscosity index is a widely used and accepted measure
of the variation in kinematic viscosity due to changes in
the temperature of a petroleum product between 40 and
100C. A higher viscosity index indicates a smaller decrease
in kinematic viscosity with increasing temperature of the
lubricant. The viscosity index is used in practice as a single
number indicating temperature dependence of kinematic
viscosity.
ui
O
o
z
hi
O
I;;
U>
in
O
<
w
z
40
50
eo
ro
80
90
100
120
Description
Range (cSt)
Temperature
I
II
III
IV
V
VI
VII
High Range
Low Range
High Range
Low Range
High Range
Low Range
Middle Range
-70to+370C
-70to+370C
- 7 0 to -l-370C
-70to+370''C
-100to-l-700F
-100to+700C
-40to+150C
Size (mm)
680 by
680 by
217 by
217 by
680 by
520 by
217 by
820
820
280
280
820
820
280
Facsimile
Reference
Fig. 28
Fig. 29
not included
not included
not included
not included
not included
CHAPTER
AND SHEAR
STABILITY
857
i U . tHOHH. MLStuS
FIG. 28Facsimile of Kinematic Viscosity-Temperature Chart 1 High Range (temperature in degrees Celsius).
Viscosity index (VI) numbers have been used for many years
in the marketing of petroleum products. It was well known
t h a t lubrication fractions of oils from various sources of
crude oils showed large differences in their variation of viscosity with a change in temperature, and a way to characterize this change was needed. As described on page 69 of the
June, 1950 edition oi Lubrication [83],
The original viscosity index system was set up by an arbitrary selection of two series of oils derived from opposite
extreme types of crude oil: The "H" series having the less
change in viscosity with temperature, and the "L" series the
greater change. Seven blends were made up in each series,
with viscosities varying from about 200 to 1200 seconds
Saybolt at WOT. Each oil in the "H"series was arbitrarily
assigned a V.I. value of 100, whereas each oil in the "L" series was assigned a V.I. value of 0. In practice, a reference
oil is selected from each series with the same viscosity at
210 as the oil to be evaluated. The numerical difference in
viscosities of these two oils at WOT will always, by defini-
(22)
L = kinematic viscosity at 100F of an oil of 0 viscosity index having the same kinematic viscosity, Y, at 210F as the oil whose viscosity index
is to be calculated, mm^/s (cSt)
H = kinematic viscosity at 100F of an oil of 100 viscosity index having the same kinematic viscosity, Y, at 210F as the oil whose viscosity index
is to be calculated, mm^/s (cSt),
U = kinematic viscosity at 100F of the oil whose
viscosity index is to be calculated, mm^/s (cSt).
The original scale was proposed by Dean and Davis in 1929
[84] and revised by Davis, Lapeyrouse, and Dean in 1932 [85]
and in ASTM D 567. The original scale was based on data for
L and H in the range of 7.29 to 75 cSt at 210F. Later, light
oils were used to extend the table between 2.0 and 3.99 cSt.
858
MANUAL
HANDBOOK
FIG. 29Facsimile of Kinematic Viscosity-Temperature Chart 11 Low Range (temperature in degrees Celsius).
Values for L and H were obtained for the range of 4.00 to 7.29
mm^/s (cSt)
. . . by a special method of calculation which was equivalent to graphic interpolation on a greatly magnified scale.
In this range of viscosity the constants are not defined by
equations [86].
It had been assumed that all oils would have Vis between 0
and 100. However, many m o d e m oils, especially those with
the additive packages, have a VI above 100. Extrapolation of
Vis u p to 120 seemed to fit the viscosity index scale without
a problem. However, there was a serious problem above 130.
Accordingly, in the late 1950s W. Andrew Wright [87,88] devised a special calculation to extend the VI calculation above
100. This was adopted into ASTM D 2270 in 1964, and for
several years the viscosity index so calculated used the
symbol Vlg to differentiate VI between the new extended VI
equation and that by extrapolation from the equation for use
u p to a VI of 100.
ASTM had published a book of viscosity index tables based
on 100 and 210F temperatures as a Special Technical Publication [89,90]. This book was replaced by another book [91]
based on D 2270 - 64, but for temperatures in degrees Celsius.
The forward states in part
The studies leading to the change in calculating the viscosity index are the result of recommendations by the Third
and Fourth World Petroleum Congress that a method be selected which would avoid the problems which ultimately
(23)
(24)
CHAPTER
where
N = (logio H - logio U)/logio Y
(25)
(26)
H = 0.1684 Y 2 + 11.85 Y - 9 7
(27)
and
The following example demonstrates the calculation of viscosity index both for values of VI below 100 and above 100
(see Table 17).
Calculation example A: Measured kinematic viscosity, U,
a t 4 0 C = 171.8
Measured kinematic viscosity, Y,
at 100C = 15.69 by interpolation,
L = 320.74 and H = 159.95
VI = 100*(320.74 171.8)/(320.74 - 159.95) = 92.63
and rounding to the nearest
whole number, VI = 93
Calculation example B: Measured kinematic viscosity, U,
a t 4 0 C = 120.1
Measured kinematic viscosity at,
Y, 100C = 15.78 by interpolation, H = 158.28
N = [(log 158.28 - log 120.1)/log
15.78] = 0.100060
VI = [((antilog 0.100060) - 1)/
0.00715] + 100 = 136.24
and rounding to the nearest
whole number, VI = 136
There are some highly waxy base stocks that can be determined at 100C but not at 40C due to wax formation. The
kinematic viscosity of such materials can often be determ i n e d at a higher t e m p e r a t u r e , e.g., SOX. Using the
MacCouU equation the kinematic viscosity at 40C can be estimated. This allows the VI to be estimated, but this value is
not to be considered the true VI of the material.
The precision attributed to the viscosity index is based
entirely on the precision of the kinematic viscosity measurement. For base and formulated oils, information in Table 18
is calculated from the repeatability and reproducibility of
ASTM D 445. Tak:e note that the precision of the kinematic
viscosity measurement is different for each of the types of
materials, and thus the precision attributed to viscosity index
is a function of the product. Table 18 indicates the precision
to be attributed to viscosity index for base and formulated
oils [94]. Because of the importance of VI in the metrketing of
petroleum products, it is important to keep in mind that the
reproducibility attributed to base and formulated oils may
vary from 2-9 VI units. Thus, the rounding of the VI to the
nearest whole n u m b e r is required.
Other proposals have been made for characterization of
the vatriation of kinematic viscosity with temperature [95,96],
especially by E. E. Klaus et al. from the Petroleum Refining
859
TJ =
T =
P =
a =
K, b =
(28)
viscosity,
the absolute temperature,
the pressure
pressure-viscosity coefficient, Euid
constants for the material.
(29)
mo: Viscosity-temperature property from the ASTMMacCoull equation and equal to (ASTM
slope)/0.2
VQ: Atmospheric kinematic viscosity at the temperature of interest, mm^ls
incO'-HrfcO'-Ht^rotf*^0\orn'iooor^i>r^r^r~^ooc>0(^\oorosoO'OfN
0^0^00'-HrH*-H^^^^^^r*^<:J-^lnln^o<?t~^t^ooooc>0^00'-H^irS(Nl<^<^':t
ti .tt 5^ vi
5 oo cc
i n o i r i o i r i o i n o t o o i o o u ^ O u - i O i n p i o p u - i o i n o i n o i o o i o o u - ) 0
II'
oo^o^OOa^c^oot^t~^ln^^ro^i-lO<?^^'^^'0^ocoO'0'-Hr^^u^l^l^o^~^'^
OOO^^(NfS^^^^0r^T^rt':tmm^0^0'^^^t^0000000^0^OOO^^(N^0
)<Navc~~-iofN(Nrnr-;'^^ooo
'iop<)rn'^oosDO(Nrt|'<t
coo^O'-H^^^ro^u^\ot^o^O'ifNro'ri-ir)'<>oo(^o^^<N(^io^r^cooN'ifNin
\o^t^c~^^~^^~-^~^^^t^t~^c^oococococoooooooooo^c^a^o^o^o^a^c7^o^ooo
i O (N
'
pr^'^_Nqooprsj'^_\qcor^'^^oooor^"^_^oqor^_-^sqoqo
1 > s "
^vJr^^^0^lr:lrH^-;^00^^q(N00Tto^0r00^^q^0pt^^^t~-'^^<
O ^ r ^ - ^ vO 0 0 ON ^ (N ^' MD l > ON ^ f S ' ^ ' l O t^' cK >--< <N '^* NO* ^ ^
OOOOOOOOOOOOCOONONCTvOvONONOOOOOO'-fT-HT-HT-HT-H,i(N<N<N(N(N<N(^
^m'lOONONf^r-^
ONrot^'-H'^cdr4N6o'^cdr4^0'^aNf^t^''-iinoN'^'odrsir^
\oi~^t-^ooooooaNONOOO'^'^rsi(Nr^ror*^-^'^'=^u^ir)^o\or~^r~--t^ooooa\o
S 'S b,^C^
E o o g cfl
c .2! 4^ E "-^
t^t~^c->^i>t^t^'i>r^'r~-^c~^'cdcdododododo6odo6o6
^ir^o6r-^-rffr^(^<^{:^cir^-<>0-\r^\6<>r*i'Sosr^^C>
000'<-H'.-HT-H^rvirNir^i(^r^f^-<^Tj--<:tioioio\o^ci\0\or^r^t^oooooooNaNO
lilt
a-5
^--1-HC^ooooooc^o^lno^o^lnoO(Noo'^o^^or^(Nr^^<-)^oor^<)r^r^oo
odON0^04rou-i^dt~--'odO\0'^*ro-rfiovor^'o6oN'^'r^^
Ou-)ONrooir)-Tro<^(N
OrslrntONOcopr^'^_t~-;0<^^oaNr^ioaNr^ioONror^O'^oor*^t^^Ht^rs)r^(N-)
corsi'=t\dcd'^<^iot^OfS'^'^av'^(^'^o6oroiricx3
t~^0000000000aNaNaN0NOOOOO'^'^'^^(N(N(N(Nf0r*-ir*-)rn-^'=1-'^'!rii-)
u
E o o
g cfl
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
0'-Hrsif*^^iri'^t^oqONO'-HrN|fO'^i/^^r^oooNO^H<NirO's1-iONOt^ooONO'-H
3>
^ ^ o '<i- ^ r^ r^
aNON'-HTtoN^'^iot^ou^rst^'^<^^cir^ONr^i>^or-^i-Hirir^-rHT-<frii^roONso
\0\dc^i>cdo\(JNC)0'-Hr4r^rn'^'^uS<JKr^odaNO'-HrNi
^ O ON
0N'!l-OO^iO'^OOr*^0N\0'O00<NO\000Nrn0vfN)Ou-ir--00O(Nf00NOrn0N
ON\Or*^pt->;'rfrNjOoo-0'^fOrNj'-Hi-HOOP'^'-Hr^iOi>0^
t^cdo^OO'-^^^'^*^^n^'l/i^dt--^o6o^O'--H^^irn^lri
iJHIi
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
lOi ^^ r^ rn rt IT) <:>t^oo o^<o ^^ C'^ rr) -^ in <> t^ CO 0\C> ^
rvi r s r^i <N fS r4 <N CM (N H r*^ rn r*^ rn ro r^ r<i fO rn
ON0'^l>r<iaNl0O\0(N00^O^0(NOin'-f00'^Ot^f0O
ioiONCi'>cii>t~~-oooNONOO'^r\ifNro(^'=l-inio>or~--i>ooav
i n o i o o i n o i o o m o i o o i n o i n o i o o i o o i o o i o o
^^^O0^0^O---^^0'^_lnO^q^^0f^^.-^O^rSC0(N-0r-<0^
^ir)'or~-ooaNO(Nro'^u-)or^ONO'-H(Nf^msoi>ooo
O'-H'(>(rN(N(Nrnr*-)rn'^'^iniOiO\0^0Or^l>000000
Ou-)Oii*)Oinoinoioomoioomomomoioo
(N(N<N(N(N(NfNr^(N<N(N(Nr^rstfs|(N<N(N
ooaNOO^ir)r^'^\OrNOr*^(N't^O'^ooror-OO^cdod^-^^D^dlOlOlO<:}-^Trr*^fn^orOr<^
T t s o 00 O
<N **. ^ _ 0 0 O
fN -^^ NO 0 0 p
(N -sf sO 0 0
OOO'''-H'--H'-H'-Hrsirjr^'fNrsir*Srnrof^rn
fN(N<N<N<NfNrs|rs|rs|<N(N(N(NfNfNfs<N(N
sq'-Hsqosq^^D'^\q'^i><Ni>rnoq'^osq
r^''^'int~-^odO'-Hr^Tt\dr^'oNO(Nrninr^'o6
ioioiomm^>sosOsOsci\os>r-r~--r~-r-r^r^
r*S s d O
r n t ^ T-H Tf od ^" l O ON fN s d O
lO
(N(^Ttio\Dr-;OoaNO'^(Nrn^iosoi>oqoN
i/SidioiouSi/iioirisd^Jsdsdsdsdsdsdsosd
O'^tNirjONOLOfSOiO'^t^
f^irit^aN'--;'^^ONT-H-^i>av(NiooO'I'^it--;
ui^dt'-^ooo^fNr'Stosdr^odo'(fS'rrinvd
OOOOOOOOOvCfNOONONONONONOOOOOO
0^^p\qfN00lO(N0^sq"^'--^O^s0'!:1-^n<Np
^^iuSo6o^OlOo6'-Hrn^do^<N^'t~-^Or^sdo^
irimin<3sosooi>i>i>t^ooooooa\a\0\a\
mor^^(Ncr\sor*^a\f^in(^'<^oO'^fO'!:l-'-H
dT-Hrsro'^ioso'i-^'o6oNd'-H(Nr*^'=^'irisdt^
sOr*-)'^ONl>'^(NOt^'=^(N(NOO(NsOONOO(N
r~^u^rOpOOsO'!:rr^a\C^inr^'-HT-H,ifS'=rC~--_
^^^^'Ou'iioioiomsosOsO'sOsor^t^t^
o o o o o o o o o o o o o o o o o o
(Nf^'^insqi^oooNO'^tNrn-^insoooqov
iniriuSi/SininuSiovD<J<J^sbsosdsdsdsd
861
HANDBOOK
Ymax
2.0
3.8
4.4
5.0
6.4
7.0
7.7
9.0
12
15
18
22
28
40
55
70
3.8
4.4
5.0
6.4
7.0
7.7
9.0
12
15
18
22
28
40
55
70
Up
1.14673
3.38095
2.5000
0.10100
3.35714
0.01191
0.41858
0.88779
0.76720
0.97305
0.97256
0.91413
0.87031
0.84703
0.85921
0.83531
1.7576
-15.4952
-7.2143
16.6350
-23.5643
21.4750
16.1558
7.5527
10.7972
5.3135
5.2500
7.4759
9.7157
12.6752
11.1009
14.6731
-0.109
33.196
13.812
-45.469
78.466
-72.870
-56.040
-16.600
-38.180
-2.200
-0.980
-21.820
-50.770
-133.310
-83.19
-216.246
0.84155
0.78571
0.82143
0.04985
0.22619
0.79762
0.05794
0.26665
0.20073
0.28889
0.24504
0.20323
0.18411
0.17029
0.17130
0.16841
1.5521
1.7929
1.5679
9.1613
7.7369
-0.7321
10.5156
6.7015
8.4658
5.9741
7.4160
9.1267
10.1015
11.4866
11.3680
11.8493
-0.077
-0.183
0.119
-18.557
-16.656
14.610
-28.240
-10.810
-22.490
-4.930
-16.730
-34.230
-46.750
-80.620
-76.940
-96.947
L = aY' +bY+ c
H = dY' + cY+f
313.9
317.5
321.1
324.6
328.3
157.0
158.6
160.1
161.6
163.1
VI = 0
Kinematic
Viscosity
at100C
(mm^/s)
4
6
8
15
30
50
Reproducibility, R
Repeatability, r
Repeatability, r
Reproducibility, R
Base Oil
Formulated
Base Oil
Formulated
Base Oil
Formulated
Base Oil
Formulated
0.98
0.71
0.57
0.45
0.39
0.36
2.31
1.68
1.35
1.06
0.92
0.85
5.77
4.20
3.38
2.56
2.29
2.11
6.75
4.91
3.95
3.11
2.68
2.47
0.73
0.40
0.30
0.20
0.14
0.11
1.73
0.94
0.70
0.48
0.33
0.26
4.32
2.35
1.75
1.19
0.82
0.65
5.05
2.75
2.05
1.39
0.96
0.76
Procedure B
VI == 200
Vl= 100
Kinematic
Viscosity
at 100C
(mm^/s)
4
6
8
15
30
50
Repeatability, r
Reproducibility, R
Repeatability, r
Reproducibility, R
Base Oil
Formulated
Base Oil
Formulated
Base Oil
Formulated
Base Oil
Formulated
0.50
0.37
0.31
0.23
0.19
0.17
1.18
0.87
0.74
0.55
0.44
0.40
2.94
2.18
1.84
1.37
1.11
0.99
3.44
2.55
2.15
1.61
1.30
1.16
0.77
0.57
0.48
0.36
0.29
0.26
1.82
1.34
1.13
0.84
0.68
0.61
4.54
3.35
2.82
2.11
1.71
1.52
5.31
3.92
3.30
2.46
2.00
1.78
soo
400
300
200
ISO
S
I/)
100
\,
>>=s^
i> s
S,
^' S
II
v ^ V-
so
t^
TT
V
^.*
\ /o s;
40
s,
-^
-^
II
1/3
HJ T^
^
i> ^^ \C
S 1
30
"^
u
^^
H
S, s^ s .
\
X s
\,
X ^
N k.
v^
20
s^
V S
v
'>
IS
SOs .
N*^
^^
^ ^
10
9.0
8.0
7.0
6.0
90
100
110
120
130
140
863
150
160
170
180
190
200
210
220
230
240
10,000
1000
o
a.
E
>-"
100 -^
h;
00
O
O
00
>
1000
2000
3000
PRESSURE, ATMOSPHERES
FIG. 31Viscosity as a function of pressure.
For almost all of the tests and procedures for the measurement of kinematic viscosity and viscosity, viscosity standards
are necessary to calibrate the equipment and to ensure that
the test is being carried out correctly.
The kinematic viscosity range of standards commercially
available is from about 0.6- to 100 000-mm^/s, over a temperature range from about 40 to 150C. These standards cover
the full range of the instruments used for the measurement of
kinematic viscosity. The viscosity range of standards commercially available is from about 0.6- to 5 000 000-mPa-s
(5000 Pa-s) over a t e m p e r a t u r e range from about 40 to
150C.
From the late 1930s to about 1959, ASTM Subcommittee
D02.07 Section A on Newtonian Viscometry made available
three API viscosity standards. These standards were sponsored by the American Petroleum Institute, and certification
was done by m e m b e r s of ASTM D02.07.A. The standards
were
API Standard
Alpha
Beta
Gamma
T A B L E 1 9 V i s c o s i t y of w a t e r .
Temperature
(C)
Viscosity
(mPa-s)
Density
(kg/m')
Kinematic
Viscosity (mm^/s)
15
20
23
25
30
40
1.1378
1.0016
0.9321
0.8899
0.7971
0.6524
999.10
998.20
997.54
997.04
995.65
992.21
1.1388
1.0034
0.9344
0.8925
0.7995
0.6575
CHAPTER
865
...40C
S3
S6
S20
S60
4.6
11
44
170
640
80
S200
S600
S2 000
S8 000
S30 000
2 400
8 700
37 000
50C
2.9
5.7
18
54
180
520
4.0
8.9
34
120
450
1 600
5 600
23 000
81000
100C'
1.2
1.8
3.9
7.2
17
32
75
280
1 700
6 700
23 000
11 000
" The actual values for these standards are established and annually reaffirmed by cooperative tests. In 1991, tests were made using 15 different types of viscometers in 28 laboratories located in 14 countries.
* Kinematic viscosities may also be supplied at 100F.
^ Kinematic viscosities may also be supplied at 210F.
2000
1000-
600
200-
30
6
10
20
30
60
100
200 300
600
KINEMATIC VISCOSITY mm V s
(30)
v = kinematic viscosity
77 = viscosity
p = density
A, B empirical constants
100)]
[1.0 +0.03264 v)]
4.6324 v +
(3930.2 + 262.7 v + 23.97 v^ + 1.646 v^) X 10"
Where:
V = kinematic viscosity, mm^s (cSt) at fF
Ut = Saybolt Universal Viscosity at ?F
Until recently, charts with SUS units as a function of temperature in degrees Fahrenheit were published by ASTM.
These charts have been replaced by kinematic viscosity in
mm^/s as a function of temperature in degrees Celsius (ASTM
D 341 - 32 T, ASTM D 341-93), as it is the custom to use the
International Systems of Units (SI).
where
v=
t] =
p =
A, B =
kinematic viscosity
viscosity
density.
empirical constants
(31)
866
HANDBOOK
O
00
CD
0.02
O
(D
O
C
CD
^._
CD
CD
s^
D
CD
CL
E
CD
100
100
200
t, X
FIG. 33Temperature correction between
IPTS-68 and ITS90 temperature scales.
Equilibrium State
T90 (K)
tso {C)
02
Ar
Hg
H2O
Ga
In
Sn
Zn
Triple point
Triple point
Triple point
Triple point
Melting point
Freezing point
Freezing point
Freezing point
54.3584
83.8058
234.3156
273.16
302.9146
429.7485
505.078
692.677
-218.7916
-189.3442
-38.8344
0.01
29.7646
156.5985
231.928
419.527
ment of one Kelvin, and t = 0C is the same as the thermodynamic temperature T = 273.15 K [118]. The practical
temperature scale now in use is the International Temperature Scale of 1990 (ITS-90). Formerly used temperature
scales include the International Practical Temperature Scale
of 1968 (IPTS-68), the International Practical Temperature
Scale of 1948 (IPTS-48), and the International Temperature
Scale of 1927. There are small differences in temperatures
between the several temperature scales, and for accurate
experimental work, the temperature scale used should be
specified. See Fig. 33 (ASTM E 1594), which describes the
differences between the ITS-90, adopted on January 1, 1990,
and the IPTS-68 temperature scale.
Liquid-in-glass thermometers are fundamental to accurate
viscosity measurements. ASTM methods El and E77 give
considerable guidance in the construction and use of thermometers. These thermometers must be calibrated against Standard Platinum Resistance Thermometers (SPRT) for the
most highly accurate temperature measurements. Once
calibrated, liquid-in-glass thermometers need only be recalibrated at one of the temperatures in the futuremost often
the ice point temperature, as follows: [119]
High quality liquid-in-glass thermometers require only one
complete calibration in their lifetime and it is possible to
avoid the usual requirement for complete recalibration of
the instrument by the recalibration of a single previously
calibrated temperature. The need for recalibration of properly manufactured liquid-in-glass thermometers is due to
the gradual relaxation of residual mechanical strains in the
glass that have a significant effect on the volume of the
bulb. The recalibration of a single point provides a reliable
indication of the effect of this change in volum^e and provides a means for the accurate adjustment of the remainder of the scale. Those calibrated, mercury-in-glass
thermometers which have an ice-point scale allow verification of the complete calibration by measurement of the
ice point. A change in the ice point reading, if any, from the
original calibration at the ice point will apply to all temperatures in addition to any corrections given in the original
calibration.
The certificate of calibration for the thermometer must state
whether the thermometer is to be used at total immersion, at
partial immersion, or at complete immersion. Total immersion thermometers require immersing those parts of the thermometer's liquid at test temperature, while keeping the
emergent stem exposed to ambient temperatures. Complete
immersion thermometers are to be completely immersed
(32)
867
the rheological tests are used in c o m m o n to the various materials, but the preparation of each material for testing is
often specific to the particular material.
Paints and Coatings Flow-Related Instruments
The paint and coatings industry has many rheological measurements made on its products. Adaptations of a n u m b e r
of these measurements are of use to petroleum products.
The viscosities of printing inks, solvents (vehicles), and similar materieils are measured by the Leiray or Duke fallingrod viscometers (ASTM D 4040). These apparatuses are
based on measurements of the time required for a weighted
rod to fall through a n aperture containing the specimen at
25C having a viscosity in the range of 1 to 30 Pa-s at a
shccir rate of 2500 s ^ ^ Calibration of the apparatus is by
the use of multiple viscosity standards at 25C, and includes
the determination of the fall time equivalent to a shear rate
of 2500 s ^ Using the power-law relationships between
shear stress and shear rate, the apparent viscosity at a shear
rate of 2500 s " ' , the degree of non-Newtonian behavior
(shear-thinning or shear-thickening) and reference temperature are determined, although the complete rheological
properties are not defined. Low shear rate properties are
not measured. Such information is useful in the practical
control and use of ink.
The viscosities of paints, varnishes, lacquers, coil coatings,
and related liquid materials are measured by dip-type and
short capillary cups such as Zahn dip cup. Shell, Ford, and
ISO cups (ASTM D 4212, ASTM D 1200, ASTM D 5125). See
Fig. 34.
Dip Cups
Zahn Cup
ISO Cup
K, B = constants
t = flow time
Ford Cup
Shell Cup
(33)
868
MANUAL
HANDBOOK
(34)
K, c = cup constants
t = flow time
^ g ( N o . 22 US. Ooge}
All Oimwsions Subject to o
,. . , ... . , ^olewnce of 0.004"
Material: Sloinless Steel
CHAPTER
AND SHEAR
STABILITY
869
rotational
Plastics
Flow-related tests are fundamental in the making of plastic
products. There are many "dilute solution" methods of tests
for plastics (ASTM D 789, ASTM D 1243, ASTM D 1601,
ASTM D 2857, ASTM D 3591, ASTM D 4603, ASTM D 4878,
ASTM D 5225, ASTM D 1823); typically there is a specific
procedure for each polymer. These methods allow the meas u r e m e n t of the viscosity ratio, which is the ratio of the
viscosity of a very dilute polymeric solution to that of the
pure solvent. Generally, a glass kinematic viscometer is used
to measure both the kinematic viscosity of the solution and
of the solvent. Because the density of the dilute solution is
nearly the same as the density of the solvent, the relative viscosity is merely the ratio of the flow time, t, of the solution to
that of the solvent, to (assuming there is no significant kinetic
energy correction to be applied to the flow time).
Viscosity Ratio: Tjr = TJ/TJO = t/to
(37)
M''
M = molecular weight
a, b = constants determined for each type of polymer.
where
FIG. 36Electronic
paint tester.
= a
Inherent Vticoilty
_(I-ogrtthn.lc Vl.coalty Number)
Incrinilc Vlscotlty
(Limiting Vlicoaity Number)
(35)
where
Relative Viscosity
Reduced Viscosity
Inherent Viscosity
Viscosity Ratio
Viscosity Number
Logarithmic Viscosity
Number
Limiting Viscosity Number
Intrinsic Viscosity
"where
Definition"
Vr = V'no
%ed = (Vr - 1)/C
ijinh = In r)r /c
[TJ]
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MANUAL
3 7: FUELS
AND LUBRICANTS
HANDBOOK
Rubber
Rheology is the science of deformation and flow of materials.
Deformation can be divided into reversible deformation
(elasticity) and irreversible deformation (flow). Many materials exhibit b o t h reversible a n d irreversible deformation,
exhibiting what is called viscoelasticity. This property is of
critical importance in the manufacture of rubber products,
although it is exhibited in many other products including
lubricants, paints, and coatings, etc.
The variety of terms used relating to the rheology of rubber
illustrate the complexity of this subject: viscosity, real
dynamic viscosity, relaxation, shear, strain, stress, modulus,
loss modulus, storage modulus, complex shear modulus, dynamic complex viscosity, elastic recovery, elastic fatigue, and
many others. Types of instruments used to measure the rheological behavior of unvulcanized raw rubbers and rubber
compounds include:
ASTM STANDARDS
No.
ASTM D 5
ASTM D 88
ASTM D 88-21 T
ASTM D 97
ASTM D 244
ASTM D 341
ASTM D 341-32 T
ASTM D 341-93
ASTM D 445
ASTM D 446
ASTM D 562
Title
Test Method for Penetration of Bituminous Materials
Test Method for Saybolt Viscosity.
Standard Test Method for Saybolt
Viscosity, 1921
Test Method for Pour Point of
Petroleum Products
Test Method for Emulsified Asphalts
Viscosity-Temperature Charts for Liquid Petroleum Products, Appendix XI
Viscometer-Temperature Charts for Liquid Petroleum Products
Viscometer-Temperature Charts for Liquid Petroleum Products
Standard Test Method for Kinematic
Viscosity of T r a n s p a r e n t a n d Opaque
Liquids (the Calculation of Dynamic
Viscosity)
Standard Specifications and Operating
Instruction for Glass Capillary Kinematic Viscometers
Test Method for Consistency of Paints
using the Stormer Viscometer
CHAPTER
Test Methods for Determination of Relative Viscosity, Melting Point and Moisture Content of Polyamide (PA)
Test Methods for Tall Oil
ASTM D 803
Test Methods of Testing Cellulose
ASTM D 871
Acetate
Test Methods of Ethylcellulose
ASTM D 914
Specification for Penetration-Graded
ASTM D 946
Asphalt Cement for Use in Pavement
Construction
ASTM D 1084
Test Methods for Viscosity of Adhesives
Methods of Testing Rosin Oils
ASTMD 1131
Test Method for Viscosity by Ford VisASTM D 1200
cosity Cup
Test Method for Dilute Solution ViscosASTM D 1243
ity of Vinyl Chloride Polymers
Test Methods for Methylcellulose
ASTM D 1347
Test Methods for Sodium CarboxymethylASTM D 1439
cellulose
Test Method for Viscosity of TransparASTMD 1545
ent Liquids by Bubble Time Method
ASTMD 1601
Test Method for Dilute Solution Viscosity of Ethylene Polymers
Test Methods for RubberViscosity,
ASTM D 1646
Stress Relaxation, and Pre-Vulcanization
Characteristics (Mooney Viscometer)
Test Method for Engler Specific ViscosASTM D 1665
ity of Tar Products
Test Method for Viscosity of Resin
ASTMD 1725
Solutions
Test Method for Intrinsic Viscosity of
ASTMD 1795
Cellulose
ASTM D 1823
Test Method for Apparent Viscosity of
Plastisols and Organosols at High Shear
Rates by Extrusion Viscometer
ASTM D 2162
Standard Test Method for Basic Calibration of Master Viscometers and Viscosity Oil Standards
Test Methods for Kinematic Viscosity of
ASTMD 2170
Asphalts
Test Methods for Viscosity of Asphalts
ASTMD 2171
by Vacuum Capillary Viscometer
Test Methods for Rheological Properties
ASTMD 2196
of Non-Newtonian Materials by Rotational (Brookfield) Viscometer
ASTM D 2270 - 93 Standard Practice for Calculating Viscosity Index From Kinematic Viscosity
at 40 and 100C. (Originally pubUshed
by ASTM as D 567 - 40T, and revised and
renumbered in 1964.)
Test Methods for
Hydroxypropyl
ASTM D 2363
Methylcellulose
ASTM D 2556
Test Method for Apparent Viscosity of
Adhesives Having Shear-Rate-Dependent Flow Properties
Test Method for Apparent Viscosity of
ASTM D 2602
Engine Oils at Low Temperature Using
the Cold-Cranking Simulator, Note: Replaced by D 5293
Sonic Shear Stability of PolymerASTM D 2603
Containing Oils
ASTM D 789
ASTM D 2994
ASTM D 3205
ASTM D 3236
ASTM D 3346
ASTM D 3451
ASTM D 3591
ASTM D 3616
ASTM D 3829
ASTM D 3835
ASTM D 3945
ASTM D 4040
ASTM D 4092
ASTM D 4212
ASTM D 4287
ASTM D 4485
ASTM D 4486
ASTM D 4499
ASTM D 4603
ASTM D 4624
ASTM D 4683
ASTM D 4741
ASTM D 4878
AND SHEAR
STABILITY
873
874
MANUAL
ASTM D 4957
ASTM D 4958
ASTM D 5023
ASTM D 5024
ASTM D 5026
ASTM D 5099
ASTM D 5125
ASTM D 5133
ASTM D 5182
ASTM D 5225
ASTM D 5275
ASTM D 5279
ASTM D 5293
ASTM D 5400
ASTM D 5418
ASTM D 5422
ASTM D 5478
ASTMD 5481
ASTM D 5621
ASTM D 5992
ASTM D 6022
ASTM D 6048
HANDBOOK
ASTM D 6049
ASTM D 6204
ASTM D 6278
ASTM D 6648
ASTM E 1
ASTM E 77
ASTM E 102
ASTM E 220
ASTM E 230
ASTM E 644
ASTM E 879
ASTM E 1137
ASTM E 1594
ASTM E 1750
OTHER STANDARDS
Saybolt
Viscosity
AASHTO T 72
Pour Point of Petroleum
Products
Measurement
and
Calculation
Shear
Stability
Test
D I N 5 1 3 8 2 : T e s t i n g of L u b r i c a n t s - D e t e r m i n a t i o n of S h e a r
S t a b i l i t y of L u b r i c a t i n g Oils C o n t a i n i n g P o l y m e r s - M e t h o d
W i t h Diesel Injection Nozzle, Relative Viscosity Loss D u e to
Shear
I P 2 9 4 : D e t e r m i n a t i o n o f S h e a r Stability of P o l y m e r - c o n t a i n i n g
Oils-Diesel I n j e c t o r R i g M e t h o d
REFERENCES
[1] Navier, C. L. M. H., Memoire Sur les Lois du Mouvement des
Fluides., Memoires de TAcademie Royal des Sciences de I'lnstitute
de France, Vol. 6, 1823, p . 389.
[2] Hagen, G., Annalen der Physik, Vol. 46, 1839, p. 423.
[3] Poiseuille, J. L. M., Memoires Savants Etrangers, Vol. 9, 1846,
p. 433.
[4] Couette, M. M., Annates de Chimie et de Physique, Vol. 21, 1890,
p. 433.
[5] Pochettino, A., "Viscosity a n d Elasticity of Highly Viscous
Materials," Nuovo Cimento, Vol. 8, 1914, p. 77.
[6] Bingham, E. C. and Jackson, R. F., Standard Substances for the
Calibration of Viscometers, Vol. 14, Scientific Paper 298, National Bureau of Standards, Washington DC, 1918-1919, p. 59.
[7] Ubbelohde, L., "Das Einfachste und Genaueste Viskosimeter
u n d Andere Appciratemit Hangendem Niveau," Journal of the
Institute of Petroleum, Vol. 19, 1933, pp. 376-^20, and Vol. 22,
1936, p. 37.
[8] Cannon, M. R. and Fenske, M. R., Industrial and Engineering
Chemistry, Analytical Edition, Vol. 10, 1938, p. 297.
[9] Appeldoorn, J. K., "The Present State of Lubrication and Its Relation to Rheology," ASME Paper #68.1.Kll-5, ASME-ASLEASTM Symposium
on Lubrication and Lubricant
Rheology,
1968.
[10] Klaus, E. E., "Energy Conservation in Road Transportation
Through Lubricant Technology," Lubrication Engineering, Vol.
34, No. 11, 1978, pp. 611-617.
[11] Wright, W. A., "An Improved Viscosity-Temperature Chart for
Hydrocarbons," Journal of Materials, JMLSA, Vol. 4, No. 1,
March 1969, pp. 19-27. See also "Changes in ISO Industrial Oil
Viscosity Classification," ASTM Standardization
News, April
1973, pp. 36-38.
[12] Yeaple, F., Ch. 1, Fluid Power Design Handbook,
Marcel
Dekker, Inc., NY, 1990, pp. 6-7.
[13] Cannon, M. R., Manning, R. E., and Bell, J. D., "Viscosity Measurement, The Kinetic Energy Correction and a New Viscometer," Analytical Chemistry, Vol. 32, March 1960, p. 355-358.
[14] Poiseuille, J. L. M., Comptes Rendus, Vol. 11, 1840, p p . 961,
1041.
[15] Barr, G., A Monograph of Viscometry, Oxford University Press,
London, 1931.
875
[99]
[100]
[101]
[102]
[103]
[104]
[105]
[106]
[107]
[108]
[109]
[110]
[Ill]
[112]
[113]
[114]
[115]
[116]
[117]
[118]
[119]
877
MNL37-EB/Jun. 2003
POUR POINT
MOLECULE will increase when the liquid is cooled. If the liquid is cooled sufficiently, the viscosity will increase until the
liquid solidifies (freezes). However, most petroleum products are composed of mixtures of many different types of
molecules, each of which has its own freezing point. When
these liquids are cooled to low temperatures, unanticipated
results can occur. The diesel fuel for cars and trucks can
form crystals that will plug the fuel filter while the vehicle
is being driven, causing the vehicle to stop. Heating oil can
be loaded into a delivery vehicle, but at very low temperatures the oil may not flow through the delivery hose to the
business or home receiving the oil. Automotive engine products in conventional quart, liter, or gallon containers may,
when left outside the filling station in the winter, solidify so
they will not pour out of the container. Some petroleum
products will form a "gel" structure at a certain low temperature. However, the same material, when cooled rapidly
from a w a r m temperature to a still lower temperature and
through a critical temperature range, will flow in a normal
manner.
As the temperature of a petroleum product is lowered, wax
contained in the product can crystallize into long crystals
thus forming a gel structure. Frequently, chemicals such as
"pour-point depressants" (wax-crystal modifiers) are added
to fluids to lower the temperature at which gels can form.
Such pour point depressants serve to lower the pour point of
the fluid by forming many smaller crystcJs at a temperature
somewhat higher t h a n the temperature at which wax crystals
form. With cooling to still lower temperatures, wax will crystallize onto the unconnected crystal sites of the pour-point
depressant instead of forming a gel structure. Without the
yield stress provided by a n interlocking gel-structure, the material will show a much lower pour point.
Lubricating oils
Distillate and residual fuels
Black oils used in heavy-duty equipment
Cylinder stock
Heat transfer fluids
Crude oils
Originally published as ASTM D 4 7 i n l 9 1 7 and revised and
renumbered D 97 in 1927, the Pour Point of Petroleum Products is among the oldest of petroleum test methods still in
use.
A test sample is placed in a jar and heated without stirring
to 9C above its expected pour point (but to a minimum of
45C) by placing the jar in a bath at a m i n i m u m of 48C. The
jar is cooled in a non-uniform manner by cooling in sequence
inside a group of successively lower temperature baths from
0 to -69C. These sequences include:
879
Copyright'
2003 by A S I M International
www.astm.org
CORK
25 MAX.
- L
COOLANT LEVEL
DISK
NOTE 1Dimensions are in miUimelres (not to scale).
Stirring Rod
Moistureproof
Collar
881
Thermometer
Cork Stopper
Refrigerant
Carbon Dioxide
Vacuum Flask
NOTE 1^AIl dimensions are in mm and 0.1 mm glass wall thickness
isl mm.
cooling and optical detection of the appearance a n d disappearance of the hydrocarbon crystals. The automated apparatus allows reporting the freezing point to the nearest 0.1 C,
and somewhat improved repeatability and reproducibility as
compared to ASTM D 2386 (Fig. 2).
The lowest temperature at which aviation fuels remain free
of solid hydrocarbon crystals is a key safety parameter in the
specification and use of fuels, because the hydrocjirbon crystals can restrict the flow of fuel through filters in an aircraft
fuel system. A cooling and warming cycle of the fuel through
a specified filter can also be used to determine the temperature, called the flow point, at which the filter becomes unblocked on weirming (ASTM D 4305). There is a small bias between the flow point t e m p e r a t u r e a n d the freezing point
temperature. This procedure can also be used to investigate
the formation of wax crystals or cold flow properties of other
products.
As low temperatures can materially affect the aircraft fuels, low temperatures can also affect the aircraft turbine lubricants (ASTM D 2532). On prolonged standing at low temperature, a structure can form in the lubricant, causing an
increase in the kinematic viscosity of the lubricant. This viscosity increase can cause lubrication problems in aircraft
engines. Thus, kinematic viscosity is measured typically
at - 6 5 F (-53.9C) by allowing the test sample to soak in
the viscometer at test temperature for periods of 35 min, 3
h, a n d 72 h. The percent increase in kinematic viscosity over
the initial m e a s u r e d value at 3 h or/and 72 h is also
reported.
Bath
1
2
3
4
5
Start to 10
10 t o - 7
-7 to-24
- 2 4 to - 4 1
- 4 1 to - 5 8
3ta- a4LB.
IP 444/99
No.
D 97
D 2386
D 2500
D 2532
IP 445/99
D 3117
D 4305
D 5771
D 5772
D 5773
D 5853
D 5901
D 5949
D 5950
D 5972
D 5985
D 6749
Title
Test Method for Pour Point of Petroleum Products
Test Method for Freezing Point of Aviation Fuels
Test Method for Cloud Point of Petroleum Products
Test Method for Viscosity and Viscosity Change After Standing at Low Temperature of Aircraft Turbine Lubricants
Test Method of Wax Appearance Point of Distillate
Fuels
Test Method for Filter Flow of Aviation Fuels at
Low Temperature
Test Method for Cloud Point of Petroleum Products
(Optical Detection Stepped Cooling Method)
Test Method for Cloud Point of Petroleum Products
(Linear Cooling Rate Method)
Test Method for Cloud Point of Petroleum Products
(Constant Cooling Rate Method)
Test Method for Pour Point of Crude Oils
Test Method for Freezing Point of Aviation Fuels
(Automated Optical Method).
Test Method for Pour Point of Petroleum Products
(Automatic Pressure Pulsing Method)
Test Method for Pour Point of Petroleum Products
(Automatic Tilt Method)
Test Method for Freezing Point of Aviation Fuels
(Automatic Phase Transition Method
Test Method for Pour Point of Petroleum Products
(Rotational Method)
Test Method for Pour Point of Petroleum (Automatic Air Pressure Method)
OTHER STANDARDS
No.
AFNOR M07-048
AFNORT60-105
DIN 51421
IP
IP
IP
IP
15/95
16
219/94
441/99
Title
Petroleum Products:
Determination
Point of the Dissipation Point of Aviation
Motor Fuel CrystcJs
Petroleum Products:
Determination
Point of Discharge
Testing of Mineral Oils; Determination of
Freezing Point of Aviation Fuels, Gasolines and Motor Benzols
Pour Point of Petroleum Products.
Freezing Point of Aviation Fuels.
Cloud Point of Petroleum Products
Pour Point of Crude Oils.
IP 446/99
ISO 3013
ISO 3015
ISO 3016
JIS K 2269
JIS K 2276
883
REFERENCES
[1] ASTM Research Report D02-1312, ASTM International, West
Conshoshocken, PA, 1993.
[2] SAE J305a: Extrapolated Oil Viscosities, SAE Handbook, Society of Automotive Engineers, Warrendale, PA, 1966, p. 299.
[3] "Development of Research Technique for Determining the LowTemperature Cranking Characteristics of Engine Oils," CRC Report No. 374, January 1964.
[4] Lowther, H. V., Meyer, W. A. P., Selby, T. W., and Vick, G. K., "Development of Research Technique for Determining the Low-Temperature Cranking Characteristics of Engine Oils," presented at
SAE Automotive Engineering Congress, Detroit, January 1964.
[5] "Prediction of Low-Temperature Cranking Characteristics of
Engine Oils by Use of Laboratory Viscometers," CRC Report No.
381, March 1965.
[6] Henderson, L. M. and Annable, W. G., "Pour Point Stability of
Lubricating Oils," Oil and Gas Journal, 9 Sept. 1943, pp. 54-59.
[7] Hodges, C. E. and Boehm, A. B., "Pour Point Stability of Treated
Oils Under Winter Storage Conditions," Oil and Gas Journal, 24
June 1943, pp. 103-6.
[8] Hodges, C. E. and Rogers, D. T., "Some New Aspects of Pour-Depressant Treated Oils," Oil and Gas Journal, 4 Oct. 1947, pp.
89-93, 99.
[9] McNab, J. G., Rogers, D. T., Michaels, A. E., and Hodges, C. E.,
The Pour-Point-Stability Characteristics of Winter-Grade Motor
Oils, SAE Quarterly Transactions, Vol. 2 No. 1, Jan. 1948, pp.
34-44.
[10] Moyer, R. G., "Low Temperature Pumpability of Oils," Journal
of the American Society of Lubrication Engineers, April 1962, pp.
165-168.
[11] Selby, T. W., "Viscosity and the Cranking Resistance of Engines
at Low Temperature," Sixth World Petroleum Congress Proceedings, Section VI, Frankfort, June 1963, pp. 241-258.
[12] McMillan, M. L. and Murphy, C. K., "The Relationship of LowTemperature Rheology to Engine Oil Pumpability," SAE National Automobile Engineering Meeting, Paper #730478, Detroit,
ML 14-18 May 1973.
MNL37-EB/Jun. 2003
Environmental Characteristics
of Fuels and Lubricants
Mark L. Hinman^
Fuels are seldom released into the environment intentionally. More often, the release is the result of spillage at transfer, during storage, disposal, or some unexpected event (e.g.,
transport collision, pipeline break, etc.). Some lubricating
fluids are intentionally introduced into the environment as a
function of their use (rail-flange grease, chainsaw oils, 2stroke oil passthrough residuals, etc.). For the remaining lubricants, between 13% (EU Countries) and 32% (USA) of
t h e m cire released to the environment after use. This results
in an annual worldwide loss to the environment of approximately 12 million tons [1].
Rationale for Standardized Testing
The potential for materials to cause harmful effects in the environment needs to be evaluated. The most straightforward
way to accomplish this might seem to be to evaluate organism populations in areas where the material has been released or spilled into the environment of interest. Although
field studies are the most realistic way of evaluating all possible chemical effects, they are usually impossible to quantitatively evaluate in terms of the level of the h a r m associated
with the magnitude of the release. This is because the expo-
885
Copyright'
2003 by A S I M International
www.astm.org
886
MANUAL
HANDBOOK
exchange and degradation rates may be combined in mathematical models to calculate the exposure concentrations and
the exposure-response relationship is used to estimate the environmental effects. Controlled laboratory test results can be
extrapolated to the environment because of the development
of predictive models ([2,3,4], E 978-92, Standard Practice for
Evaluating Mathematical Models for the Environmental Fate
of Chemicals).
Another benefit of standardized testing is that different
materials m a y be c o m p a r e d on a c o m m o n basis. For instance, testing toxicity with the same species of fish in water
of the same quality allows one to compare the relative toxicity of the substances. Such comparisons have led to the development of scientific relationships between the chemical
structures and their physico-chemical and biological properties. For example, when a homologous series of chemicals is
tested, such as alcohols of increasing carbon chain length,
there is a fairly continuous change in the physical properties
and toxicity. The predictable change may be used to extend
the result (through interpolation) to untested members of the
series. This process is often called "read-across."
Correlations developed between chemical structure, physical properties, and biological activity have led to validated relationships referred to as Quantitative Structure Activity Relationships (QSAR). The most widely accepted QSARs are the
relationship between the lipophilicity of a material and the
water solubility, soil sorption, bioconcentration, and toxicity.
The precision of the QSAR estimates for some classes of
chemicals has led to the acceptance of QSAR generated data
for some regulatory activities and substitution for missing
data [4].
PHYSICO-CHEMICAL PROPERTIES
A number of physical properties are especially relevant to the
environmental behavior of substances. Some of these characteristics (e.g., water solubility, vapor pressure, etc.) are measured on a routine basis for products. However, complex mixtures often require more detailed information about the range
of the property than pure substances (i.e., for a product that is
a mixture of components with greatly differing boiling points).
T5rpically, the boiling range is reported as a n average. When
the boiling range is broad, there is also a broad range in vapor
pressures of the components. This leads to differences in the
environmental compartmentcilization of the components. The
more volatile components will partition into the air phase to a
greater extent and so will be present to a lesser extent in the soil
and aquatic environments than the less volatile components.
Consequently, for substances with multiple components, specific test methods need to be applied eind reported which measure the range rather than the average of a property.
Chemical Structure
The properties of chemicals depend u p o n their chemical
structures. For fuels, this may involve a n u m b e r of hydrocarb o n structures having a range of molecular weights and
chemical types, as well as a variety of organic and inorganic
compounds included in additive treatments. Knowledge of
the relative hydrocarbon and specific additive composition is
important (see Table 1).
For lubricants, the structure types range widely. Mineral
hydroccirbon basestocks, synthetic basestocks, or plant oil
TABLE 1Physical properties that are of environmental importance (Adapted from Ref. 7).
Definition
Physical Property
Environmental Importance
Water Solubility"
Aqueous concentration at
saturation
Equilibrium concentration
between soil and water
Chemical Structure
OctanolAVater
Partition Coefficient" (Kow)
CHAPTER
34: ENVIRONMENTAL
CHARACTERISTICS
in
ifl
Water Solubility
The persistence, biodegradation, and toxicity of a material in
the aquatic environment are very dependent upon its water
solubility. Generally, the solubility of hydrocarbons decreases as the carbon n u m b e r increases [8]. However, this
parameter is cdso affected by the structure. Water solubility
will be different for linear, branched, and cyclic paraffins
with t h e s a m e c a r b o n n u m b e r . The m e a s u r e m e n t of this
characteristic Ccin be very straightforwEird:
Increasing additions of the pure material are made to water and the water analyzed until saturation is reached. The
analysis must be specific to the material.
An QSAR method is available for hydrocarbons that provide good water solubility estimates.
For complex mixtures, the individual components in the mixture have different water solubility limits. Once the least soluble component saturates the water, an undissolved phase
begins to form (typically at the water's surface). The remaining c o m p o n e n t s will partition between the water and the
undissolved phase and therefore never reach their individual
water solubility limit. The composition of the water extract
will be different than the composition of the complete mixture as it also depends on the ratio of material volume to the
water volume (Fig. 1). This solubility behavior is very complex. It should be remembered that the definition of solubility as it relates to pure substances does not readily apply to
complex mixtures [7].
100
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X
Pure Gasoline
0.01
887
100
888
MANUAL
HANDBOOK
Vapor Pressure
The vapor pressure of a substance is a measure of its tendency to enter the gas phase. This is important for determining both the rate of evaporation and the relative amount of
the substance that will be in the air phase. Vapor pressure
tends to decrease with increasing molecular weight, thus the
materials that are the most water soluble tend to have high
vapor pressures and move from the water to the air fairly
quickly [7,8]
For pure materials, direct pressure measurements may be
used. For materials with very low vapor pressure values or for
a mixture, a vapor saturation method is used. The stationeiry
medium in a generator column is coated with the material
and air is cycled over the medium until it is saturated [7].
Henry's Law Constant
Henry's Law Constant (HLC or H) is essentially the partition
coefficient of a material between air and water. It is important in estimating the degree and rate of volatilization of a
material from water into air. It may be measured directly by
analytical means within a test system or taken as the ratio of
the vapor pressure to the molar water solubility. Henry's Law
Constant is generally expressed as Pa-m^ / mole.
For complex mixtures, each component has a different water solubility and vapor pressure, so the HLC may cover a
wide range. The low water solubility and relatively high vapor
pressure of hydrocarbons result in high HLC values. Generally, an HLC value of 10 Pa-m^/mole or higher indicates that
volatilization is a significant fate process for the material.
Hydrocarbons are particularly likely to volatilize from water.
This is more likely for paraffins than for aromatics, which
have somewhat greater water solubilities. The solubility of
most substances decreases faster then the vapor pressure
with increasing molecular weight, so that the HLC values
increase with increasing molecular weight. For large
molecules, the vapor pressure becomes too low for volatilization to be an important fate process [7].
Adsorption / Desorption
Adsorption is the taking u p of a gas, vapor, or dissolved material on the surface of a solid. Desorption is the release of a
gas, vapor, or dissolved material from a solid under the same
conditions. The adsorption of organic chemicals from water
into organisms, sediment, or soil plays an important role in
the fate of materials. This process is also important in accumulation of materials by aquatic, sediment dwelling, and soil
organisms. The soil/water equilibrium also has a determining influence on the rate at which chemicals will leach into
ground water. For simple un-ionized organic chemicals, the
adsorption/desorption behavior is strongly affected by the organic matter contained in the soil or sediment.
This concentrating behavior is not always a simple linear
relationship and is usually described as an "isotherm." However, for most materials, the assumption of a constant distribution coefficient between soil and water (Ka) is adequate.
For organic substances, the important determinant of adsorption is the organic matter contents of the soil or sediment. As a result, the values for various soils/sediments are
"normalized" by calculating the partitioning coefficient be-
CHAPTER
34: ENVIRONMENTAL
CHARACTERISTICS
UV/Visible Light
889
Volatilization
Hydrolysis
\
Biotransformation - ^
- - Adsorption
Biological \ \
*
Uptake
\ \ Dissolved Organic
\ \ Materials
Biodegradation
/
Food Web Transfer
Suspended Particles
Sediment
FIG. 2Possible degradation pathways for a substance in the aquatic environment.
TABLE 2Examples of important environmental transport
processes (adapted from [7]).
Movement within Media
the atmosphere is composed of air and particulates. An important driving force for diffusive transport is the tendency of
a material to reach equilibrium between these phases. Partition coefficients quantify the equilibrium distribution of a
material between these different phases. The use of equilibrium partitioning theory is an important element of current
environmental fate assessments, since the form and compartmentalization of the material influences subsequent
transformations and accumulation processes in the environment [7].
Transformation Processes
Hydrolysis
Standardized tests have been developed to allow some prediction of the degradability of materials in the environment.
These are generally divided into chemical (abiotic) degradation and biodegradation tests. Standardized tests for determining the degradation rates are available from many Standards Developing Organizations (e.g., ASTM, ISO, etc.).
International Consortia (e.g., OECD, CONCAWE, etc.), and
Regulatory Bodies (e.g., U.S. EPA, Environment Canada, European Union, etc).
Abiotic degradation of fuels and lubricants is primarily due
to photolysis, hydrolysis, and photooxidation. These reac-
890
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
Solutions). Stability for more than a week indicates n o significant hydrolysis has occurred.
The bonds in most hydrocarbons do not tend to hydrolyze.
In general, only those materials with ester bonds are expected
to be affected by this process. Hydrolysis half-lives can range
from days to years for these materials, with the rate of hydrolysis of organic compounds increasing with temperature
in an exponential relationship [2]. Hydrolysis in not expected
to be a major fate pathway for hydrocarbon-based fuels and
lubricants, while synthetic and vegetable oil based lubricants
may be more susceptible.
Photolysis
Photolysis is a light-initiated transformation reaction that is
a function of the incident light energy (typically at wavelengths between 290 and 400 nm) and the structure of the
material. Different classes of molecules absorb sunlight
at different wavelengths a n d with different efficiencies.
Molecules need to have a strong adsorption band in this region to undergo significant photolysis in the environment, so
the UVA'isible spectrum of chemicals is used to screen for the
likehhood of photolysis (E 896-92 (1997) S t a n d a r d Test
Method for Conducting Aqueous Direct Photolysis Tests). It
is not necessary that the material directly absorb the light to
undergo photolysis. With indirect (or sensitized) photolysis,
an intermediary chemical becomes energized and then energizes the material of interest. Generally, phenols, furans, aromatic amines, sulfides, and nitro-aromatics are susceptible
to indirect photolysis [2],
Some polynuclear aromatic hydrocarbons (PAHs) can undergo a light-mediated increase in toxicity. Some intermediate weight PAHs, such as anthracene, fluoranthene, a n d
pyrene, have demonstrated photo-induced toxicity (greatly
enhance toxicity when compared to the inherent toxicity of
the material). When the PAH is present in the tissues of a n organism, phototoxicity can occur when UV radiation is absorbed by the molecule. The current theory is that oxygen
free radicals are produced that are highly oxidizing and can
destroy the molecules in the tissue [9].
Photooxidation
Atmospheric photooxidation is the degradation of chemicals
in air due to reaction with ozone or hydroxyl radicals and is
dependent upon the structure of the chemical, its concentration, and the ozone/hydroxyl radical concentration. Hydroxyl
radical attack is the predominant degradation mechanism
for alkanes, olefins, alcohols, and simple aromatics, which
are rapidly oxidized in air [2]. Hydroxyl radicals are produced through the interaction of sunlight with oxygen and
other substances in the atmosphere. The volatility of hydrocarbons and the rapid oxidation in air promotes photooxidation as a significant fate process for most hydrocarbons.
There is a significant amount of test data on the rate of hydroxyl radical reaction for chemicals that has allowed for the
development of effective QSAR models that ceJculate atmospheric half-lives.
Biodegradation
As indicated by the name, biodegradation is the biologically
mediated transformation of a material. The microorganisms
891
Categories
Ultimate
Ease of
Biodegradation
Measurement
Properties
Measures total conversion to inorganic forms (e.g.,
CO2, etc.)
Mineralization
Based on analysis of specific chemical or chemical or
chemical class
abiotic losses controlled
O2
CO2
CH3
Primary
Specific Analysis
Removal
Specific Analysis
Ready
O2
CO2
Primary biodegradation
Both abiotic and biodegradation
Regulatory definition of "rapid" biodegradation
Uses <30 mg/L non-adapted inoculum
reaches minimum 60% degradation to O2 or CO2 or
70% removal of DOC in 28 days
must go from 10% to the pass level (60 or 70%) in 10
days
DOC
Inherent
O2
CO2
CH3
DOC
Specific Ansilysis
Specific Analysis
Simulation
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Day of Test
FIG. 3Typical biodegradation curves for the same material when analyzed for different endpoints (adapted from [7]).
carbon (DOC) is more rapid than the utilization of O2 or the
production of CO2 (Fig. 3). Table 4 provides a list of commonly used standardized tests, the general characteristics of
the test, Emd general applicability.
Comparing the results from different test methods for the
same or similar materials can be problematic. The "percent
biodegradation" is very dependent u p o n what type of
biodegradability was tested. A result of 100% p r i m a r y
degradation in an inherent test cannot be compared to the
results of a Ready test, where 100% mineralization is not
possible emd where conditions are much more stringent.
Even within similar test methods, the inoculum makes a
great deal of difference in the outcome of the test. The number of competent organisms greatly affects the duration of
the lag phases. If the n u m b e r of these organisms in sewage
sludge is low, different tests could show either good
biodegradation or none at all. The microorganisms in the
inoculum may vary significantly over time. The tests for
biodegradation, even using a "standard" inoculum, will give
much more variable results than the tests for physical properties or toxicity. As a result of this and various complications resulting from use of inappropriate tests for the physical characteristics of the material, the comparison of
biodegradability between materials is only quantitative if
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894
MANUAL
HANDBOOK
they are tested in the same test systems using the same ino c u l u m p r e p a r e d at the same time. The major use of
biodegradation tests is to provide an estimate of the potential of a material to degrade in the environment.
In general, hydrocarbons are biodegradable to varying degrees [14,15]. Fuels and lubricants are mixtures with some
components having low water solubility. This low water solubility often limits the concentration in solution and thus
their availability to the microorganisms. The aromatics tend
to be slightly more water-soluble and give "better" results in
standardized tests than the paraffins. Among the paraffins,
the linear hydrocarbons are considered more biodegradable
t h a n the branched hydrocarbons. This results from microbial
oxidation of one end of the linear molecule to a carboxylic
acid. The metabolic processes in nearly all organisms can
easily degrade the resulting fatty acid. The presence of
branching hinders degradation to some extent.
Much of the older data for volatile hydrocarbons used the
Closed Bottle test (OECD 301D)[12]. This is an un-stirred test
system with a low inoculum. Using this method resulted in most
of these hydrocarbons being considered as non-Readily
biodegradable. Recent testing of the same materials using the
Manometric Respirometry Test system (OECD 30IF)[12] has
identified many of them to be readily biodegradable (Fig. 4)[ 16].
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'
Accumulation Processes
Accumulation processes result in the transfer of a substance
from a primary environmental m e d i u m (e.g., air, water, soil,
and sediment) to a plant or animal. Materials that pose the
greatest concern for accumulation potential enter the environment from diffuse sources, are poorly degraded in the primary medium, exhibit a high affinity for lipids, and are resistant to the metabolic breakdown by plants and animals (E
T
3
T
7
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20
24
Day Of Test
^^J^
Termination
TABLE 5Comparison of acute and ciironic environmental toxicology tests (adapted from [7]).
Test
Onset of effect
Concentration of test material
Exposure frequency
Test duration
Chronic
Acute
Objective
28
Sudden or delayed
Delayed
Relatively high
Relatively low
Static
Static renewal
Continuous (Flow-through)
Pulsed
Static renewal
Continuous (Flow-through)
Pulsed
Mortality
Immobilization
Changes in growth rates (algae)
CHAPTER
34: ENVIRONMENTAL
CHARACTERISTICS
OF FUELS
AND LUBRICANTS
895
HANDBOOK
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899
900
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
the LCso calculation may be based upon the measured concentrations [20].
Low
Solubility
There are a n u m b e r of issues related to low solubility materials. The acute LC50 values for a homologous series of chemicals may sometimes seem confusing. In general, the members of the series with lower water solubility will have greater
toxicity. However, as the n u m b e r of carbon atoms in the series increases, the water solubility decreases. The decrease in
solubility is usucJly greater than the increase in toxicity. So a
point will be reached when no acute mortality is evident. This
is sometimes referred as the "solubility cut-off." Larger members of the series are too insoluble to cause acute mortality
(Fig. 6). Although it is possible that the small amount of the
larger members in solution may cause chronic toxicity and
may contribute to the acute toxicity caused by other dissolved substances, they contribute little or no acute toxicity
unto themselves. Further additions of a single material above
its solubility limit will not increase the dissolved portion that
is absorbable by the test organisms, a n d therefore is not
bioavailable. The conclusion of these tests should be "no
acute toxicity at the m a x i m u m water solubility of the substance."
Sometimes tests are conducted as limit tests. These are tests
in which the substance is added in an a m o u n t greater than its
solubility to meet arbitrary toxicity limits (usually regulatory), such as 100 mg/L. In this example, if less than 50% mortality is observed, the LC50 is reported as >100 mg/L and is
considered to have minimal toxicity. There are two potential
sources of error inherent in this approach:
The presence of minor components that are water-soluble
may affect the results. At additions above the water solubility of the main substance, the contaminants may continue to dissolve and may constitute a higher percentage of
the water solution than the substance itself. In these cases,
the toxicity observed is generally erroneously ascribed to
the main substance.
a. S
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v..-js!if-.:A'.v-;'r'.':"''-'L!--'' ,
^ >.(iV;7.':><'f;',jiS';r,;:,i.,.Xi .1
'f>viTSr'!ift'Vr'fsdl'iibility is less than.Lc;
<-i -'^'''il'Jo' w ' - . ' . - i
-5 rt''t>.'.,,i,'.T.-^ ', and (toxicity
toxicity is not expect
-6 -r4
-.X-
10
12
14
Carbon Number
Igggi Log Water Solubility of n-Paratfin (mM / L)
The occurrence of physical effects caused by the undissolved test material. Such effects may become confused
with the chemiccJ toxicity of the bioavailable portion. Examples of such problems cire the fouling of fish gills by oil
droplets, which causes suffocation, or surface entrapment
of Daphnia in a surface film of a chemical, causing immobility (an endpoint in the Daphnia acute toxicity test).
In some cases, emulsifiers or solvents are used to attain solution of poorly soluble substances. Generally, these aids only
speed dissolution to equilibrium and do not significantly influence solubility. If there is n o associated toxicity with these
dissolution aids, there is n o problem with this procedure. If
large amounts of such materials are used and the water properties are significantly affected, material a m o u n t s may be put
into solution above its water solubility. In this case, there are
concerns with this approach. It may distort the environmental conditions prevailing in the test system a n d may significantly alter the test results, which further complicates its interpretation [20].
Complex
Mixture
Toxicity
Fuels and lubricants do not consist of a single chemiccJ compound. Some products consist of isomers with a similar number of carbons that differ primarily in branching pattern. As
a result, the toxicity of these materieds is similar between individual components, since isomeric differences tj^sically
have little effect on aquatic toxicity. In contrast, other materials are composed of components that vary significantly in
carbon n u m b e r and chemical characteristics. Consequently,
evaluating the toxicity of these materials is more complicated
and involves both the amount and toxicity of individual components. Most hydrocarbons are believed to be toxic by the
same mode of action and so are considered to have additive
toxicity. Thus, the toxic unit (TU) approach can be used to
predict the acute toxicity of such products [21]. This approach involves the following steps:
1. A TU for each component in the product is determined. A
TU is defined as the aqueous concentration of the component divided by the component's corresponding LC50.
2. The TUs for each component in the mixture are summed.
3. If the s u m of TUs > 1 , toxicity is expected; whereas, if the
sum of TUs is < 1, toxicity is not expected.
For complex mixtures of poorly water-soluble substances,
another challenge becomes apparent in testing and evaluating the results. For complex mixtures there is n o exact definition of water solubility. Each component may have a different water solubility so that with increasing additions of the
substance to water, some components reach their solubility
limit, become insoluble and float on the surface, while other
components continue to dissolve. In fact, a complex equilibrium is established between the insoluble chemical component phase (usually at the surface) and the water, never quite
reaching true saturation for any but the least soluble component (Fig. 1).
Additions of a complex material to water at levels beyond
the water solubility of the components results in a solution
and a toxicity measurement which does not accurately reflect
the composition or toxicity of the complete material. Some
scientific and regulatory organizations have suggested using
the "Lethal Loading" approach to overcome these difficulties
901
Toxicity
Tests
Tests With
Algae
Cultures of algae in their exponential growth phase are exposed to various concentrations of a substEince over several
generations under defined conditions. Cell density is determined by microscopic counting of cells or by a spectrophotometric m e a s u r e m e n t of chlorophyll. The inhibition of
growth in relation to a control (non-exposed) culture over a
fixed period of time is determined. The algal cell density in
each flask is determined at 24, 48, and 72 h (and 96 h for
some test methods) after the start of the test. The mean cell
density for each concentration is plotted against time to
produce growth curves. The growth endpoint is determined
by comparing the area under the growth curves for each
concentration against the control. The average specific
growth rate (the increase in cell density over time) is also
evaluated (D 3978-80 (1998) Standard Practice for Algal
Growth Potential Testing with Selenastrum capricomutum;
902
HANDBOOK
E 1218-97a Standard Guide for Conducting Static 96-h Toxicity Tests with Microalgae). Examples of growth curves and
exposure-response curves (for both endpoints) for the effects of Light Naphtha on Selenastrum capricomutum are
depicted in Fig. 7. Because several generations of algal cells
are exposed in this test system, it is sometimes referred to
as a chronic test.
Tests With Invertebrates
Acute toxicity tests with invertebrates generally expose organisms to a potentially toxic substance for 2-4 days. This period of exposure encompasses at least one sensitive period of
growth during the juvenile life-stage. In the acute immobilization test with Daphnia, effects on the swimming capability are investigated. The number of immobile organisms for
each concentration is compared to the control to calculate
the ECso value. An example of the exposure-response curve
100
ii 3 x
0 (0
."- o>
t - *-
80
60
*0
4U
20
S!
DC
FIG. 7Exposure-Response curves for acute toxicity tests with algae, Daphnia,
and Rainbow Trout for exposure to light naphtha (adapted from [7]).
CHAPTER
34: ENVIRONMENTAL
Invertebrates
CHARACTERISTICS
903
Toxicity
Tests
Toxicity
Tests
Fish
Tests With
Plants
Worms
904
MANUAL
HANDBOOK
SUMMARY
Over the past decade or more, n u m e r o u s standard testing
methods and computer-based predictive models have been
developed to help assess the environmental persistence,
biodegradation, and toxicity of materials. Most of these
m e t h o d s have been developed for simple, soluble, nonvolatile substances. In contrast, most fuels and lubricant
products are not defined as such, but rather are mixtures
(simple and complex) of organic molecules, often relatively
insoluble in water, and/or volatile. Further, additives can introduce metals and other inorganic compounds into the mixture. Nevertheless, the same standard methods were and are
used to test these products. This often produces misleading
results and interpretations.
In a mixture, each c o m p o n e n t has properties that are
unique to its structure and composition. As such, a range of
values for a specific characteristic is often more meaningful
than the average value when describing mixtures. Care must
be taken when choosing the test method for producing these
values. Characteristics such as water solubility, vapor pressure, dissociation constant, and sorption can render a specific test method inappropriate for many of these materials.
In many cases, the results of different test methods for the
same basic characteristic (e.g., biodegradation) cannot be directly compared.
Toxicity testing of these materials requires that specicJ
care and consideration be given to the characteristics of the
material. The key to any toxicity test is ensuring that the
test organism is properly exposed to the material being
tested, thus the preparation and maintenance (or appropriate quantification) of the exposure matrix is critical to the
success of the test. For fuels and lubricants, the "Lethal
Loading" approach is preferred when developing informa-
tion on the quantity of released material that might be required to initiate significant ecological risk or for labeling.
This approach is not a reliable surrogate for quantified exposure data. An uninformed reader may confuse the loading
values for the exposure values (which are usually much
smaller than the loading values) and underestimate the inherent toxicity of a material. Various standards, practices,
and guidelines have recently been published that address
the different approaches that are successful and those that
aren't for difficult to test materials.
Terminology
Acute
Aerobic
Anaerobic
BAF
BCF
Bioaccumulation
Bioaccumulation
Factor
Bioconcentration
Factor
Biodegradation
Biota-Sediment
Accumulation
Factor
CHAPTER
BSAF
Chronic
Dissolved
Orgcinic
Carbon
DOC
EC50 or EC50
Effect
Henry's Law
Constant
HLC
Incipient LC50
Indicator
Species
Inherent
BiodegradabiHty
Inhibition
Concentration xx
34: ENVIRONMENTAL
CHARACTERISTICS
Inoculum
LC50 or LC50
Lethal Load xx
Loading Rate
LOEC
Lowest Observed
Effect
Concentration
Median Effective
Concentration
Median Lethal
Concentration
OF FUELS
AND LUBRICANTS
905
Living spores, bacteria single celled organisms, or other live materials that are
introduced into a test medium (D 638499a).
See Octanol-water Partition Coefficient.
See Median Lethal Concentration.
A statistically or graphically estimated
loading rate of test material that is expected to be lethal to xx% of a subpopulation of organisms under specified conditions.
DiscussionThis terminology should be
used for lubricants instead of the standard LCxx to designate that the material
is not completely soluble at the test treatment rates (D 6384-99a).
The ratio of test material to water (in
mg/L) used in the preparation of a WAF
[20].
See Lowest Observed Effect Concentration.
The lowest concentration of a material
used in a toxicity test that has a statisti
cally significant adverse effect on the exposed population of test organisms compared with the controls. Also called the
lowest observed adverse effect level
(LOAEL) [26].
The concentration of a material in water
to which test organisms are exposed
that is estimated to be effective in producing some sublethal response in 50%
of the test organisms. The EC50 is usually expressed as a time-dependent
value (e.g., 24 h or 96 hr EC50). The sublethal response elicited form the test organisms as a result of exposure to the
test material must be clearly defined.
For example, test organisms may be immobilized, lose equilibrium, or undergo
physiological or behavioral changes
[26].
The concentration of material in water
to which test organisms are exposed that
is estimated to be lethal to 50% of the
test organisms. The LC50 is often expressed as a time-dependent value (e.g.,
24 h or 96 h LC50; the concentration estimated to be lethal to 50% of the test organisms after 24 or 96 h of exposure).
The LC50 may be derived by observation
(i.e., 50% of the test organisms may be
observed to be dead in one test material),
by interpolation (i.e., mortality of more
than 50% of the test organisms occurred
at one test concentration and mortality
of fewer than 50% of the test organisms
died at a lower test concentration, and
the LC50 is estimated by interpolation
between the two data points), or by calculation (i.e., the LC50 is statically de-
NOEC
No Observed
Effect
Concentration
Octanol-Water
Partition
Coefficient
Primary
Biodegration
QSAR
Quantitative
Structure
Activity
Relationship
Readily
Biodegradable
SAR
Sorption
Structure-Activity
Relationship
Toxic Unit
Toxicity
TU
Ultimate
Biodegradation
WAF
Water
Accommodated
Fraction
Water Soluble
Fraction
WSF
REFERENCES
[1] Bartz, W. J., "Lubricants and the Environment," Tribology International, Vol. 31, Nos. 1-2, 1998, pp. 3 5 ^ 7 .
[2] Lyman, W. J., "Transport and Transformation Processes, in
Fundamentals of Aquatic Toxicology: Effects," Environmental
Fate and Risk Assessment, G. M. Rand, Ed., Taylor & Francis,
Washington, DC, 1995, pp. 449-492.
[3] Mackay, D., Bums, L. A., sind Rand, G. M., "Fate Modeling, in
Fundamentals of Aquatic Toxicology: Effects," Environmental
Fate and Risk Assessment, G. M. Rand, Ed., Taylor & Francis,
Washington, DC, 1995, pp. 563-588.
[4] Lipnick, R. L., "Structure-Activity Relationships, in Fundamentals of Aquatic Toxicology: Effects," Environmental Fate and
Risk Assessment, G. M. Rand, Ed., Taylor & Francis, Washington, DC, 1995, pp. 609-656.
[5] Cisson, C. M., Rausina, G. A., and Stonebraker, P. M. "Human
Health and Environmental Hazard Characterization of Lubricating Oil Additives," Lubrication Science, Vol. 8, No. 2, 1996,
pp. 145-177.
907
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
MNL37-EB/Jun. 2003
ELECTRONIC, automotive, aerospace, forestry, naval, and numerous others. Lubrication failure m a y result in thousands
of dollars of p r o d u c t i o n losses including downtime a n d
equipment failure. Therefore, the general area of lubrication
is one of the most important in industrialized societies.
A lubricant may be a gas, a liquid or a solid and operates by
preventing direct interfaciaJ contact of surfaces in relative
motion to each other and/or minimizing damage when interfacial contact does occur. In this chapter, the fundamental
concept of lubrication a n d w e a r will be discussed. Wear
surfaces, contact geometry and stress, wear mechanisms,
materials properties, and lubrication mechanisms will be addressed. Wear mechanisms will include corrosive, abrasive,
adhesive, fretting, ploughing, and rolling contact fatigue failure. Identification a n d troubleshooting of these w e a r
regimes, particuleirly with respect to bearing and gear wear
under varying lubrication regimes, will be included.
This is the first in a series of three chapters; Chapter 35 (Lubrication Fundamentals), Chapter 36 (Bench Test Modeling),
and Chapter 37 (Lubrication Friction and Wear Testing). In
this chapter, the fundamental principles involved in lubrication and wear processes and how these basic principles are applied to lubrication testing will be discussed. In Chapter 36,
the most commonly encountered bench tests will be discussed
in detail. In addition to describing all of the pertinent engineering details of the standardized tests such as wear contact
conformity, loading, speed, reciprocating or linear motion,
and testing principle being measured, this chapter will provide guidelines for actual testing such as test selection, cleaning, material pair chemistry, and other factors related to currently existing bench tests and those in development. In
Chapter 37, the elements and application tribological design
as it relates to new test development will be outlined in detail.
ASTM G 40 defines tribology as "the science and technology concerned with interacting surfaces in relative motion,
including friction, lubrication, wear and erosion." Since this
chapter addresses basic design principles of tribological
processes involved in lubrication and weeir testing, various
equations are utilized. The applicability of these relationships to tribological testing is an important consideration.
The structure of this chapter is to first address basic principles involved in friction and wear. After friction and wear,
principles of fluid lubrication will be discussed. The last sec-
DISCUSSION
Friction
The ASTM D 996 definition of friction is "resistance to relative motion of two bodies in contact." The force (Fp) that
must be applied to an object to initiate and maintain relative
motion is proportional to the applied load (L). The proportionality constant is the coefficient of friction (/A).
F = liL
There are two values reported for the coefficient of friction.
The static co-efficient of friction is used in reference to the initial movement of the object from the rest position and is defined by ASTM D 996 as "the ratio of force required to move
one surface over another, to the total force applied normal to
those surfaces, at the instant motion starts." The kinetic coefficient of friction is used for two surfaces in relative motion
and is defined by ASTM D 996 as "the ratio of force required
to move one body over another, to the total force applied normal to those surfaces, once that motion is in progress." Representative of diy static and kinetic coefficients of friction for
various material pairs are provided in Table 1[1]. It has been
suggested that the best material pair candidates for non-lubricated contacts should exhibit ;u, < 2 [2].
Factors that affect dry sliding friction include [3]:
1. True area of contact between the sliding surface
2. Bond strength between the two bodies at the contact interface
3. Mechzinism of material shear and rupture processes in the
contacting region
The coefficient of friction is often used as a measure of the
transition between boundary lubrication and elastohydrodynamic (EHD) lubrication. The transition between these two
regimes is designated as either "mixed" lubrication or "mixed
EHD." Variation of the coefficient of friction with increasing
film thickness between two metal surfaces is shown schematically in Fig. 1 [4].
Area of True
' Department of Mechanical Engineering, University of Alaska Fairbanks, P.O. Box 755905, Fairbanks, AK 99775-5905.
^ G. E. Totten & Associates, LLC, P.O. Box 30108, 514 N. 86* St.,
Seattle, WA 98103.
909
Copyright'
2003 by A S I M International
Contact
www.astm.org
/x (Static)
/A (Kinetic)
0.78
0.74
0.21
0.70
0.42
0.42
0.57
0.95
0.61
0.6
0.04
0.04
0.53
1.10
0.51
0.85
1.05
1.05
1.10
0.33
0.35
0.34
0.95
0.47
0.46
0.53
0.53
0.44
0.30
0.21
0.29
0.32
0.43
1.40
0.15
0.22
O
-I-'
LL
d
^
O
0.020.01
o
O
Adsorption! Multiple Multiple Multiple
iLayer
: Reaction Reaction 1 Reaction
i Layers
Layers
! Layers
+
+
Liquid
Liquid
Film
Layers
FIG. 1Dependence of coefficient of friction (/u) on the layer thickness between two
metal sliding contact pairs.
Although conceptually illustrative, in practice the calculation of the coefficient of friction is much more complex requiring the integration of other interfacial bonding and failure modes including [5]:
1. area of true contact
2. friction due to adhesion
3. friction due to ploughing
4. friction due to deformation
Adhesion, ploughing, and deformation are wear processes
that will be described in detail subsequently.
Another wear mode is scuffing, which ASTM G 40 defines
as "a form of weeir occurring in inadequately lubricated tribosystems that is characterized by macroscopically observable changes in surface texture, with features related to the
direction of relative force." Alternatively, ASTM D 4175 defines scuffing as "surface damage resulting from localized
welding at the interface of rubbing surfaces with subsequent
fracture in the proximity of the weld area." An acceptable
scuffing criterion for metals may be estimated from the plasticity index (i/*), which is dependent on the area of true contact [5]:
^=
where : E is the elastic modulus,
Py is the yield pressure,
cr is the root mean square average asperity height
and
P is the radius of contact.
It ^< 0.6, the contact is classified as elastic and if ^ > 1,
the plastic deformation will occur within the contact. From
this relationship, the area of true contact (Ar) is estimated [5]:
For elastic contact:
Ar-
wY
^ Py
911
Table 2 provides a correlation of A factors with fatigue cracking of roller bearings [8]. T3^ically, A factors of 1.2-1.5 are
used for bearing life calculations [9]. Representative surface
roughness values for different types of bearing applications
are summarized in Table 3 [3,8].
The Lambda ratio provides Ein indication of the lubricant
film thickness relative to the surface roughness (asperity
height <T) and clearly ought to be greater than 1 if asperity
contact is to be minimized. Table 2 illustrates reported levels
of damage and fatigue cracking for roller bearings as a function of Lambda value [8].
Increasing Lambda values provide greater fatigue life. In
addition to the general observations indicated in Table 2,
Zaretsky a n d Moyer [10] described this relationship for
rolling element bearings. Townsend a n d Shimski showed
that increasing Lambda values increase surface fatigue life of
gears, as shown in Fig. 5 [11]. The Lambda factor relationship also means that as the surface asperity size increases (increasing surface roughness), the thickness of the lubricating
film m u s t also increase to maintain the magnitude of the
Wear Observation
< 1.0
1-1.5
1.5-3.0
a3.0
/im (rms)
Large Industrial
Industrial Off-the-Shelf
Aerospace
0.25
0.12
0.65
Height (^m)
Depth (|i,m)
Width (|im)
FIG. 4Illustration of surface roughness. The peaks covering this sample area
are called "asperities."
(U.in (rms)
10
5
25
913
(a) M-system
5
I
I
&
/lin
Grade
50
25
12,5
8.3
3.2
1.6
0.8
0.4
0.2
0.1
0.05
0.025
2000
1000
500
250
125
63
32
16
8
4
2
1
N12
Nil
NIO
N9
N8
N7
N6
N5
N4
N3
N2
Nl
1 '^
\Zi\
Ra = N
"ll/2
^ ^ '
Kn
Rt
Conformity
Arithmetic
Average (Ra) /iM
ju.m.
Gears
Plain Bearing-Journal
Plain Bearing-Bearing
Rolling Elements
Rolling Bearing
Tracks - Roller Bearing
0.25-10
0.12-0.5
0.25-1.2
0.025
0.12
0.1-0.3
10-400
5-20
10-50
1-5
5
4-12
FIG. 7The geometry of the contacting surfaces are classified as conformal or non-conformal (or counter-formal).
Pressure-,
(a)
I Outlet Region
(b)
FIG. 8a) Hertzian contact region, b)
Hertzian contact area.
equations of elastic deformation." The pressure at this contact is called the Hertzian Contact Pressure and is defined by
ASTM G 40 as: "the magnitude of the pressure at any specified location in a Hertzian contact area, as calculated from
Heitz's equations of elastic deformation."
The geometry of a tribocontact is usually defined as a point
contact (ball or pin-on-disk), line contact (vane-on-ring,
roUer-on-disk), emd area contact (flat surface-on-disk). Tribo-
CHAPTER
35: LUBRICATION
contact classifications are illustrated in Fig. 9. However, contact geometry may veiry. Contact geometry affects the load
actually applied, surface area, and conformation. Contact geometry, taken together with other variables such as sliding
speed, material chemistry, and the physical and chemical
properties of the lubricant presents a specific tribological
problem. This is important because a bench test is selected to
evaluate certain lubricating properties of a fluid/additive system with a specific material pair of interest or to model real
wear systems of interest in industrial equipment. Therefore,
the specific contact geometry selected for wear testing is dependent on the tribological system being modeled (or generated) by the test. Figure lOa-h illustrates eight different wear
contact variations that may be used with a single test machine, including the well-known 4-ball test [15]. (Other test
geometries are also possible.) Bench tests, such as the 4-ball
test, are often used to examine lubricant additive reactivity
[15]. However, ranking of lubrication properties depends on
the test conditions and performance criteria.
Line
Area
Point
H
FIG. 10Illustration of various tribocontact geometries that were used by
Matveesky with a 4-ball machine: a) four
ball, 8 mm dia. balls made from chromium
steel Re = 61-62; b) four roller, 5 mm dia.
rollers and 45(contact; c) ball-ring, ball
from chromium steel of Re = 61-62, dia.
12.7 mm, ring from different materials
with geometry-20 x 18 x 4 mm; d) diskball; ball from chromium steel, Re =
61-62, d = 8 mm, disk from different materials with geometry 60 x 18 x 4 mm;
e) ball-three-roller; ball from chromium
steel. Re = 61-62, d = 12.7 mm, 5 mm dia.
rollers made from different materials;
f) ball-three plates, ball and materials the
same as: "e"; g) conical-ring, cone (110),
geometry of ring 20 x 8 x 4 mm; h) ballplate, plate from different materials with
geometry 40 x 40 x 5 mm, ball from
chromium steel Re = 61-62 and d = 8
mm.
AND TRIBOLOGY
FUNDAMENTALS
915
916
xlO
5
T^
o'
HANDBOOK
A
'
2" 2
1
T^
0
0.1
(a)
10
too
Contact pressure ,
woo
M Pa
xlO,
xlO
XlO
3
3
'in
1
0
XlO
,X
T^"
partial plane
7 contact
6
S
4
3 ("whole
,
plane contact
0.01
(b)
0.1
S l i d i n g velocity ,
1
m-s'
CHAPTER
35: LUBRICATION
AND TRIBOLOGY
FUNDAMENTALS
917
EHD/Mlcro-EHD Films
(<1nm)
Surface Films
(<1nm)
Lubricant
Near Surface
(< 50 urn)
Residual
Stress
(Bulk)
Hardness
(case)
Principal
Shearing
Stress ( X )
Subsurface
(<50-1000^m)
Core
Surface Films
Adsorbed,
Film
li
Oxide
Metal
Metal
FIG. 14Surface asperities and lubricating thin films determine tribological behavior and types of lubrication modes.
where:
= Voe
T? (r, P = 1 atm)
dP
V iP, T)
The advantage of a* is that all of the variations of viscosity
with pressure over the entire pressure range are included in
the calculation as illustrated in Fig. \5b [21],
In many cases, the value of a is not available. One early attempt to predict a for petroleum oils at pressures u p to 10 000
psi was reported by Fresco et al. [23]. Fresco's a- prediction
chart is shown in Fig. 16 and is based on the viscosity-temperature properties of a fluid, which are represented by the
so-called "ASTM Slope" [24]. The ASTM slope is the slope of
the viscosity temperature line of the McCouU-Walther equation that is plotted as described in ASTM D 341. In addition
to a graphical solution, it can also be calculated from:
ASTM Slope =
where: v is the kinematic viscosity and T is the absolute temperature. The ASTM slope is the slope of the viscosity-temperature line of the Walther equation that is described in
ASTM D 341. Note: The ASTM slope is n o t equivalent to the
value B in the Walther equation [25]:
log log {v + 0.7) = A - 5 log r
918
HANDBOOK
"OSIOK*"'
10
(a)
(b)
3x10'
Pressure (N/nf )
i
I
30 X 10'
20
Pressure (PSI)
Pressure
FIG. 15a) Viscosity-pressure beliavior witli aor and uos (Barus Equation); b) Illustration of a viscosity-pressure isotherm and the calculation of a*.
CHAPTER
35: LUBRICATION
AND TRIBOLOGY
FUNDAMENTALS
919
0.90
Surface
Films
There are numerous t5rpes of surface films that are used to reduce wear. Physical or chemical adsorption also provides a
protecting film for lubrication. A thin surface film is formed
by adsorption of polar lubricant molecules onto the surface,
providing an effective barrier against metal-to-metal contact.
Physical adsorption (vein der Waals adsorption or physisorption), as defined by ASTM D 2652, refers to "the binding of an
adsorbate to the surface of a solid by forces whose energy
levels approximate those of condensation." Chemical adsorption (chemisorption) is defined by ASTM D 2652 as: "the
binding of an adsorbate to a surface of a solid by forces
whose energy levels approximate those of a chemical bond
without the formation of a new chemical bond." Chemisorption may be irreversible.
2 3 45
10
20 30 50
100 200
500
1000
Both A and B are fluid dependent constants. Since fluid viscosity usually decreases with increasing temperature, the
slope of B will be negative.
The viscosity-temperature coefficient is obtained from the
first derivative of the McCouU-Walther equation and is equal
to [25]:
Slope B =
dr
The effectiveness of the adsorbed film is dependent on temperature. A thicker film provides better surface protection.
Two types of protective films, adsorbed films and reaction
films, are illustrated in Fig. 14, respectively [18]. Examples of
the use of adsorbed films that will reduce interfacial friction
include the ionically adsorbed (chemisorption) fatty acids on
steel (and other metal) surface layers as shown in Fig. 18 [ 18],
or the physical adsorption of hydrocarbons as illustrated in
Fig. 19 [18].
Metal surfaces may also be modified by the formation of
reaction films. Some reaction films are formed during heat
treating processes such as carburizing, carbonitriding and
nitriding. Others are formed in situ by surface chemical reactions between a n additive such as ZDDP (zinc dialkydithophosphates) as shown in Fig. 20 [18]. The formation of
a chemical film produced by a paraffinic base oil containing
ZDDP as an additive is illustrated in Fig. 20b. An illustration
of the ability of a n oil additive to reduce wear is provided by
comparing Fig. 3c and Fig. 21. Some surface films are formed
by tribochemical processes such as tribopolymerization
[37-40] during the lubrication process.
Surface topographical structure is shown in Fig. 22 [18].
Lubrication failure in this region will produce plastic flow
and failure mecheinisms such as ploughing caused by a hard
asperity sliding in the softer plastically deformed metal.
Various illustrations of ploughing wear are provided in
Fig. 3c.
Near Surface
Structure
Structure
Correlation
Kouzel
log ^
Roelands, Vlugter
and Wateman
=( P V
i g ^ = i5ooo; [ ( 0 . 0 0 2 C A
Reference
= 3 ^ ( 0 . 0 2 3 9 + 0.01638^;
[29]
[30]
3L
+ 0.003Cw
[31]
[32]
So and Klaus
log
Voj
[33]
a(98.1 XP)
log ( ^ ) = 16 log 1 +
[34]
for naphthenics
log (^]
Worster
Johnston
PEr
a, ICRT^
Shibada
a = 0 . 6 2 0 4 4 ^d"^'^
[35]
[36]
^2.04746 ^0.29292
[26]
^ 100,000
O, 10,000
"^
(0
o
o
(A
1000
Fluid
38C
99C
149C
2-Ethylhexyl Sebacate
Paraffinic Oil
Naphthenic Oil A
Naphthenic Oil A + VI
Improver'
Naphthenic Oil B
Polybutene (Mn = 409)
a. VI Improver = 4% PMA
(Mv = 560,000)
11
29
22
60
1.39
2.18
2.15
1.83
1.19
1.78
1.44
1.24
68
90
3.07
3.18
1.81
2.22
100
10
1
0.1
0
Paraffinic OH
Napthenic Oil
FIG. 18Adsorbed films which will reduce interfaclal friction include the ionic adsorbed fatty acids to
the steel (and other metal) surface layer.
AND TRIBOLOGY
FUNDAMENTALS
921
n-Hexadecane (Cetane)
(C16H34)
FIG. 19Physical adsorption of hydrocarbons. Note the weaker van der Waals interactions and related orientational effects between the hydrocarbon and the metallic substrate relative to those illustrated for chemisorbed additives illustrated in
Fig. 18.
922
HANDBOOK
FIG. 20Surface additive reactions are tribochemical processes which are driven by the conditions within the wear
contact. This is illustrated by the following examples: a) The
in situ reaction film is formed by surface chemical reactions
between an additive such as ZDDP (zinc dialkydithophosphates). b) Illustration of cracking of a chemical reaction film
produced on a gray cast iron surface lubricated with a paraffininc base oil containing ZDDP as an additive under a contact pressure of 16.7 MPa and at 135C for 17 h. The sliding
velocity was 1.4 m/s and the base oil viscosity was 0.053 Pa
at 38C. (Source: Prof. Hon So, Dept. of Mechanical Engineering, iviational Taiwan University, Taipei, Taiwan.)
CHAPTER
35: LUBRICATION
AND TRIBOLOGY
FUNDAMENTALS
923
Severe Deformation
Gross Deformation
Bulk
Wear Mechanisms
The primetiy wear mechaxiisras that occur in non-lubricated
contacts are: adhesive wear, abrasive wear, tribochemical
wear, and fatigue wear.
Adhesive
Wear
Adhesive wear occurs when surface asperities come into sUding contact under a load. If sufficient heat is generated, microwelding of the two contacting asperities with subsequent
shearing and material transfer will be observed, as illustrated
schematically in Fig. 28a. When two interacting surfaces are
not sufficiently lubricated, adhesive transfer or removal of
near-surface material may be observed. Surface adhesion is
dependent on the nature of the contacting surface. Wear material transfer in this region h a s been called "solid-phase
welding" (also known as the micro and macro-welding pro-
(a,b)
FIG. 25Gears may wear by several modes and the FZG test may be used to evaluate wear resistance by Identifying
failure modes. Illustration of various potential gear wear modes observed in the FZG gear test are shown here: a) pitting/spalling on a case carburized test gear; b) pitting/spalling from a micropitted area on a case carburized test gear; c)
severe micropitting on a case carburized test gear; d) pitting on a through-hardened gear in practice; e) rippling on a
case-carburized test gear; f) scuffing on a case-carburized test gear; g) severe wear on a case carburized test gear; h)
scuffing on a case carburized test gear (compare to Fig. 24 e on the same gear geometry); i. "tears" on a nitrlded test
gear; j) severe scuffing on a case carburized test gear. (Source: Dr. K. Michaelis, Lehrstuhl fur Maschine Elemente, Technical University of Munich, Munich, Germany.)
(g,h)
(i)
FIG. 25(continued)
T A B L E 8 P r o p e r t i e s of m e t a l l i c e l e m e n t s .
Metals
Melting
Temp.
(C)
Young's
Modulus (E)
Dyne/cm2
Aluminum
Cadmium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Tin
Zinc
660
270
1083
1534
325
650
1245
2.08
232
420
0.63
0.32
1.20
2.04
0.16
0.44
Yield
Strength (<7y)
109 Dyne/cm2
Hardness
(P) K=/mm^
erg/cm2
1.0
27
7
80
82
4
46
300
210
5.3
38
3.2
2.5
0.09
1.5
2.5
3.2
0.15
1.3
0.44
0.91
900
y+Fe,C
I
'
600 ^
Cementite ( FesC )
+ Pearlite
Ferrite + Pearlite
Pearlite
-1
0.0
11I1I
0.2
0.4
0.6
1
1.0
'
1
1.2
Surface
Energy
900
390
1100
1500
450
560
1700
570
790
2
tn
0)
T3
(U
_N
ID
. Ultra' Mild
Wear
Normalized Velocity V
FIG. 27Effect of steel martensitic structural transition on wear as
shown by a wear mechanism map for a non-lubricated sliding steel pinon-desk pair. Contours of wear rates (which are normalized) are superimposed on regions with different wear mechanisms. Wear rates in
parentheses represent mild wear. The transition between mild and
severe wear are indicated by the shaded area.
Ferrite
Comment
a) Surfaces
being pressed
together
(b)
(a)
(d)
FIG. 28Mechanism and illustration of adhesive wear, a) A schematic illustration
of the mechanism of adhesive wear, b) Illustration of adhesive wear with an Fe/IVIg
wear contact under the following conditions: 5 N/cm^, 1 m/s, > 10 l<m, 2x10"^ Torr
and n = 0.29. (Source: E. Santner, BAM, Berlin Germany.) c) Adhesive wear from an
AISI52100 steel ball on an AIS11045 steel disk under lubricated conditions loaded at
150N and sliding speed of 1.5 m/s (Source: Prof. Liu Jiajun, Tsinghua University, Beijing, PRC.) d) Adhesive wear from a lubricated AISI 52100 steel ball and an AIS11045
steel disk loaded at 300 N and a sliding speed of 2.0 m/s. (Source: Prof. Liu Jiajun,
Tsinghua University, Beijing, PRC.) e) Adhesive wear obtained with a medium carbon steel pair block-on-shaft, load = 110-184 N, 156-220 rpm and the picture has
750X magnification. (Source: Dr. Sergey Tarasov, Institute of Strength Physics and
Materials Sciences, Tomsk, Russia.) f) 2 steel ball on an SUS 304 3/8 inch brass
(YbsC2) ball on an 18 mm nickel disk with a test load of 14.7N, sliding speed of 1 m/s
over a 15 m distance and a vacuum of 10~^ Pa (Source: Prof. T. Kawazoe, Nagasake
University, Nagasaki City, Japan.) g) Severe adhesive wear with a 3/8 in SUJ stainless steel disk with a load of 49 N, sliding speed of 1 m/min, over a total distance of
15 m and a vacuum of 10~^ Pa. (Source: Prof. T. Kawazoe, Nagasake University, Nagasaki City, Japan.)
927
BS
(3/8" brass ball)
((|)18x*30Nidisk)
Ni - BS (1.5 kgf)
(f)
200^
I
x50
SUS 304
(({)18 X* 30 stainless steel disk)
(g)
SUJ2
(3/8" stainless steel ball)
(b)
FIG. 29a) Cam ring smearing damage and discoloration. (Courtesy of Caterpillar
Inc, Peoria, IL.) b. Hydraulic pump piston with polishing wear by a smearing mechanism. (Courtesy of Caterpillar Inc., Peoria, IL)
(a)
(b)
FIG.
30P!n-on-V-block
test results of an lubricant
showing: a) when the machine was sufficiently loaded,
a change of color (blueing)
was observed due to the high
frictional temperature of the
material pair; b) when the lubricant failed, welding of the
metal test specimens occurred resulting in adhesive
wear. (Courtesy of D. Drees,
Falex Triboiogy NV, Heverlee,
Belgium.)
929
930
MANUAL
HANDBOOK
obtained with two copper cylinders tested in a crossedcylinder geometric configuration u n d e r dry sliding conditions. This figure is an SEM photograph, which shows typical signs of galling or seizure, with grooves, a heavily
deformed surface layer, and material transfer.
The classic expression to quantitatively describe the volu m e (V) of adhesive wear debris removed for a given load (L),
on a material over the sliding distance (x) for a dry wear contact is known as Archard's equation.
V
k Lx
H
tan e
TTH
where dV/dl is the change in volume (dV) due to the wear that
is removed after sliding a distance dl, L is the load being applied, 0 is the angle of the hypothetical cone indenting the
horizontal surface, and H is the hardness of the softer surface.
Archard's equation shows that material hardness is an important variable in the wear process. However, hardness is a
complex value that is dependent on: position and time, temperature, sliding speed, and environment. Localized hardness
Zinc on Zinc
Low Carbon Steel on Low Carbon Steel
Copper on Copper
Stainless Steel on Stainless Steel
Copper on Low Carbon Steel
Carbon Steel on Copper
Wear
Constant
(k 3 103)
160
45
32
21
L5
0.5
Wear
Abrasive wear refers to the cutting of a metal by a hard particle or a rough surface by a ploughing or microcutting
(scratching) mechanism [10,48]. ASTM G 40 defines spalling
as: "the separation of macroscopic particles from a surface in
the form of flakes, or chips, usually associated with rolling element bearings and gear teeth, but also resulting from impact events."
Abrasive wear is dependent on particle size distribution,
shape, toughness (capacity of a material to absorb energy),
and hardness. Giltrow has demonstrated that an excellent, although non-linear, correlation exists between abrasive wear
and cohesive energy for both thermoplastic polymers and
metals [49]. Cohesive energy is that energy, composed of
physical and chemical forces, that holds the constituents of a
mass of material together. It is desirable to use a value such
as cohesive energy since it can be calculated based on chemical composition of the material and thus provides the opportunity to interrelate wear with chemical composition.
Giltrow reported that abrasive wear of many metals was inversely proportional to the cube of the cohesive energy and
inversely proportional to the square root of the cohesive energy of thermoplastic polymers [49]. Note: cohesive energy of
metals may be related to the latent heat of sublimation (at
25C) minus the work (RT) required to expand atoms beyond
their sphere of influence. Latent heats of metals are readily
available from thermodynamic tables [49].
The abrasive wear mechanism involves the penetration of
a surface by a hard particle that is subsequently embedded
into one of the wear surfaces. Abrasive wear occurs when one
of the contacting surfaces is harder than the other. The observed wear behavior involves plastic deformation and material displacement during ploughing or smearing. Ploughing
was described in the Friction Due to Ploughing section. This
results in surface-initiated fatigue spalling. EHD and microEHD films reduce or eliminate local surface plastic flow.
Abrasive wear m a y also be measured by determining the
wear volume, as discussed previously.
When abrasive wear is caused by a hard particle between
two surfaces, it is called three-body wear, as illustrated in Fig.
33a [50]. Hard particles causing three-body wear may be introduced into a system from the manufacturing process, gen-
V Bearing
surface
CHAPTER
35: LUBRICATION
AND TRIBOLOGY
FUNDAMENTALS
931
"Hard" Surface
"Soft" Surface
Cavitation Wear
Cavitation refers to the formation and rapid collapse, by implosion, of cavities or bubbles that contain vapor or gas or
both (ASTM G 15). The collection of a large n u m b e r of cavitation bubbles is called a cavitation cloud. The bubbles in a
cloud are small, typically less than 1 m m in cross section. A
surface that is being eroded by cavitation is typically obscured by a cavitation cloud (ASTM G 40). Different studies
have shown that every bubble in the cloud does not cause
damage upon implosion and that the damage frequency is reported to vary from 1 in 16 000 to 1 in 30 000. A cavitation
bubble m a y undergo multiple collapse a n d reformation
processes. A single bubble may undergo as many as seven collapse and reformation processes. A wide range of bubblecollapse pressures, u p to > 7 0 Mpa, have been reported [52].
Cavitation damage is exemplified by pitting and the formation of holes and craters on the wear surface, as illustrated in
Fig. 34.
(a)
'Soft" Surface
Hard" Surface
(b)
(d)
(c)
FIG. 33Mechanisms and examples of abrasive wear, a) Schematic illustration of a threebody abrasive wear model; b) schematic illustration of a two-body abrasive wear process;
c) illustration of abrasive wear: Fe/AI material
pair, 2.3 N/cm^, 1 m/s, ? 10 km, 5 x 10~ Torr,
and fji varies from 0.61-1.3 (Source: E. Santner,
BAM, Berlin Germany); d) abrasive wear obtained with AISI52100 steel ball on an AtSI Type
304 stainless steel disk, load = 150 N, sliding
speed = 1.5 m/s. (Source: Prof. Liu Jiajun, Tsinghua University, Beijing, PRC.)
Erosion
Wear
Wear
Corrosion wear is surface damage related to chemical electrochemical attack of a metal surface, resulting in significant
surface damage as illustrated in Figs. 36 and 37. Common
causes of corrosive wear include:
1. Water from humid air ingression and subsequent condensation, liquid water from spray or splash contamination,
water ingression from defective enclosure, cooling coil
leakage and water-contaminated lubricant.
FIG. 34Surface damage by pitting and cratering due to cavitation. (Reprinted with permission of IFAS, Aachen, Germany.)
932
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
plate in seawater. In this case, electrons wiU flow from steel
to copper, resulting in a deposit of iron oxide on copper. This
is gcilvanic corrosion.
Combinations
of Cavitation/Erosion/Corrosion
(a)
Wear
There are various combinations of cavitation/erosion/corrosion wear. These will be briefly summarized as defined by
ASTM specifications.
Cavitation CorrosionThis is a form of localized, accelerated
corrosion characterized by deep pitting and caused by high
mechanical forces resulting from coolant vapor bubble collapse at the surface of a metal. (ASTM D 4725)
Cavitation ErosionDefined as the loss of material from a
solid surface from exposure to cavitation. This may include
(b)
(c)
FIG. 37Corrosive wear obtained with
an AISI 52100 steel ball on cast iron with
0%, 5%, and 10% palm oil methyl ester
(POME) used added to an oil lubricant.
The test was conducted at 80C, 0.34 m/s
for 50 h. (Source: Dr. M. Maleque, Univ. of
Malasia, Kuala Lumpur, Maylasia.)
are complicated and they Eire still under investigation. Tribochemical wear can be controlled by the use of appropriate inhibiting additives.
Fatigue Wear
ASTM G 40 defines fatigue wear as "wear of a solid surface
caused by fracture arising from material fatigue." Material
fatigue, as defined by ASTM E 1823, refers to "the process of
progressive locedized permanent structural change occurring
in a material subjected to conditions that produce fluctuating
stresses and strains at some point or points that may culminate in cracks or complete fracture after a sufficient number
of fluctuations."
Fatigue wear prior to cracking is indicated microscopically
by surface pitting and spalling, which are caused by induced
subsurface shear stresses that exceed the critical shear stress
of the material. Pitting is defined by ASTM G 40 as "a form of
wear characterized by the presence of surface cavities the formation of which is attributed to processes such as fatigue, localized adhesion, or cavitation."
Spalling is defined as "the separation of macroscopic particles from a surface in the form of flakes or chips, usually associated with rolling element bearings and gear teeth but also
resulting from impact events." Various examples of pitting
and spalling due to fatigue wear processes are illustrated in
Figs. 39-41. Severe types of wear often involve scuffing, as
shown in Fig. 42.
Fatigue life is influenced by EHD lubricant film/surface
roughness ratio [10,11]. High localized stresses at surface defect sites, asperities, dents, and material inhomogeneity, will
reduce fatigue life [55b]. Figure 39 is an example of the fatigue wear in a diesel engine lifter. The effect of surface
roughness and lubricant film thickness on fatigue wear was
provided previously.
Bench tests may be used for fatigue evaluation. Figures 40
and 41 provide examples of fatigue wear evaluation using
bench test equipment. It should be noted that the fatigue lives
of nominally identical rolling contact bearings tested under
identical conditions could be widely different. This results in
the generation of a fatigue pit (see Fig. 41), which typifies incipient fatigue failure as dependent upon the action of cyclic
stresses and the motion of the rolling elements that randomly
contacted at asperities. The fatigue strength at N cycles, SN
(FL ^) of a material may be determined by ASTM D 1823.
(a)
FIG. 38Illustrations of oxidative wear, a) Oxidative wear obtained witli a medium carbon steel block-on-shaft lubricated
with a mineral oil in the presence of a copper nanometal additive, load = 110-184 N, 156-220 rpm and the picture has 750X
magnification. (Source: Dr. Sergey Tarasov, Institute of
Strength Physics and IVIaterials Sciences, Tomsit, Russia);
b) tribooxidation (oxidative wear) occurring om a Fe pin run on
a Co disk run under the following conditions: 14 N/cm^, 1 m/s,
> 10 km, 760 Torr and ft, = 0.25-0.28 (Source: E. Santner, BAM,
Berlin, Germany).
933
934
HANDBOOK
.->"- ..i.=^=,.--.
^pn
(a)
(b)
FIG. 40Examples of fatigue wear: a) Co pin/Fe disk material pair at 14 N/ cm^, 1 m/s, 710 km, 1 Torr, and
fi = 0.33-0.34. (Source: E. Santner, BAM, Berlin Germany.), b) An AISI52100 pin on an AIS11015 steel disk,
load = 15 kg, sliding speed = 500 rpm and lubricated with a liquid paraffin. (Source: Prof. Liu Jiajun, Tsinghua University, Beijing, PRC.)
Direction of Rotation
^
FIG. 41Pitting fatigue wear obtained with twin 60 mm rotating S25C carbon steel disks The /u value for the driver is 1.0 and
the ft value for the follower is 0.40. The load is 1.6 x 10^
''Hertz = 950 MPa, and the rotating pair was lubricated with a
paraffin oil at 2 L/min. (Source: Prof. T. Kawazoe, Nagasake
University, Nagasaki City, Japan.)
The SN value is a value of stress at exactly N cycles as determined by an S-N diagram. The value of SN, thus determined,
is subject to the same conditions as those that apply for the
S-N diagram [50].
Fretting WearFretting is small amplitude oscillatory motion, usucdly tangential, between two surfaces in contact and
fretting wecir is wear that results from fretting motion (ASTM
G 40). Fretting is a form of adhesive wear that may occur
when the tips of the asperities of adjacent moving surfaces
come into contact and microwelding occurs. Continued
surface movement causes the tip of microwelded asperities to
pull off, producing a pitting effect. The heat of the microwelding process enhances oxidation of the fresh metal surfaces. If water is present, corrosion will result (fretting
corrosion). Waterhouse has reported that the fretting process
of steel is dependent on amplitude of slip; frequency and
normal force of the oscillatory process; condition of the steel,
particularly hardness; and temperature and humidity of the
environment [56,57].
Fretting wear will occur in locations where there are oscillatory deflections of clamped joints, spline and gear couplings, and connecting rod joints in internal combustion engines. Fretting wear is often accompanied by the production
of finely powdered and oxidized wear debris [58].
The four regimes of wear that are dependent on the displacement amplitude have been observed by Baker and Olver
CHAPTER
35: LUBRICATION
[59]. These four regimes, which are shown in Fig. 43, are designated as:
Regime 1"Stick" occurs at very small amplitudes producing very little damage,
Regime 2"Stick-slip" occurs with increasing displacement and wear rates increase slowly,
Regime 3Gross slip produces severe damage by oxidation
assisted wear which is the "fretting wear" regime
Regime 4In this region, reciprocating sliding wear occurs
eind if the amplitude is sufficient, the wear rate becomes
approximately constant which is characteristic of unidirectional sliding wecir.
i 1 1 = Slip
2 = Stick-Slip
3 = Gross Stick-Slip (Fretting)
4 = Oscillating Wear
c
0)
o
!^
^__4____
/
(D
O
3 /
o(D
<4mJ
CO
,1
on
L_
CD
<D
^ -t ^
1 y"^
AND TRIBOLOGY
^^
935
eOOtim
lOOtom
(a)
FUNDAMENTALS
.e?^
(c)
(b)
FIG. 44Fretting wear test results obtained with aluminum alloys: a) Al-Li (2091) alloy, N = 5 x 10^ cycles,
Fn = 500 N, f = 1 Hz, cracl( depth is 200 fjitn; b) Al-Zn (7075) alloy, N = 10^ cycles, Fn = 1000 N, f = 5 Hz, crack
depth is 3500 /tm (Source: Z.R. Zhou, Southwest Jiaotong University, Chengdu, China.)
936
MANUAL
HANDBOOK
Scuffing
Scuffing is defined as "a form of wear occurring in inadequately lubricated tribosystems that is characterized by
macroscopically-observable changes in surface texture, with
features related to the direction of relative motion" (ASTM G
40). Surface texture is a term relating to surface finish, which
is described by the roughness (peak) height in microinches
and the n u m b e r of peaks per inch or it may be described as a
surface pattern relative to a smooth finish. In lubrication,
ASTM D 4175 defines scuffing as "surface damage resulting
from localized welding at the interface of rubbing surfaces
with subsequent fracture in the proximity of the weld area."
An example of scuffing wear is provided in Fig. 42.
The "Borsoff effect," which was originally published in
1959 [64], assumes that surfaces will scuff when adsorbed
(polar) molecules, which are used to provide extreme pressure (EP) activity, become critically depleted or disoriented.
A four-ball machine test was conducted to determine the
scuffing loads for hexadecane containing various concentrations of hexadecanoic acid. (The EN31 steel balls contained
1% chromium.) The rotational speed of the moving ball was
200 rpm. A plot of the scuffing load as a function of hexadecanoic acid is shown in Fig. 46 [65]. It was assumed that the
rotational speeds were sufficiently slow to permit molecular
response to the adsorption/desorption equilibrium process
and that scuffing occurred at the rear of the contact where
the contact temperature is maximum and surface coverage is
reduced to a constant, although unknown, value.
To explain this wear process. Spikes a n d Cameron assumed that scuffing failure will occur by an additive desorption process. At the point where this occurs, there is n o EP
activity that would be analogous to a base oil with no EP additives. This effect may be shown thermodynamically using
the Langmuir adsorption equation for adsorbed (physisorption) polar molecules [66,67].
1 - 0
kC exp
-AH
RT
CHAPTER
35: LUBRICATION
AND TRIBOLOGY
FUNDAMENTALS
600
0.002
0.004
Concentration (molar)
FIG. 46Scuffing load as a function of hexadecanolc acid in hexadecane obtained using a four-ball
machine at 200 rpm.
where: 6 is the proportion of surface covered by adsorbed polar molecules, k is a temperature-independent adsorption
constant, AH is the enthalpy of adsorption, T is absolute temperature, R is the gas constant, and C is a proportionality
constant. AH for reversible adsorption of additives is a constant and a value of 40 cal/mol has been reported by Spikes
and Cameron [67] and a value of 46 cal/mol was reported
by Grew and Cameron [68] for a dodecanoic acid/dodecane
system.
This work provides a reasonable explanation of the generally accepted view that a thick oil film is "safer" than a thin
film, even w h e n there is continual intermittent contact.
When there is a thick film, the tips of the asperities alone will
touch and touch only momentarily. This means that the time
when there is metal-to-metal contact is very short. Due to the
short time duration of the contact, a considerably higher
temperature is needed to desorb the polar materials than the
equilibrium value. As the film gets thinner, the areas in contact increase so each asperity is in contact longer and the
molecules have a longer time to respond to the asperity tip
temperature. For constant friction load, the load that can be
carried safely is also lowered. This means that a large film
thickness requires a higher surface temperature for scuffing
than does a thin film, therefore, thick films may carry greater
loads. Recent studies show that the scuffing is based on the
residence time of molecules physically or chemically adsorbed [66]. Scuffing wear is illustrated in Figs. 25a,b,c and
Fig. 42.
Delamination
937
(a)
Wear
(b)
FIG. 47a) Subsurface deformation of AISI
1020 steel; load = 2.25 kh after sliding 54 m in
argon atmosphere; b) three segments of a subsurface crack in cold-worked AIS11020 steel, a
and c show the ends of the crack and b shows
the mid-section of the crack. (Source: S. Janhanmir, NIST, Gaithersburg, MD.)
938
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
Surfaca^.
FIG. 48Photomicrographs of void formation around inclusions and crack propagation from these voids near the surface
in annealed Fe-1.3% Mo alloy. (Source: S.C. LIm, National University of Singapore, Singapore.)
O)
CO
Testing
10"
5r
10-'
o
10"
"TO
(0
0)
>
10
J_
10"
10
J-
10^
10
10^
800
c 55
<D
600
CO
0)
/c
a
/
/
c
1
(b)
25
~20
CO o
400
o ^
<D
<s>
a.
CO
30
^
// o)
0)
- O (/)
.ii
E
-a
o S
- c
c
^ri-2kg
,
5^1
iilO
200
(c)
Load (g)
(a)
0.2
3 kg
1
0.4
Thermal Conductivity
(caL/cm-sec^C)
<u
E
o
>
SO
-r'9-7
0.1
0.2
0.3
J
0.4
i_j.
0.5
FIG. 49Wear is dependent on several factors, a) load and material; b) sliding distance and material;
c) thermal conductivity, load and speed on the conditions to produce a photographic hot spot; d) wear
dependence on load and hardness.
(d)
Metallic Bearing
Surfaces
Transferred
Metallic
Wear
Debris
Corroded
Surfaces
Corrosion
Product
Debris
1 Plowing or Fatiguo
SAdhosion
3 Corrotioii
C
FIG. 51Pin-on-V-block tests
conducted by progressively increasing the load on the rotating pin
to evaluate the lubricating properties of a petroleum oil loaded with
EP additives. The test results indicated that the steel pin would
undergo extrusion without wear indicating excellent lubricating properties. (Source: D. Drees, Falex Tribology NV, Heverlee, Belgium.)
systematically consider materials, contact geometry, lubricants, applied pressure, and surface speeds in order to appropriately model the expected wear in a particular lubrication process. It is also necessary to develop test conditions
that simulate actual use conditions and failure modes that
are typically encountered during the use of the lubricant
through a tribological wear test design process.
There are numerous bench testing machines and standardized testing protocol. Current testing machines and procedures will be discussed in the next chapter and will not be discussed further here. However, two illustrations of the value
of lubricant testing will be provided here from the standpoint
of wear analysis.
In one test, the lubricant properties of a petroleum oil containing extreme pressure (EP) additives was evaluated using
a pin-on-V-block machine. In this case, the rotating pin was
AND TRIBOLOGY
FUNDAMENTALS
939
ho
940
HANDBOOK
(a,b)
(c)
FIG. 52Illustration of lubricant evaluation using the block-on ring tests by wear mode identification. The
tests conducted include: a) an example of adhesive wear on the test block caused by a bad lubricant; b) micrograph of the test block indicating mostly uniform wear, but in some parts of the wear track there is adhesive wear. This behavior is often called "scoring" but it signifies the limiting load that a lubricant can carry,
c) General adhesive wear, also called seizure, indicated by excessive scoring of the test block; d) some parts
of the ring (of the block-on-ring pair) show that adhesive failure occurred; e) in this case, there is uniform
wear on the test block which, in this case, indicates that the lubricant prevented adhesive wear. The extent
of the wear scar (width) can be used to characterize "antiwear" properties. (Courtesy of D. Drees, Falex Tribology NV, Heverlee, Belgium.)
10'-
/Pseudo - Scuffing
^
scumng
Corrosive IVIod^
Severe
Scuffing
^
y'^
<,#^/Mixed
^"S^- /Mixed
\<^
^'X^
_cp' C!^
/ ^
/
\,
Corrosive I
\
.
Corrosive
and Transfer I
1 Modes
L.
IVIodes
Violently Corrosive
\
\
\
10-*
)
| /
"S '
/ ^/
ro I Transfer / v. /
%>^ Mode
f/
r|.5l
11
^ a j
1 ^
w:
Vv
Sliding
(Contact)
Fatigue
Mixed
Corrosive
Fatigue
X.
\
\
Ideal System ^
I "Molecular Wear"
I
I I
0.5
1.0
1.5
2.0
2.5
3.0
Mode
_L
3.5
4.0
1/2
A=ho/ (oi+ai)'
FIG. 53Wear map for lubricated steel wear variation with changes in specific oil film
thickness.
941
Flash Temperature
Flash
^Tn
Temperatures
AT
1.61nW^'V
k[l + 0.627(W/a)]0
Tm - y ( factor of 3)
Value
760 kg/mm^
0.109 cal/cm C-s
0.11caygC
7.78 g/cm^
0.127 cm^/s
TABLE 11Composition of AISI 52100 used for test balls for 4-ball machine.
Composition
C
Mn
Si
Cr
0.95-1.10
0.25-0.45
0.025 max
0.025 max
0.20-0.35
1.30-1.60
942
MANUAL
HANDBOOK
90C
Pure Sliding
Pure Rolling
Maps
yfVa
Eac
kCl-r
10'
a.
3
(A
(0
Wear Region
10
Conditional Wear Region
10 y
9>
c
10
CQ
(D
10'
CO
M
c
o
'm
c
(D
E
b
No Wear Region
lO"!
10
10^
10 '
10'
10
1_
micro-contact
(G,<1.7X10'')
10'
TI
10'
G,
10'
J
macro-contact
(10 < G t < 1.7x10^)
CHAPTER
35: LUBRICATION
0.5
0.4-
0
0.2
0.4
0.6
0.8
1.0
Shear Strength at the Contact Surface (f)
FIG. 56Wear mapping procedures have also
been developed to elucidate the classification
of specific types of wear such as the model for
abrasive wear.
= ^
^ -
AND TRIBOLOGY
Dp = R
UH,
2W
UH
rR^
2W
III
"Scuffing Regime"
\ 1
II
"Boundary"
f= 0.3-0.5
\
\
E
o
"5.
943
1/2
D =
FUNDAMENTALS
Q.
<
f= 0.2-0.4
^I
Al
I
^ \ .
"(Partial) EHD"
f= 0.04-0.1,
"^
1
1
1
1
- _ ^
A3
v
Velocity (V) FIG. 57de Gee, Begelinger and Solomon wear map (transition diagram) for n AISI 52100 ball-cylinder wear contact in a
super refined paraffin oil at 30C and a viscosity of 1.4 x 10~^
Pa.s in dry air.
944
MANUAL
HANDBOOK
Microattrition
# Micro-abrasion
-Mechanical fatigue
* Thermal fatigue
+ Chipping
.500
H.275
T3.200
60
360
FIG. 58Wear map illustrating the wear mechanisms involved in cutting of preheat treated AISI4140 steel using an uncoated C5 carbide insert.
the contact exceed the oxidation and tribochemical modification rate and incipient scuffing (Region II) or full-scale
scuffing (Region III) begins (Vs).
De Gee and coworkers have shown that the contact temperatures in this system may be as high as 500C at the A2-S
transition, which would be sufficient to lead to metallurgiccJ
transformations [90]. It is therefore proposed that the onset
of scuffing may be "triggered" by a metallurgical transformation. The general subject of metallurgical transformations
that may occur on the wear surface will not be discussed further here, however, the reader is referred to Refs. 91-97 for a
more detailed discussion of these processes.
As a result of this work de Gee cited that the often widely
varying wear rates reported in the literature may be more due
to differences in the wear regime during testing than differences in additive performance. Furthermore, meaningful additive evaluation could only b e achieved with identical conditions of boundary lubrication.
De Gee et al. have studied the wear mechanisms involved
in the cutting of preheat treated AISI 4140 steel [98]. The
mechanisms of flank wear of a n uncoated C5 carbide insert
(as well as various nitride coated inserts) were determined
and mapped as a function of cutting speed and feed rate. The
predominant wear mechanisms were determined to be adhesion wear (also referred to as attrition wear) abrasion wear,
mechanical fatigue, cind thermal fracture. The wear map for
the use of a C5 carbide insert to cut preheat treated AISI 4140
steel is provided in Fig. 58 [98]. Figure 59 is SEM photographs of flank face wear, which illustrates the trend of mi-
0.275
mm/rev.
0.200
mm/rev.
3"
(D
Q.
3J
0.125
mm/rev.
59.9 m/min
119.7 m/min
179.6 m/min
239.4 m/min
359.1 m/min
7m/s
2m/s
3m/s
4m/s
6m/s
Speed
FIG. 59Wear of the flank face using a scanning electron microscope (SEIU) at 1000X magnification to illustrate the trend of microattrition wear, microabrasion wear and thermal pitting for cutting of preheat treated
AISI 4140 steel using a C5 carbide insert under "wet cutting" conditions. Increasing cutting speed is shown
going from left to right and increasing feed rate is shown going from bottom to top of the photo array.
(Source: S. Tung, GM Research and Development Center, USA.)
CHAPTER
35: LUBRICATION
AND TRIBOLOGY
FUNDAMENTALS
identified by plotting the onset of scuffing after testing the lubricant on a precision ball-on-disk machine at various rotational and sliding speeds at a given load as shown in Fig. 60
[18].
These examples show that development of a wear m a p permits a more global illustration of various lubrication and wear
mechanisms that may potentially be involved in a wear process and provide a much greater and more useful overview of
lubricant performance than a single bench test [99].
Lubrication Mechanisms
Lubricants are delivered to two surfaces undergoing relative
motion to reduce friction. Although lubricants may be in liquid, gaseous, and solid states, this chapter will focus on liquid lubricants, primarily those derived from petroleum oil. It
is genercdly accepted that liquids exhibit three lubrication
regimes: boundsiry lubrication, elastohydrodynamic lubrication, and hydrodynamic lubrication.
The Stribeck curve is a plot of the friction coefficient (/i) as
a function of the product of absolute viscosity (17) and the rotation speed in revolutions per unit second (N) divided by the
load per unit projected bearing area (P), as illustrated in Fig.
61 [100]. Because the Stribeck curve exhibits a characteristic
minimum, this suggested to McKee and McKee as early as
1929 that more than one lubrication mechanism is involved
[101]:
M
At least four lubrication regimes [18] are indicated in Fig.
62, which is a plot of the coefficient of friction versus the
Performance Map
Herco-A, 300 KSI Stress
"HG" M50 Ball (Ra=10), M50 Disc (Ra=3)
6S0
600 -
NA276-NA306
sso 1^
500
1,30
IS
400
o
>
(SO
MO
g
j3
250
200 -
XTl
ISO 100 -
945
Scufr
50
^
so
250
946
MANUAL
HANDBOOK
substantially greater t h a n surface asperity heights. EHD lubrication is characterized by thin film lubrication with film
thickness of approximately 0.025-2.5 fim. Although these are
thin films, they are greater than the asperity contact heights.
Boundary lubrication is characterized by film thickness of ^
0.025 /u,m, which is less than the height of the asperity contacts. Mixed film, or EHD/boundary lubrication, occurs at
the transition from boundary to EHD lubrication. For comparison, the relative sizes of various components of a wear
contact are provided in Table 13 [102].
Hertzian
Contact
If one body is pressed against another with sufficient pressure, an elastic deformation will result, as shown in Fig. 8
[103]. The pressure generated in this contact is the Hertzian
200
Z = centipoise
N" = rev/min
400
600
stress (CTH):
ZN'
P
(TH
1.5 LE^
TT^r^dv'Y
rBoundary
rMixed
rElastohydrodynamic
Ar = 2.9 [L rf^
c
o
Hydrodynamic
c
o
(D
O
o
0
10
20
A=.
JL^
(af+ai)
0.5
FIG. 62Characterization of lubrication regimes as a function of the coefficient of friction and the dimensionless film
parameter.
"Typical" Component
Approximate Size
Range (lira)
Monomolecular Layer
Sliding Wear Debris
Boundary Film
EHD Film
Asperity Height
Rolling Wear Debris
Asperity Contact
Hydrodynamic Film
Asperity Tip Radius
Concentrated Contact Width
Engineered Counterformal Radius
Engineered Conformal Radius
0.2-2 X 10^^
0.002-0.1
0.002-3
0.01-5
0.01-5
0.7-10
0.7-10
2-100
10-1000
30-500
1-100 X 10^
12-2500 X 0*
Materials
Aluminum
Copper
Stainless steal
Alumina
Silicon nitride
Polyethylene-high density
PTFE (25% glass fiber)
70.6
12.98
180-220
300-400
280-310
0.5-1.2
1.7
gether at the same location to fill the gap between the surfaces. Due to surface convergence, fluid in the interior must
slow down, as shown in Fig. 63, or even flow in the reverse direction. The reduction in velocity causes an increase in hydrodjmamic pressure of the fluid. Because of the viscositypressure relationship of the fluid, as illustrated in Fig. 64,
fluid viscosity increases as the pressure increases within the
inlet region [18]. (See the Pressure-Viscosity Coefficient section for more discussion on the viscosity-pressure relationship of fluids.)
EHD Film Thickness Measurements by InterferometryEHD
film thickness measurements may be experimentally determined using the optical fringe color in the center of the contact as a function of rolling velocity. Optical film thickness is
measured at the "center" of each fringe and at the transition
between each fringe. The optical film thickness data is con-
Rlm
FIG. 63Illustration of fluid flow contours with the Inlet region. Pure
rolling motion at relative velocities Ui and U2 is assumed for this illustration.
O Fluorinated Polyether
Linear Polyperfluoroalkylether
A Super-Refined Naphthenic Mineral Oil
V Synthetic Hydrocarbon (traction fluid)
V- Advanced Ester
50
947
100
Temperature C
FIG. 64Fluid viscosity increases with increasing pressure as the fluid enters the inlet region and Hertzian contact region. Typical viscosity pressure relationships of different base fluids is provided.
First yellow
Red
Blue
Green
Second Yellow
Red
Blue
Green
Third Yellow
Red
Blue
Green
2.0
2.7
3.4
4.3
4.7
5.6
6.1
6.7
7.6
8.6
9.0
9.6
h
Where:
0.7 ,0.54
DO.43
2.65 (rjo f/r^
a'
R"
An important feature of EHD lubrication is that the influence of load on film thickness is relatively small since increasing the contact load would result in an increase in the
maximum Hertzian pressure, which increases the Hertzian
contact region. Therefore, there is little effect on the inlet region where hydrodynamic pressure is generated.
Although the effect of pressure on lubricant viscosity is an
i m p o r t a n t p a r a m e t e r in lubricant fluid-film analysis, the
pressure-viscosity coefficient is often unavailable. However,
this data can be obtained by calculation using the Reynolds
equation if film thickness can be measured in the contact region [108]. This is obtained from a plot of the dimensionless
film thickness parameter (ho/R) where:
ho = film thickness in the center of the contact,
R = combined radius of curvature of the Hertzian contact
Ue =
E' =
R =
T/o =
"l+A(f^^*"""^
Dimensionless Film Thickness vs Speed Parameter
E'R
FIG. 65Dimensionless film thickness versus speed for different fluids at 23C.
CHAPTER
35: LUBRICATION
RMS
+Ritr'
(^q,a
Lubrication
,
A
vn
1000
AND TRIBOLOGY
FUNDAMENTALS
949
Lubrication
Modifiers
Name
Probe
Detection Signal
Information
Space Resolution
Applications to Tribology
Elemental
analysis of the
surface
= 50 nm.
depth
1.5 m m
Illumination
spectrum,
composition
Electronic
status of very
small portion
= 5 fan
Depth direction
profile of each
element at friction
surface (+ ion gun)
Lattice defects and
compression analysis
{+ EPMA)
Elemental
analysis, electron
state analysis
(4-TEM)
Stress due to slip.
film thickness
changes, etc.
50 n m
Analysis of slip
products
AED
Auger electron
spectroscopy
Electron
CL
Cathode
luminescence
Electron
Photon
EELS
Electron
energy loss
spectroscopy
Electron
Electron
(Scattered)
ELL
EUipsometry
Light (laser)
Light
(polarized)
Optical
constant, film
thickness
EPMA
Electron probe
microanalysis
Electron
Characteristic xray
EDX, WDX
quantitative
analysis
ESR
Electron spin
resonance
Magnetic
field
Electromagnetic
wave
Unpaired
electron
(radicals, etc.)
XAFS
X-ray
absorption fine
structure
X-ray
X-ray
absorption
0.2 n m
FIM
Field ion
microscopy
Neutal
molecule +
electric
field
Cation
EXAFS
(distcince to
surrounding
atoms,
number):
XANES
(atmic value
configuration)
Atomic
configuration
NMR
Nuclear
magnetic
resonance
Magnetic
field
Electromagnetic
wave
Molecular
bonding
condition
> 10 fim
IR
Infrared
absorption
spectroscopy
Light
(infrared)
Light
(infrared)
Vibration
condition
Thin film
acceptable
LEED
Low energy
electron
diffraction
Electron
Electron
(diffraction)
Molecular
bonding
condition
RBS
Rutherford
backscattering
spectroscopy
Optical
profilometry
Ion beam
Scattered ion
Vibration
condition
Several
atom layers
below the
surface
> 100 fjLm
Light (laser)
Light
(interference)
Surface atomic
structure
RS
Raman
scattering
Light (laser)
Light (Ramsin
scattering)
SEM
Scanning
electron
microscope
Electron
Electron
(secondary
scattering)
Trace
elements,
atomic
configuration
Surface
topography
OPM
Auger electron
= 10 n m
Depth
direction
50 fjon
Several 10
/Lim, depth
direction
= 0.5 /xm.
depth
direction
0.3 to
several ^ m
10' spins
Sub - /jan.
depth
direction
0.5several n m
1 fj,m
= 1 nm.
depth
direction
0,3several /nm
Lubricant
deterioration and
dangling bond
analysis
Composition of
adsorbed
substances
Three dimension
structure at atomic
level resolution,
(+ electric field
evaporation)
Adsorption
condition of
lubricant,
molecular
mobility, surface
functioned radicals
Analysis of
adsorption
performance of
gases and
lubricants (FT-IP,
RAS, ATR,
polarization)
Gas adsorption at
surface (+AES,
RHEED)
Alalysis of slip
products, thin film
density)
Imaging to slip
surface
Electronic
properties of thin
films, etc
Damage forms
(In-situ as well.
+ EPMA)
(continues)
951
TABLE 16(continued).
Acronym
Name
SIMS
Secondary ion
mass
spectroscopy
SPA
Surface
potential
analysis
Scanning
probe
microscopy
SPM
STEM
TA
TEM
TOFSIMS
TDS
TXRF
Probe
Ion beam
Detection Signal
Information
Secondary ion
Combination
condition
Electric field
Topography
Space Resolution
Applications to Tribology
Several
fan, depth
direction
0.5several n m
Several 10s
Exrtremely small
quantity elements
detection including
hydrogen
Slip charge
fjm
Electric
field
Tunnel current
Sixrface and
subsurface
formation
Scanning
transmission
microscopy
Thermal
analysis
Electron
Electron
(transmission)
Polarization
Thermal
energy
Heat dissipation
Transmission
electron
microscopy
Time of flight
SIMS
Electron
Ion beam
Electron
(transmission.
diffraction)
Secondary ion
Thermal
desorption
spectroscopy
Total-relection
x-ray
flourescence
spectroscopy
Thermal
energy
Desorbed atoms,
molecules
Microscopic
surface
structure
Shape,
structure
elements
Heat of
adsorption,
heat of
transition
Imaging
X-ray
Fluorescent
x-ray
Composition
distribution
0.1 nm.
depth
direction =
0.1 n m
< 1 n m
10 n m
0.1 n m
100 fjim.
depth
direction 1
nm
10^
atoms/cm^
depth
direction
several n m
1 fim
UPS
Ultraviolet
photoelectron
spectroscopy
Light
(tdtraviolet)
Photoelectron
Adsorption,
material
decomposition
XRD
X-ray
diffraction
X-ray
X-ray diffraction
Trace element
cmalysis
Several
100s fjan,
depth
direction
XPS
X-ray
Photoelectron
spectroscopy
X-ray
Photoelectron
Chemical
composition
100 /xm.
depth
direction
several n m
Various
applications
including STM
and AFM
Crystallization in
very fine regions
(+ EDX, + EELS)
Adsorption energy.
lubricant
deterioration, etc.
Transition cell
structure, reaction
products, etc.
Lubrication
distribution,
deterioration
Identification of
adsorbed and
stored materials
Surface
contaminants
Surface oriented
tribological
anedysisbonding
state
Thin film
structure, internal
pressure defects,
etc. (including
neutron
diffraction)
Surface oriented
tribological
analysis, bonding
state, lubricant
film thickness
(+ ion gun)
Purpose
Reduce friction under
near-boundary
conditions
Antiwear Additive
Reduce wear
Prevent, galling,
scoring and seizure
666666666666
Typical Compounds
High molecular weight
compounds such as fatty oils,
oxides, waxes, fatty acids,
fatty alcohols
Organic phosphates, phosphites,
zinc dithiophosphates
Sulfur, phosphorous, chlorinecontaining materials
It
EsSSJ^
(a)
Function
Adherence of polar
materials to metal surfaces
Forms a film on metallic
contacting surfaces
Formation of low-shear
films on metal surfaces at
the wear contact
C-ssO
1 ;
0 .'
IV
H
t
OCu 0 Cu 0
OCuO CuO
FIG. 67A hydrogen exchange interaction for fatty acids on a copper substrate.
iJjggJjgffivjSJi
(b)
FIG. 66Adsorption models for: a) physisorptlon; b) chemisorption.
-or
8 x 1 0
heptane, as shown in Fig. 69 [102,130]. In general, adsorption efficiency decreases as the polar group is moved from
the end (1-octadecanol) to the middle (5-acdecanol), which is
due to increasing stearic hinderance of the adsorbing group.
Hironaka illustrated the dramatic differences in the heat of
adsorption of stearic acid as a function of the surface condition of the metal substrate, as shown by the heat of adsorption of stearic acid on FeS, Fe304 and Fe203 in Fig. 70 [120].
Experimental determination of adsorption isotherms, such
as those shown in Figs. 68 and 69, m a y b e performed through
procedures described earlier by Forbes and Reid and others
[130] where a tumbling a p p a r a t u s described by Clunie is
used [131]. For these experiments, 5 mL borosilicate glass adsorption tubes are used into which 1.0 g of the iron powder
953
Glass Tube
1-Octadecanol
Solution
2-Octaclecanol
5-Octadecanol
J_
O.S
1.0
1.S
2.0
2.S
3 . 0 x 1 0- 1
0
0.5
10.0
Heat of Adsorption, (mJ/m^) Adsorbent
FIG. 70The dramatic differences in the heat of adsorption of stearic acid as a function of the surface
condition of the metal substrate.
954
MANUAL
HANDBOOK
m i c a d s o r p t i o n free e n e r g y d e c r e a s e s l i n e a r l y w i t h s u r f a c e
coverage [140]:
AGads = AGo + aO
w h e r e AGQ = t h e p r i m a r y a d s o r p t i o n free e n e r g y a t fl = 0 a n d
a = p o s i t i v e c o n s t a n t t h a t is d e p e n d e n t o n t h e i n t e r a c t i o n of
t h e additive with t h e surface.
At l o w a d s o r b a t e c o n c e n t r a t i o n s w h e r e 0 a fl a 0.2, t h e n :
e ( R T / a ) (C/Ko)
w h e r e : C i s t h e a d d i t i v e c o n c e n t r a t i o n i n m o l e fraction
Ko is t h e p r i m a r y a d s o r p t i o n c o n s t a n t d e f i n e d a s :
and
Ko = e x p ( d G o / R T )
At i n t e r m e d i a t e a d d i t i v e s u r f a c e c o v e r a g e w h e r e : 0.2 < 6 s
0.8, t h e f o l l o w i n g i s o t h e r m m a y b e u s e d [ 1 3 3 ] :
e = ( R T / a ) In (C/Ko)
At h i g h levels of c o v e r a g e , 0.8 ^ fl s 1.0, t h e T e m k i n i s o t h e r m
becomes:
9 1 - ( R T / a ) [ e x p ( a / R T ) - 1] (Ko/C)
Using this a p p r o a c h , J a h a n m i r d e t e r m i n e d the friction coefficients a n d free e n e r g y of a d s o r p t i o n for a s e r i e s of c a r boxylic acids in a solvent-refined, dewaxed, hydrorefined
n e u t r a l l u b r i c a n t b a s e s t o c k w i t h a v i s c o s i t y of 32 c S a t 40C.
T h e d a t a o b t a i n e d is s u m m a r i z e d i n T a b l e 18. T h i s d a t a
s h o w s t h a t t h e f r i c t i o n coefficient d e c r e a s e s w i t h i n c r e a s i n g
h y d r o c a r b o n c h a i n l e n g t h ind w i t h i n c r e a s i n g free e n e r g y of
adsorption [133,141,142].
T h e a n t i w e a r a c t i v i t y i s d u e t o t h e f o r m a t i o n of a m o n o l a y e r of s t e a r a t e a s t h e l u b r i c a t i n g film. As s h o w n b y J a h a n m i r , I n c r e a s i n g c h a i n l e n g t h s of c a r b o x y l i c a c i d s g e n e r a l l y
d e c r e a s e coefficient of f r i c t i o n [ 1 2 7 , 1 2 8 , 1 3 3 ] . H o w e v e r , it h a s
b e e n p r o p o s e d t h a t a l t h o u g h at lower sliding speeds the coefficient of friction is c o n t r o l l e d b y m o n o l a y e r f o r m a t i o n , a t
higher sliding speeds, o r d e r e d multilayers control friction
[125,127].
G r o s z e k , d e s c r i b e d t h e u s e of a p u l s e flow m i c r o c a l o r i m e t e r t o s t u d y t h e a d s o r b a n c e of m o l e c u l e s of v a r y i n g polctrity
o n t o different s u b s t r a t e s including: graphite, cast iron, i r o n
a n d steel p o w d e r s , i r o n oxides, nickel oxide a n d lithium
s t e a r a t e [ 1 4 3 a ] . Also, v a r i o u s s o l v e n t m e d i a w e r e e v a l u a t e d .
This w o r k showed t h a t certain metal oxides a n d graphite
preferentially adsorb molecules with long hydrocarbon
c h a i n s from l o w m o l e c u l a r w e i g h t s o l v e n t s . H o w e v e r , i r o n ,
steel a n d F e 2 0 3 d o n o t e x h i b i t a n y t e n d e n c y t o p r e f e r e n t i a l l y
a d s o r b l o n g c h a i n h y d r o c a r b o n s . I n a d d i t i o n , it w a s s h o w n
that detergent additives are strongly adsorbed o n a l u m i n a
a n d engine deposits.
H i r o n a k a a n d o t h e r s h a v e a l s o s h o w n t h a t t h e effectiveness
of v a r i o u s friction m o d i f i e r s o n f r i c t i o n a n d w e a r r e d u c t i o n
is r e l a t e d t o t h e h e a t of a d s o r p t i o n . T h i s is i l l u s t r a t e d b y t h e
d a t a s h o w n i n T a b l e 19 [ 1 2 4 ] a n d T a b l e 2 0 [ 1 2 0 ] . F r o m t h e s e
r e s u l t s a n d o t h e r s , t h e f o l l o w i n g r u l e of t h u m b is u s e d : " t h e
g r e a t e r t h e h e a t of a d s o r p t i o n , t h e b e t t e r t h e l u b r i c i t y " [ 1 2 0 ] .
Antiwear a n d E P additives are classified by t h e t e m p e r a t u r e s r e q u i r e d t o activate t h e m . Antiwear additives typically
act by a d s o r p t i o n a n d E P additives r e q u i r e a t h e r m a l activat i o n as illustrated schematically in Fig. 72 a n d Fig. 7 3 .
TABLE 18Effects of hydrocarbon chain length on friction coefficient and free energy of adsorption.
Carboxylic Acid
Acid Structure
Friction Coefficient
AGo (kcal/mole)
Capiic Acid
Laurie Acid
Myiistic Acid
Palmitic Acid
Stearic Acid
Oleic Acid
CH3(CH2)sCOOH
CH3(CH2)ioCOOH
CH3(CH2)i2COOH
CH3(CH2)i4C00H
CH3(CH2)i6COOH
CH3(CH2)7 CHBCH (CHj)? COOH
0.111
0.104
0.099
0.086
0.077
0.099
-5.5
-5.4
-4.9
-5.2
-5.0
-4.8
TABLE 19Friction and wear metal transfer for cadmium surfaces at r o o m temperature.
Lubricant
None
Cetane-C 15H31CH3
Cetyl Alcohol-Ci5H3iCH20H
Palmitic Acid-C,5H3iCOOH
Coefficient of Friction
0.8
0.6
0.4
0.07
Metal Pick-Up
X lO^g/cmof Track
50 000
500
100
1
CHAPTER
35: LUBRICATION
Paraffin Oil
c
o
0)
o
O
l_ EP and Polar
Film Formers
Temperature
FIG. 72Increasing temperatures will lead to failure of lubricating films formed by friction modifiers.
j 1
-t>
1> s
S
1> S
II
S +2R-
II
Alkane,
Olefin, etc.
Fe Surface
I
11 Surface Extrusion
[Adsorption
Bond Formationll Into Steel Surface
AW Region
EP Region
I > > >^)
11 >'i I > I > 11 > } \ > > I > 11 >} > > > ) \ > I > >\ > > I > >
Temperature
FIG. 73Illustration of the difference of surface reactions for
antiwear and EP additives.
Increasing temperatures will lead to failure of lubricating
films formed by friction modifiers t h a t are related to:
[32,124]
Adsorption films undergo two-dimensional melting at temperatures close to the bulk melting point, disorienting temperature, of the additive. This disorientation temperature
distinguishes physisorbed additives from chemiadsorbed
additives. In some cases, it has been reported that if the
temperatures are sufficiently high, the adsorbed films will
"bum" forming carbonaceous residues [143b]
While physisorbed films become detached from their surface at the melting point of the additive, chemisorbed additives are effective above their bulk melting point although they do ultimately fail with further increases in
temperature [32].
Therefore, the relatively limited film strength and thermal
instability of the friction reducing films formed by friction
modifiers necessitates the use of additives that Eire more effective in this region.
Antiwear AdditivesAntiwear
additives often contain phosphorous such as those compounds illustrated in Fig. 74 [144].
Generally, eintiwear additives are most effective under mixed
lubrication conditions where low-medium loads or high temperature conditions Eire encountered. In this region, there is
intermittent asperity contact. The antiwear additive reacts
with the metal asperities at the wear contact temperatures to
AND TRIBOLOGY
FUNDAMENTALS
955
Metal dialkyl
dithiophosphate
RO
\ )
Tricresyl phosphate
(R = cresyl)
I.e.
Dialkyl phosphite
XM
(S
CH,
Phosphate
956
HANDBOOK
representative
thickness (nm) - 9 0 0
alkylphosphate
precipitates
(poly)idiospbate
sulphide/oxide
ferrous
substrate
FIG. 75Multiple reaction pathways, which occur tribochemically within the wear contact, are evident
when considering the complexity of a recently determined structure of zinc dithiophosphate reaction film.
4-
1 Sutfur-type
/ EP agents
#3.5.
1
(0
o
c
O)
1
1
/
/
/
S o
2-
1 1.5- J/ / r
7
1 //
DC
//
1 .
/
1
1
j
f2.5.
0
.2
/
/
^,,,^
fi--<7.
Phosphorus-type
EP agents
/
/
^A--
^^-"^'^
Chlorine-type
EP agents
~ ,, . -
1.1
1.2
1.3
1.4
Relative chemical reactivity
1.5
FIG. 76Correlation of relative reactivity and load carrying capacity of EP additives with respect to the functionality
class.
shear strength, friction is reduced, as is the tendency for severe adhesive failure. [144]
There is often no clear division between the mechanism of
activity between antiwear and EP additives. In some cases, a
given additive may exhibit activity by either mechanism, depending on the use conditions. This is illustrated in Fig. 73
where the disulfide additive is adsorbed on wear surface with
subsequent disulfide bond cleavage to form an iron sulfide
[148]. As the load increases and the lubrication regime undergoes a transition from mixed film to boundary lubrication, the contact temperatures increase causing a cleavage of
the carbon sulfur bond resulting in an iron sulfide layer similar to that shown in Fig. 73. Thus a given additive may exhibit both antiwear and EP activity.
It has been shown that EP activity is dependent on the reaction or wear contact temperature. Therefore, it is important to determine the reaction temperature of an additive if
an assessment of its ability to continuously form, or regenerate, boundary lubrication films in the wear contact [79]. Figure 77 provides a summary of the additive EP requirements
as a function of the contact temperature [103] which provides a useful guideline for additive classification.
One of the problems in applying Fein's EP additive selection criteria is that additive activation temperatures are often
unknown. One method that may be used for studying the influence of contact temperature on the generation of EP films
is to use the "hot-wire method", originally developed by Barcroft and Rossett et al. [148,149] This method permits the
fast generation of surface temperatures of several hundred C
with significantly increasing the bulk fluid temperatures.
Surface analysis is then used to characterize the reaction
products formed under these conditions.
5 350
Strong
EP
s
a
E 300
0)
H
I 200
o
150"-
NonEP
CONCLUSIONS
An overview of fundamental principles involved in lubrication
has been provided. This included fundamental material and
surface properties along with an overview of friction. Also
provided was an extensive overview of weeir mechanisms and
their identification. This discussion was followed by a review
of fluid film lubrication and the role and criteria of additive
chemistry in friction reduction. The fluid was treated as a
component of the tribocontact and methodologies of examining and classifying -wear mechanisms was provided. Finally,
the role of additives in lubrication was discussed. This information can be applied to the test procedures and experimental designs proposed in the following chapters to provide a
greater depth of understanding of the data obtained. This information, in combination with the discussion provided in
Chapters 25 and 26, will provide the reader with a reasonably
in-depth overview of the basic principles of lubrication and
wear: its measurement and test methodologies and design.
ASTM STANDARDS
D 996
D 2652
D4175
D 4725
E 6
E 7
E 1823
G 15
G 40
ASME
ASME Y14.36M: Surface Texture Symbols.
ASME B46.1: Surface Texture (Surface Roughness, Waviness, and Lay).
ISO
B 374
D 653
957
Mild
EP
.2 250
No.
A 902
FUNDAMENTALS
OTHER STANDARDS
O 400
u
c
AND TRIBOLOGY
Title
Standard Terminology Relating to Metallic Coated
Steel Products
Standard Terminology Relating to Electroplating
Standard Terminology Relating to Soil, Rock, and
Contained Fluids
Standard Terminology of Packaging a n d Distribution Environments
Standard Terminology Relating to Activated Carbon
S t a n d a r d Terminology Relating to Petroleum,
Petroleum Products, and Lubricants
Standard Terminology for Engine Coolants
Standard Terminology Relating to Methods of Mechanical Testing
Standard Terminology Relating to Metallography
Standard Terminology Relating to Fatigue and Fracture Testing
Standard Terminology Relating to Corrosion and
Corrosion Testing
Standard Terminology Relating to Wear and Erosion
REFERENCES
[1] Ludema, K. C, "Friction," in Handbook of Lubrication Theory
and Practive of Tribology: Vol 2, E. R. Booser, Ed., CRC Press,
Inc., Boca Raton, FL 1988, pp. 31-48.
[2] Czichos, H., Klaffke, D., Santher, E., and Woydt, M., "Advances
in Tribology: The Materials Point of View," Wear, 1995, Vol.
190, pp. 155-161
[3] Tabor, D., "Friction-The Present State of Our Understanding,"
Transactions of the ASME Journal of Lubrication Technology,
1981, Vol. 103, pp. 169-179.
[4] Dunken, H., "The Importance of Tribochemical Reactions Between Additives and Metals in Friction and Weair Processes,"
Journal of Chemistry, 1971, Vol. 11, No. 6, pp. 213-219.
[5] Stolarski, T. A., "Basic Principles in Tribology," Tribology in
Machine Design, Industrial Press Inc., Oxford, England, 1990,
pp. 13-63.
[6] Park, K. B. and Ludema, K. C, "Evaluation of the Plasticity Index as a Scuffing Criterion," Wear, 1994, Vol. 175, pp. 123-131.
[30] Roelands, C. J. A. and Druk, V. R. B., Kleine der A3-4 Groningen, Holland, 1966.
[31] Fresco, G. P., "Measurement and Predicting of Viscosity-Pressure Characteristics of Liquids," M. S. Thesis, The Pennsylvania State University, University Park, PA, 1962.
[32] Kim, H. W., "The Viscosity-Pressure Studies of Polymer Solutions," Ph. D. Thesis, The Permsylvcinia State University, Uiiiversity Park, PA, 1970.
[33] So, B. Y. and Klaus, E. E., "Viscosity-Pressure Correlation of
Liquids," ASLE Transactions, Vol. 23, No. 4, 1980, pp. 4 0 9 421.
[34] Chu, P. S. Y. and Cameron, A., "Pressure Viscosity Characteristics of Lubricating Oils," Journal of the Institute of Petroleum,
Vol. 48, 461m, 1962, p p . 147-155.
[35] Worcester, R. C , Discussion of paper presented by A. E. Bingham, "Some Problems of Fluids For Hydraulic Power Transmission," Proceedings of the Institution of Mechanical Engineers, Vol. 165, Institution of Mechanical Engineers, London,
1951, p p . 254-261, 269-270.
[36] Johnson, W. G., "A Method to Calculate The Pressure-Viscosity
Coefficient From Bulk Properties of Lubricants," ASLE Transactions, Vol. 24, No. 2, 1981, p p . 232-238.
[37] Lauer, J. L. and Dwyer, S. R., "Tribochemical Lubrication of
Ceramics by Carbonaceous Vapors," STLE Preprints, Preprint
No. 90-TC-6A, STLE, Park Ridge, IL, 1991.
[38] Kempinski, R., Kedzierska, E., Kardaze, K., Wilkanowicz L.,
and Konopku, M., "Tribopolymerization - Type Additives for
Lubricants, Part I: C12- Cis Alkyl Methacrylates," Trihologia,
Vol. 26, No. 3, 1995, p p . 277-298.
[39] Novotny, V. J., Pan, X., and Bhatia, C. S., "Tribochemistry at
Lubricated Interfaces," / . Vac. Sci. Technical., 1994, Vol. 12,
No. 5, p p . 2879-2886.
[40] Kajdas, C , Lafleche, P. M., Furey, M. J., Hellgeth, J. W., and
Ward, T. C , "A Study of Tribopolymerization Under Fretting
Contact Conditions," Lubrication Science, Vol. 6, No. 1, 1993,
pp. 51-89.
[41] Selected data from Appendix Table A.1, "Physical Properties of
Metallic Element," Friction and Wear of Materials, E. Rabinowicz, John Wiley & Sons, NY, 1964, p. 235.
[42] Rigney, D. A., "The Roles of Hardness in the Sliding Behavior
of Materials," Wear, Vol. 175, 1994, p. 63-69.
[43] Barwell, F. T., "Metallic Wear," Handbook of Lubrication Theory and Practice of Tribology-Vol. 2, Theory and Design, E. R.
Boose, Ed., CRC Press, Boca Raton, FL,1988, p . l 7 9 .
[44] Dorinson, A. and Ludema, K. C , Mechanics and Chemistry in
Lubrication, Elsevier, NY, 1985.
[45] Rabinowicz, E., Friction and Wear of Materials, John Wiley &
Sons, NY, 1964, p. 35.
[46] Rigney, D. A., "The Rules of Hardness in the Sliding Behavior
of Materials," Wear, Vol. 175, 1994, pp. 63-69.
[47] Meng, H. C. and Ludema, K. C , "Wear Models and Predictive
Equation: Their Form and Content," Wear, Vol. 181-183, 1995,
pp. 4 4 3 ^ 5 7 .
[48] Godfrey, D., "Gear Wear Caused by Contaminated OUs," Gear
Technology, September-October, 1996, pp. 45-49.
[49] Giltrow, J. P., "A Relationship Between Abrasive Wear and the
Cohesive Energy of Materials," Wear, Vol. 15, 1970, pp. 71-78.
[50] Fitch, E. C , Hong, I. T., and Xuan, J. L., "Abrasion Wear,"
BFPR Journal, Vol. 2 1 , 1988, pp. 9-29.
[51] Tomsic, J., Dictionary of Materials and Testing, 2"^ Edition, Society of Automotive Engineers, Wartendale, PA, 2000.
[52] Totten, G. E., Webster, G. M., and Yeaple, F. D., "Physical
Properties and Their Determination" Chapter 4, Handbook of
Hydraulic Fluid Technology, G. E. Totten, Ed., Marcel Dekker,
Inc., NY, 2000, pp. 195-304.
[53] Shi, J., Gao, M. Z., Wang, T. M., Wen, X. Y., and Shi, W. D.,
"Corrosion Wear Behavior of loji Implanted Steel," Wear, Vol.
175, 1994, p p . 145-149.
959
MNL37-EB/Jun. 2003
In this chapter, the Systematic Tribology theme is illustrated by highly stressed Hertzian contacts commonly represented by rolling element bearings, gears, and other contacts
with non-conformal geometry. The sections from Dynamic
Mechanisms of the Tribo-System through Generalized Performance Map identify the key tribology parameters that control
lubrication and failure mechanisms and allow linkage to service performance. The sections from Simulation of Gear Lubrication with Systematic Tribology Testing through Load Capacity Database for Qualified Aviation Gas Turbine Oils
illustrate the bench test modeling process with the simulation of lubrication and failure mechanisms in a gear mesh.
Surface
Film
Region
The surface film region contains the thin outer layers of the
surface. They may consist of surface oxides, adsorbed films,
ctnd chemical reaction films derived from the lubricant and
963
2003 by A S I M International
Region
Copyright'
Film
www.astm.org
TritwttYStem
Hydrodi/nainio fflm
QnBiatl^lBMjutahlea
Contact sifeki
Kiiwniatlca
Teoiperatultt
gtturtwral.QlwTiBnte
Siirhinm
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Hydrodynamic fihn
Suffece film
Near-surface
Sub-surface
Hoar surftca
Input
I I
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Tribo-system
/ interations^
Trtbo-agtein
m^chpnisma
atemm^chpnisma
Viscous film generation
SurfacA filiti formation
Hsapurbce accommodation
AdheslDii', chemical reaction
PMSlie fldvi^
Fatigue
Output
fc\
^ ^ t
^p
I
'
Tribology Induced
changes In
structural
elements
Triht^-watem neifbrmanca
'Wear, fatigue Me
Souffins 'luatiility
its additives. These surface films Eire Ejmost always less than
1 /u-m thick. While the surface film region is extremely thin,
its formation by mechanisms of surface forces and chemical
reactions has a profound effect on surface lubrication. In
highly stressed long-life mechanical systems, surface films
maintciin the integrity of the surface topography to promote
hydrodjTiamic jtnd EHD mechanisms.
Near-Surface
Region
The near-surface region contains the inner layers of the surface. During operation this region may include a finely structured and highly worked or mechanicEilly mixed layer. It may
also include compacted wear debris or transferred material
from a mating surface. The deformed layers, which are of a
different microstructure than the matericJ below them, may
arise from surface preparation techniques such as grinding
and honing. They may EJSO be induced during operation; for
example, during run-in. Hardness and residual stress may
vary significantly in this region. They may also be substantially different from the bulk material below. The nearsurface region may be on the order of 50 ^im below the surface. For life and durability, the mechanistic processes in this
region are designed to provide near-surface accommodation
of tangenticJ stress without loss of surface integrity.
Subsurface
Region
TRIBO-SYSTEM SIMULATION
Tribo-system tests generally have two practical purposes: (1)
they provide fundamental material property data as well as
mechanistic understanding and (2) they are used to predict
performance in service. For any test to have practical value,
there must be a clear link between testing and hardware performance. The challenge associated with this task is due to
the complexity of p e r f o r m a n c e m e c h a n i s m s in a tribosystem. An effective linkage between testing and hardware
performance can only be obtained with suitable simulation
of the mechanistic processes that control performance. In
most cases, it is more important to simulate lubrication and
failure mechanisms than it is to simulate the mechanical parameters of loads and speeds of component hardware. An important ingredient in test simulation is the pathway to failure. Performance limits of bearings, gears, a n d other
component hardware are defined as much by the lubrication
and deterioration mechanisms on the way to failure as by the
final failure mode itself.
^PRESSURE
(^oUe)""a"^^R'
hm= 3.07
ijfh-
965
,0.03 ^ 0 . 1 1
HANDBOOK
EHD pressure
Entraining
Lubr mechanisms
Surface film
EHD
Micro-EHD
Failure mechanisms
Wear
Scuffing
Fatigue
Sliding
FIG. 3Entraining veiocity affects asperity normal stress; sliding velocity affects tangential shear.
It is recognized that contact load or stress is an important engineering parameter. Contact stress is certainly important with respect to subsurface initiated fatigue, where
material crack initiation is directly related to shear stresses
below the surface. From a tribological perspective of processes at the surface interface, particularly under highspeed lubricated conditions, load is translated into contact
size, heat generation, and to some degree, asperity stress
and strain. While engineers like to work in terms of load
and stress, the critical phenomena within the contact is really seen to a greater degree as temperature or tangential
stress and strain.
Theories have gone a long way in prediction of EHD film
thickness including micro-EHD mechanisms associated with
interaction of roughness features. These modeling activities
support theories of rolling contact fatigue, where stresses and
strains within the material or at the surfaces are used to predict fatigue initiation. What is missing from these theories is
the chemical and physical boundary lubricating mechanisms
that control surface topography, friction phenomena and the
strength properties of the surface and near-surface material.
While surface analytical tools can probe the chemical elements of the surface, little is known about the shear strength
of the interfacial material under stress. The only way forward
is to conduct tests for surface durability under service-like
simulated conditions. These tests are essential for oil and material development as well as for oil qualification. To make
tests relevant to service performance, the key parameters and
their domain of operation must be understood. The lubrication and failure mechanisms that these key parameters invoke must then be properly simulated.
dependent control of the entraining velocity and sliding velocity. The spindles are said to be aligned when the velocity
vector of the ball is coUinear with the velocity vector of the
disk at the point of contact. To obtain pure rolling across the
contact interface, the axis of the ball is tilted.
The test machine allows the direction of the velocity vectors to be changed by moving away from the aligned position.
The angle Z between the ball and disk velocity vectors can be
continuously varied between 0 and 180. The entraining velocity is defined as one-hsdf the sum of the ball and disk velocity vectors. The sliding velocity is defined as the vector difference between the ball and disk velocity vectors. The ability
to vary surface velocities in direction and magnitude
provides a large range of entraining velocities and sliding velocities. The independent control of entraining velocity and
sliding velocity allows the formation of EHD film separation
PLATE
VERTICa.L--'
LOAD CELL
967
A:R BEARING
LOAD CELL
BALL SPINDLE
SALi.
DISC
Ball angle
0m ,
1
I i f ^ i^'^\K\f"'
>
(c)
Disc velocity
Entraining velocity
_X
Sliding velocity
968
MANUAL
HANDBOOK
between the surfaces to be m a d e independent of the tangential strain within the contact. The decoupUng of film thickness from teingential strain provides the opportunity to control EHD and boundary lubrication mechanisms along with
their failure pathways.
The EHD mechanism is a remarkably powerful lubrication feature that is fundamentally linked to oil properties. As
long as a minute quantity of fluid is captured in the inlet region of a moving contact, EHD pressure and film thickness
is generated. With proper oil supply, EHD film generation is
a highly stable process. The separating film has enormous
"stiffness." The thickness of the film is precisely determined
from the entraining motion of the surfaces, geometry of the
contacting bodies, Eind temperature of the fluid in the confined space upstream of the contact. Other t h a n temperature, most of the controlling parameters are readily available. These features make EHD film thickness an obvious
tool to control surface separation a n d the failure processes
associated with the degree of asperity penetration between
surfaces. The following sections describe the use of EHD
film thickness with lubricating oils for controlling wear and
scuffing modes of failure.
M u l t i - d i m e n s i o n a l Oil C h a r a c t e r i z a t i o n
(Performance Mapping)
The performance of oils and materials can be mapped out by
conducting tests over a range of entraining velocities, Ue, (i.e.,
EHD film thicknesses) and sliding velocities Us. In addition, the
mapping of performcince with these parameters can be directly
connected to gear and bearing hardware. This linkage is made
possible by specific relationships between Ue and Us that exist
in bearing emd gear contacts. With this linkage, the characterization of oils and materials can potentially be translated into
design and performance prediction. In addition, oil and material characterization tests can b e linked to service hardweire.
Performance mapping is illustrated below with two DODL-85734 aviation oils. These oils, which have "load-carrying"
or "EP" additives, are used in helicopter transmissions and
supersonic aircraft (Concorde) [2]. The tests were carried out
u n d e r the following conditions:
Scuff
DOD-L-85734 Oil PE-5-L1761
Severe wear
and scuffing
region
o 400 c
200
Scuff
EHD_regioD - soi50
100
200
150
500
450
JO
250 C
550
400
350
300
250
D)
Bulk temp,
of test ball
Severe wear
and scuffing
Testing
direction
=> 200
150
100
50
0
EHD region
75
100
125
150
175
200
225
970
HANDBOOK
Traction Coefficient
PE-5-L1705
PE-5-L1761
30
100
170
0.0845
0.0747
0.0739
0.0857
0.0776
0.0744
0.5
0.4
0.3
50
100
150
200
250
300
350
400
450
500
550
600
650
700
-i
1.3
1.2
Scuff
1.1
0.5
0.4
0.3
0
50
100
150
200
250
300
350
400
450
500
550
600
650
700
971
HANDBOOK
1.2
1.1
0.5
0.4
0.3
0
50
100
150
200
250
300
350
400
450
500
550
600
650
700
Sliding
Velocity, e
Us (m/sec)
cS.
, ^
: #
600
500
400
Sliding
Velocity, ^^
Us (in/sec)
100
-100
-200
973
974
MANUAL
HANDBOOK
must exist a sufficient local surface stress to initiate cyclic fatigue. The formation of micro-cracks may be a low cycle or
high cycle fatigue process, depending on the severity of the
local stresses produced. The severity of loccJ stresses is controlled by the ratio of h/cr. However, the h/cr ratio is not a sufficient parameter to control the details of the local stresses
within a lubricated contact. The average roughness height (a)
does not reflect the shape of surface features that control asperity pressure. Peak asperity pressures depend on the slope
of asperities near their summits. One also has to consider asperity size relative to the Hertzian contact width and the size
of the inlet region, which generates the EHD film thickness.
A stylus trace of the surface finish generated for surface
distress tests is shown in Fig. 12. The disk surface has a
roughness of 24 ^lin, Ra as measured by a stylus instrument.
Figure 12 also includes a calculation of the EHD film thickness (h) relative to the combined surface roughness height
(cr). A 5 cSt oil operating at 180C under the prescribed test
conditions gives a calculated h/cr of 0.10. The relatively rough
surfaces of the specimens are designed to accelerate the surface distress process so that micro-pitting can be achieved
within a relatively short testing period.
975
^ ^ j ^ ^
^J^ V H I * ^ ' * . * ^
r-
0.0 Itin
-50.0 iiin
I-
I
Hertzian contact width
/^VM^Ww'
Contact stress:
Entraining velocity:
Contact slip:
Temperature:
h/a (5 cSt oil):
The micro-pitting tests discussed above were conducted under conditions with 2% micro-sUp. Surface distress, particularly for gear contacts, encounter a range of sliding that goes
well beyond incipient sliding found in rolling element besirings. An increase in the sliding component of velocity promotes wear and generates more frictional heat.
An accelerated test protocol for surface distress with gross
sliding is shown in Fig. 15a and 15b. The test protocol continuously decreases the entraining velocity and increases the
applied load. The entraining velocity provides a continued reduction in EHD film thickness. As the surface features lose
their geometric sharpness due to wear, the load is increased
to continue the application of local stress at each roughness
feature. With independent control of the entraining and sliding velocities, the test can be run with a near-constant or decreasing sliding velocity so that the frictional heat generation
within the contact can be maintained at a desired level.
The test protocol can be completed in approximately one
hour. With properly selected test conditions, this approach
causes the surfaces to wear without initiation of scuffing. The
degree of contact severity can be continually increased by
running multiple tests at progressively increasing temperatures. The final operating temperature can be selected to correspond to the operating temperature of the component
hardware of interest.
The traction data for three tests run at ambient temperature, 50C and 90C, are shown in Fig. I5b. The traction coefficient progressively increases at each incremental change
976
HANDBOOK
PE-9-G0041
(Load additive)
Condition 3.2 + 2 hrs
EX482
4500
4000
1
o
6
3500
3000
2500
1500
Heroo-A
(Basestocit) y^
Condition 3.2 \ /
EX429
PE-9-G0041
(Load additive)
Condition 3.2 + 2 hrs
EX480
2000
1000
500
Condition 3.2
EX470
^
PE-5-L1785
(Anti-wear additive)
Condition 3.2 + 2 lirs
EX483
PE-6-L1785
(Anti-wear additive)
Condition 3.2 + 2 tire
EX479
Condition 3.2
EX472
1.0
1.1
1.2
1.3
1.4
1.5
1.6
lOOx
(a)
Traction During WAM3 Wear/Micro-pitting Tests
500
1000
1S0O
977
2000
2S00
3000
3SO0
4000
(b)
FIG. 15Test protocol for micro-pitting and micro-cracking, a) Transverse cracks and micro-pitting; b)
Traction results from wear and micro-pitting test protocol.
CHAPTER
surface distress and the stochastic processes of fatigue mzike
surface-initiated failure processes complex.
A flexible test machine can be programmed to provide a
controlled decrease in h/crin order to cause micro-pitting and
wear within a few hours of testing. The degree of test acceleration, as well as the sequence of wecir and micro-pitting
events along the p a t h w a y t o w a r d failure, can be easily
changed. In most cases, due to the mystery behind what actucdly tremspires in real hardware, the practical relevEuice of
simulation testing for micro-pitting may be questionable. To
obtain a short-term screening test with meaningful connection to specific hardware, a good understanding of the wear
and surface fatigue process in service hardware is needed.
Until controlled data from the field is obtained, there is no assurance that these test methods for surface distress are giving
meaningful information for oil formulation, material construction, design or operating condition.
Oil a n d M a t e r i a l T e s t i n g f o r A d h e s i v e W e a r
The above sections focused on testing for oil or material attributes with respect to wear, scuffing and surface-initiated
fatigue. Traditional testing of oil attributes for weeir, scuffing,
and fatigue resistance is less than adequate to fully characterize an oil and to predict performance in service. The same
can be said about bearing and gear materials. Traditional
bearing material test methods, which generally focus on subsurface-initiated fatigue, do not assure success in component
hardware. The whole notion of oil and material testing and
development is rccilly intimately linked in the real world. One
cannot address oil eveiluation without immediately crossing
the boundary into material evaluation.
Load, speed, temperature and corrosion protection are driving bearing and gesir materials toward greater rolling contact
fatigue life, wear/scuffing resistance, and corrosion resistance.
The introduction of hybrid ceramic/metal materials presents
new surface chemistry that may be incompatible with conventional lubricating oils. Corrosion resistant bearing materials
with different surface chemistry, as the result of chrome oxides
instead of iron oxides on the surface, can significantly affect
the reaction rates between material and oil chemistry to form
surface films. Surface distress tests with some corrosion resistant materials, conducted with low EHD film thickness relative to surface roughness, show that surface fatigue mechanisms ccin be preempted by local adhesion events.
The term "adhesive wear" is commonly used when failed
surfaces appear to have undergone plastic flow due to local
"adhesion" at the interface. Surface failure by adhesive wear
can be initiated at microscopic sites of insufficient surface
film lubrication or at sites of debris encounters. With limited
chemical reactivity between lubricating oil and some corrosion resistant materials, locEil adhesion events, which are not
able to recover, propagate into broad patches of adhesive
wear damage. In addition, material microstructure and properties, like hardness, that affect plastic flow seem to influence
the onset of adhesive wear. With sufficient sliding velocity
and contact stress, adhesive wear can transition into a major
scuffing event. A scuffing event is characterized by a rapid
rise in friction and temperature. These tribological features,
as measured with Ein adhesive wear test method, correlate
with experience in full-scale bearing tests.
36: BENCH
TEST MODELING
979
At the heart of surface durability is material compatibility with lubricating oil chemistry to form surface films,
which prevents local adhesion. The adhesive wear test
method described below progressively increases the degree
of asperity encounter at the interface u n d e r rolling/sliding
conditions. The test method invokes tribological interactions, which are measured in terms of friction (traction),
gentle polishing wear of surface features, adhesive wear
events, and scuffing.
Adhesive
Wear Test
Method
Adhesive wear tests, run with the WAM test machines, use
ball and disk specimens representing bearing rolling element
and raceway surfaces. Ball specimens are supplied by beeiring vendors. The disk specimens are heat treated and finished
to simulate bearing ring specifications. Surface preparation
of the disks consists of fine grinding, followed by abrasive
lapping to a surface finish of 2 /A-inch, Ra. The lapping operation is done with specimen rotation about its centerline to
create a circumferentieJ lay in the direction of rolling motion.
The finishing method consists of several lapping stages to obtain a consistent surface texture. Care is taken to avoid microscopic bends and folds ("leafing") in the surface texture.
The final finish is similar to a finely honed bearing raceway
of aircraft quality.
Ball sizes may range from 0.5 in. (12.7 m m ) to 1.125-in.
(28.58 m m ) diameter. The selection of ball size and quality is
determined by availability. The test ball specimens, which
are production quality, have m u c h better surface finish than
the disk specimen. Highlights of the test conditions are given
below.
Maximum
Hertzian
contact stress:
Entraining
(rolling)
velocity, Ug:
Contact slip:
1 0 . 1 6 - 1.27m/sec
(400 - 50 in/s)
Ue reduced in four stages of 180 s each
15%, subsequent tests 30% and 50% until
failure
If adhesive wear occurs at 15% slip, 8%
slip is run
% slip = (Ub - Ud)/ l/2(Ub + Ud) X 100
where Ub = surface velocity of ball
Ud = surface velocity of disk
MIL-PRF-23699 (Mobil Jet II), reference
Test oil;
oil
Test temperature: 200C (392F)
An adhesive wear test series for a materieJ generally consists of three tests: one each at 15% slip, 30% slip, and 50%
slip. If an adhesive wccir event occurs at 15% slip, the test is
repeated at 8% slip. Generally, two test series are run for each
material pair. At the end of each test, the running tracks on
the ball and disk specimens are photographed at lOOX. Traction coefficient is plotted over time for each test. The surfaces
of ball and disk specimens are documented with photomicrographs, which are stored as digital images.
At 200C the disk surface can become lightly discolored
with oxide or surface films from the oil. To avoid the influence of accumulated surface chemistry on the disk, the test
track on the disk specimen is refinished after each test.
980
MANUAL
Traction
Test
HANDBOOK
Plots
Tj^ical traction test plots are shown in Fig. 17. Initial operation at an entraining velocity of 10.16 m/s gives an EHD film
thickness to surface roughness ratio (h/cr) close to 1.0 and a
traction coefficient on the order of 0.02. Incremental reductions in entraining velocity increase the traction coefficient
due to thinner EHD films and greater surface interaction. A
gradual decrease in traction coefficient is attributed to polishing wear of surface features.
An adhesive wear event is identified by a rapid excursion in
traction coefficient. While the traction may recover after a few
seconds, the local surface damage that occurs during the adhesive wear event is permanent. The local adhesive wear damage becomes a vulnerable site for surface-initiated fatigue.
Ranking
Adhesive
Wear
Resistance
A system of ranking adhesive wear performance has been developed to characterize the overall lubricating performance
of various material pairs and lubricants. Performance is
based on measured behavior reflecting the ability of the material pair to accommodate low h/cr and high slip operation
without adhesive wear and with traction behavior reflecting
good lubrication at the interface. A point system is used to
give weighting factors for tribology attributes that we feel are
important for high-speed rolling element bearings. The criteria and weighting factors for performance ranking are shown
in Table 1.
100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400
Run Time (seconds)
FIG. 17Adhesive wear test protocol and traction results.
CHAPTER
36: BENCH
TEST MODELING
981
M50/M50
M50/M50
MSO/Stainless M50/Stainless M50/Stainless M50/Stainless M50/Stainless
High qual. STD Low qual. STD High qual. STD Run-in with
Low qual.
High qual. HTS NTS brand of
IMIL-PRF-23699IHIL-PRF-23699 MIL-PRF-23699 DOD-L-85734 MIL-PRF-23699 MIL-PRF-23699 IMIL-PRF-23699
Operation with
High qual. STD
Mafis tested in
bearing
MIL-PRF-23699
rig
Discussion
of Adhesive
Wear
Testing
Oil Evaluation
with Adhesive
Wear
Testing
HANDBOOK
moved from the test area immediately following oil shut off.
Oil-off tests can be conducted with various criteria for test
termination. These include: (1) oil-off operation until a rapid
rise in traction coefficient to an arbitrary value; (2) oil-off operation until a rise in traction coefficient to 0.15; and (3) oiloff operation for 220 s, which is beyond the time typically required to reach a maximum traction coefficient (0.4) and
the onset of a high wear rate.
Except where noted, the test oil is Mobil Jet II. From testing with qualified jet engine oil products, Mobil Jet II has excellent lubricating ability compjired to most oil brands on the
qualified products list for MIL-PRF-23699.
Typical Oil-off Test Results
To establish the role of oil lubricating characteristics during
oil-off conditions, two tests were run with a 4 cSt MIL-PRF7808 oil (TEL-0004), which has known difficulties in certain
applications. Oil-off tests were also conducted with high
load-carrying DOD-L-85734 oil, which is used in aircraft
gearboxes and demanding engine applications.
Typical oil-off traction behavior for M50/M50 materials
and the three oil types are shown in Fig. 19. With continuous
oil supply and a test temperature of 200C, the traction coefficient for a full EHD oil film is on the order of 0.025. A t3rpical traction coefficient for jet engine oil at ambient temperature (~23C) is on the order of 0.07.
The rise in traction coefficient after oil-off is associated with
local adhesion and transfer of matericJ from the ridges of the
finishing marks on the disk specimen. The local material transfer, smearing, and oxidation creates material pileup and a loss
of surface integrity. At this stage the surfaces encounter high
local friction events due to material pileup and high friction oxides. The amount of wear is not significant. While the surface
disturbance appears to be minor at the time of test termination,
the situation is in a run-away condition heading for gross surface failure and a traction coefficient on the order of 0.4.
The maximum traction coefficient of 0.4 is attributed to
massive adhesion and material transfer between the surfaces.
The rise in traction coefficient is associated with the spread
of adhesive events across the operating track on the specimens. A momentary departure from an increase in traction is
believed to be the result of lower tangenticil shear caused by
the onset of wear.
These tests show that oil starvation leads to local adhesion
and pileup of material on the surfaces with a corresponding
rise in traction coefficient. Once this process starts (and without subsequent oil replenishment) adhesion and oxidation of
transferred material become a run-away process. The runaway process seems to be well on its way by the time the traction coefficient has increased from 0.025-0.15a six-fold increase in traction coefficient.
Effect of Material or Oil Lubricating
Quality
The above results show that the initiation of run-away traction is due to adhesion and oxide growth at local sites. Resistcmce against adhesion depends upon the material pair, along
with protection against removal of surface films that prevent
atomic bonding between the surfaces. If this is the case, the
important attributes of the material for oil-off performance
cire associated with the material's response to chemistry or
"tribo-chemistry" of the oil.
0.40
0.35 -
- 250
0.30 1 of 2 heat
sources removed
Disc Temperature
200
8 0.25 ^
S 0.20
c
.g
150 I
MIL-PRF-7808K
(TEL-0004)
Gra.de 4
Q.
DOD-L-85734
MIL-PRF-23699
S 0.15
e
100 "
PWM53
0.10
PWM55
Lube supply
removed @ 600 sec
0.05
50
Traction Coefficient
0.00 1
500
j _
550
600
650
700
The oil-off test results with the three test oils in Fig. 19 are
summarized below with respect to the average time to a traction coefficient of 0.15.
Test Oil
10.5 s (2 tests)
42.0 s (3 tests)
81.0 s ( l test)
Oil additive chemistry and other factors affecting the lubricating ability of the oil are significant contributors to oiloff capability. An eight-fold difference between the time-tofailure is evident between a low queility oil for lubrication
compared to a high quality oil. The traction data in Fig. 19
show that the onset of failure for oil TEL-0004 is a sudden
event. The additive chemistry in the DOD-L-85734 oil results
in a gradual rise in traction coefficient. The gradual rise in
traction coefficient is associated with a controlled tribological process, which results in less severe local damage to the
surfaces. There are noticeably fewer areas of material transfer or islands of oxidized material on the surfaces with the
DOD-L-85734 oil.
Discussion
of Oil-off Test
Results
984
MANUAL
HANDBOOK
The direct and sensitive connection between entraining velocity and EHD film thickness holds the key to linking practical engineering peirameters to tribology phenomena within
a lubricated contact. This linkage makes the task of deeding
with chemical attributes of oils and materieds m u c h easier.
EHD theory provides the only useful design guide among all
the complex mechanisms in tribology. EHD film generation
mechanisms give a n opportunity to establish a c o m m o n denominator between testing and service performance. The importance of entraining velocity is its association with the entrainment of oil into the contact to generate a hydrodynamic
or EHD film. Since the ratio (h/cr) representing EHD film
thickness (h) and surface roughness (cr) is important with respect to the degree of asperity penetration within the confines of the contact, fundamental fluid properties of viscosity
and pressure-viscosity coefficient are essenticJ for oil characterization. Viscosity and pressure-viscosity coefficient give
rise to an inherent capability of oil to generate Ein EHD film
for surface separation. The sections below describe a test
method for determining EHD film-forming capability and
the determination of pressure-viscosity coefficient.
If EHD film thickness can be measured, it can be used to
calculate pressure-viscosity coefficient. If the EHD filmforming capability of cin oil can be determined directly from
oil film thickness m e a s u r e m e n t s , the characterization of
a n oil can go beyond the standard viscosity properties used
in oil specifications. These viscosity features include nonNewtonian effects and enhanced viscosity due to molecular
forces at the surface. The sections below s u m m a r i z e the
method used to measure EHD film thickness. Discussions include the role of pressure-viscosity coefficient on EHD filmforming capability and its impact on oil specification.
WAM Configuration for Optical E H D Film
Thickness Measurement
The oil film thickness of test oils can be m e a s u r e d between ball and disk test specimens under dynamic EHD con-
FIG. 20WAM machine with optical configuration to measure EHD film thickness with
interferometry.
CHAPTER
TEST MODELING
985
CO
c
o
i
36: BENCH
CO
Q.
(0
PE-9-G0041
PE-5-L1876
O)
c
H/IIL-L7808
Herco-A
0.1
O
I
LU
20
30
40
50
60
70
80
90 100
Temperature (C)
FIG. 21EHD film-forming capability versus temperature at 2 m/s.
(^oUe)"
3RO
(1)
where
film thickness, center of contact
combined radius of curvature 1/R = 1/Ri -II/R2
vis at atm. press and test t e m p
^o
a
pressure-viscosity coefficient
Ue
entraining vel., Ue = l/2(Ui + U2)
E'
combined elastic modulus, 1/E' = 1/2[(1
o^/Ei) + (1 - o^/Ez)]
Film thickness decreases with temperature due to the sensitivity of viscosity with temperature. The pressure-viscosity
coefficient (a) can also decrease with temperature. Because
the thickness of the EHD film is sensitive to temperature and
to the difficulty in controlling each test at exactly the required temperature, the test results are plotted in terms of
film-forming capability versus temperature. To do this we
have selected a reference entraining velocity of 2 m/s.
Using a reference entraining velocity of 2 m/s, the film
thickness for test oils is determined from the test plots of film
thickness versus speed for each test temperature. These EHD
film thickness values are then plotted as a function of temperature. The EHD film-forming capability for a number of
polyolester t5^e aviation oils supplied by the U.S. Navy is
shown in Fig. 2 1 . These aviation oils cover a range of viscosities from 3-9 cSt. The property data provided for these oils
are given in Table 2.
ho
Pressure-Viscosity Coefficients
The film thickness results of the test oils can b e plotted in dimensionless form where a film thickness parameter (ho/R) is
plotted against a dimensionless speed parameter (T7oUe/E'R).
986
HANDBOOK
TABLE 2Properties
of test oils.
Code
Oil Type
Viscosity @100C
Viscosity @ 40C
SpecGr@15C
SpecGr@40C
SpecGr@70C
Refractive Index
PE-5-L1557
PE-5-L1818
PE-5-L1876
PE-5-G0041
MIL-L-7808J
PE-5-L1274
Krytox 143AB
16350, lot 12
5 cSt basestock
5 cSt basestock
5 cSt basestock
9 cSt formulated
3 cSt formulated
4.5 cSt Herco-A
lOcStPFPE
80 cSt PFPE
4.84 cSt
4.93 cSt
5.06 cSt
8.79 cSt
3.15 cSt
4.5 cSt
9.8 cSt
80cSt
23.47 cSt
22.98 cSt
24.61 cSt
50.99 cSt
12.22 cSt
20.0 cSt
75cSt
900 cSt
0.9954
0.9683
0.9961
0.9858
0.955
1.003
1.902
1.925
0.9829
0.9574
0.9836
0.9739
0.938
0.9900
1.861
1.882
0.9743
0.9491
0.9736
0.9663
0.910
0.9808
1.808
1.830
1.4513
1.4526
1.4511
1.4610
1.56
1.56
1.36
1.3
r-
<u
o
Krytox 16350
it
0)
o ;r2?
s.
Referance fluid
(Kiytox 143AB)
8 -5
=?
fl)
3
CO
10
<a
3
^
ro
(1) r
n
LL <
2-
a)
>
o
(1)
11=
20
110
30
Temperature (C)
(ho/R)refoil
(Low speed)
(High speed)
Slide to
Roll Ratio
(S/R)
L ong I rt- - I EHD nim-tomiinB capablll^
987
^ --^^"^
Number of teeth: 28
Surface finish: 0.45-0.63 ;u,m (18-25
fiin.), Ra
Load Chamber
FIG. 24Cross section of Ryder Gear machine test head and gear mesh.
990
MANUAL
HANDBOOK
ous tip relief. Tip relief reduces the stress at the tip of the
tooth where the sliding velocity is high. This results in higher
than average load capacity with these geeirs. Because of this,
tests r u n with high load carrying DOD-L-85734 oils, suspended prior to the 22.5% scuffing point. Nevertheless, the
tests are very useful for establishing the onset of scuffing and
the progression of the scuffing phenomena.
Scuff Initiation Features o n Ryder Gears
Figure 25 shows side 'A' of the Ryder tests gears (Allison
T630603R) used to evaluate a DOD-L-85734 oil with Navy
reference n u m b e r PE-5-L1761. This test was suspended at an
80 psi load pressure (8th load stage) which gives a tooth load
of 3696 ppi (pounds per inch). The Allison geeirs with generous tip relief resulted in only 4.21% scuffed area. The n u m b e r
1 tooth of the narrow test gear is shown in the upper photo of
Fig. 25 and its mating tooth on the wide gear is shown in the
lower photo. The Ryder operator counted 5% scuff on the
n u m b e r 1 tooth of the test gear surface. The lighting used on
the tooth face for the photograph in Fig. 25 is similar to what
is used in the Ryder test to illuminate the test gear surface for
inspection with a TV camera. The small dark patches on the
dedendum of the test gear are areas where the grinding fea-
(b)
tures have been polished. The polished areas appear dark because the oblique lighting reflects the light away from the
camera, which is mounted normal to the face of the gear
tooth. These dark areas of polishing wear are also seen by the
Ryder operator on the TV monitor, but they are ignored by
the Ryder operator with regard to its contribution to the
scuffed area.
The wide gear in Fig. 25 shows similar polishing areas, but
they appear at the addendum rather than the dedendum. The
narrow test gear drives the wide gear. As the gear teeth mesh,
the initial contact occurs at the dedendum of the test gear
and the a d d e n d u m of the wide gear. There is much less polishing wear on the opposite ends to the tooth face where the
teeth go out of mesh, at least for this gear set. The polishing
wear footprint on the wide gear clearly shows the axial movement of the wide gear that occurs as the torque is increased
for each load stage. The amount of axial movement seems to
decrease with loading stage. The axial movement of the wide
gear causes the right hand edge of the test gear to run against
fresh material on the wide gear for each load stage. This explains why there is frequently more scuffing on the right side
of the test gear.
(a)
100 nm
991
damage in these areas seem to contribute very little to the total traction across the contact. In the Ryder test, polishing
wear seems to precede scuff initiation. The first few % scuff
that is counted may be nothing more than polishing wear of
the grinding ridges with abrasive scratches in the direction of
the sliding velocity. It seems that the scuff criteria for the Ryder operator is a disruption of the cixial grinding features by
perpendicular smearing of material, even to the relatively minor level of abrasive scratches.
Further evidence of scuff initiation is shown in Figs. 28 and
29, which aire taken from Ryder gears supplied by the U.S.
Navy from tests conducted with the reference fluid Herco-A
and a MIL-PRF-23699 oil (PE-5-L1790), respectively. These
tests were conducted with Pratt & Whitney gears. The two
teeth represent only a minor degree of scuffing compared to
the other teeth on the test gears. In both cases, scuff initiation
occurs at the dedendum of the test gear, where the meshing
teeth initiate contact and where the sliding velocity is maximum. The scuffed Eirea grows in the direction of the pitch
line. The scuffing damage is more advanced on the right side
of the tooth, which, as discussed above, is due to the presence
of fresh material on the wide gear introduced into the contact
100 nm
(b)
100 Jim
HANDBOOK
Herco-A. From the severity of the scuffed area, one would
judge that a notable increase in traction would result as the
tooth contact traverses this area of the tooth face. The increase in traction will accelerate the frictional heating of the
tooth surface.
Propagation of the Scuffing Front
In the above sections we determined that scuff initiation,
where the scuffed area is less than 10%, consists of superficial scuffing associated with the grinding features only. The
Ryder operator will even include narrow abrasive scratches
as part of the scuffed area. Polishing wear, even when quite
extensive, is not included. Scuff initiation, at least in this
case, occurs at the dedendum of the test gear where the sliding velocity is maximum. But the final judgment of load capacity is not made until, on average, 22.5% of the tooth face
surfaces are scuffed. The percent area scuffed counted for
each load stage as the scuffing progresses to, or just beyond,
22.5% is used to extrapolate, or interpolate, the load at which
22.5% is reached. This is accomplished by plotting the log of
the percent scuff versus the load pressure. The progression of
scuffing is frequently, but not always, an extension of the
scuffed area that has initiated at the dedendum, or possibly
the addendum. The scuffed area grows in the direction of the
pitch line, even though the sliding velocity decreases in that
direction. The "scuffing front" is able to move in that direction with increasing load.
(a)
100 ^m
by the axial movement of the wide gear as the load is increased. The photomicrographs in Figs. 28 and 29 show that
polishing wear precedes scuff initiation. In Fig. 28, where 7%
scuff has accumulated with Herco-A, the scuffed area is composed of smeared surface material. Some original grinding
furrows are still present indicating that the smeared materiEd
is quite shallow, involving primarily the grinding features of
the surface. Some of the protruding material in the scuffed
area shows polishing wear, indicating that the scuffing event
is followed by some degree of recovery with continued running. The degree of surface disturbance in the scuffed area
appears to be similar to what we call a "micro-scuff," which
is surface damage confined to the roughness features. From
this, we would judge that the 7% scuff damage on this tooth
has occurred with a less than significant perturbation in
traction.
The Ryder tooth in Fig. 29 has accumulated 10% scuff with
oil PE-5-L1790. The scuffed area appears more severe than
the 7% scuff in Fig. 28. This oil, which includes an anti-wear
additive (TCP), shows more brown and blue surface films in
the unscuffed area than the test run with Herco-A, which has
no anti-wear additive. The scuffed area shows much wider
paths of smeared material than the 7% scuffed material with
'tew
993
face films. Surface films become visible on the unscuffed areas as well as the scuffed areas. It can be postulated that if the
test conditions are not appropriate to invoke the load additive, the ranking of the oils could be quite different. Also, it is
clear that oil ranking may vary if the selected scuff criteria
were different from the arbitrary selection of 22.5%.
Tribological Processes During Scuff Progression
For oils with the same viscosity, the tribological processes
that control the progression of the scuffing front will determine the scuffing load capacity and the relative ranking of
test oils. An understanding of the tribological progression of
events is important with respect to how the oil functions as
well as how a Ryder load capacity test should be simulated.
While scuffing on the narrow test gear is used to determine
load capacity, it is the wide gear that provides more useful information on the progression of events that lead to the scuff
criteria. Figure 33 shows the #15 gear tooth pair that has encountered 33% scuff with DOD-L-85734 oil FE-5-L1705. The
axial movement of the wide gear with load preserves a history
of the surfaces for each load stage. The upper photomicro-
s. 4 # i \ i^,.^^':^,'
"ff'tfit
'ff-i
tiation, which may only be minor abrasive scratches, the progression of the scuff for this oil with the Sier Bath gears is
much less than the reference oil PE-5-L1274 (Herco-A) as
well as the MIL-L-23699 oil, PE-5-L1664. The results are not
plotted in semi-log fashion, as is customary for Ryder data,
so that the real progression of scuffing versus load can be
illustrated.
It is interesting that in the early days of the Ryder test,
Earle Ryder acknowledged that the slope of the data on a
semi-log plot vsiried from test to test. He attributed this to "a
random effect that can never be tamed" [4]. Actually, the
slope has a tribological explanation. The slope is a measure
of the rate of propagation of the scuffing front on the tooth
face from the dedendum or addendum toward the pitch line.
The slope is lower for oils with a load additive because once
a scuff is initiated the additive inhibits its propagation. From
the data in Fig. 32, it seems that the presence of a load additive does not influence the first evidence of a scuff. This could
be due to insufficient surface temperature or asperity interaction to cause the additive to react. Once the scuff progresses beyond 5 or 10%, the tooth temperature increases,
and the additive chemistry is activated to form protective sur-
(a)
I-
100 (un
50
45
40
HANDBOOK
DOD-L-85734
PE-5-L1304(A)
PE-5-L1761 (B)
Sler Bath #6
gears
Herco-A
PE-5-L1274
SierBath#3
gears
CQ
u.
u.
3
CO
i
DOD-L-85734
PE-5-L1705
side 'A' only
30
40
50
60
70
100
graph in Fig. 34 shows the left edge of the load path during
the first load stage where polishing wear of the grinding
ridges is clearly evident. Calculation of the ratio of elastohydrodynamic (EHD) film thickness to surface roughness (h/cr)
for a surface temperature equal to the inlet oil temperature of
74C (165F) is less than one. If this is correct, some sort of
polishing wear or surface damage is expected. In fact, with
such a small h/a, more surface interaction would be expected
than shown in Fig. 34. This leads one to question the assumption that the tooth surface temperature for the first load
stage is as high as the inlet oil temperature of 74C (165F).
Prior to the start of test, the gear mesh exit, which is located
at the bottom of the gear pair, is heated with the oil supply at
a flow rate of 270 ml/min for a period of 1/2 h. The gears are
not rotated during this heat-up period. The oil supply is the
only source to control gear temperature. The actual gear
tooth temperature will depend on the rate of heat dissipation
through the gear and shaft support system. The inlet oil temperature cam be viewed as an upper bound for the tooth surface temperature. The actual temperature, at least when the
test is initiated, will be less than the inlet oil temperature.
The lower photomicrograph in Figure 34 shows the left
edge of the scuffed area as well as the surface areas adjacent
to the scuff, which have only seen contact at previous load
stages. As one views the photomicrograph from left to right,
the tribological history of the surfaces is revealed. When the
load (and surface temperature) increases, the surfaces en-
995
From the scuffing data in Fig. 32, it seems that the selected Ryder operating conditions cause typical MIL-L23699 oils and DOD-L-85734 oils to transition into a macroscuff failure mode about the time that the 22.5% scuff
criteria is reached. This is a tentative statement because
most of the gear teeth examined were from Allison gears
with generous tip relief that fail at relatively high loads
where a macro-scuff event is more likely (see scuff data for
Allison gears in Fig. 32).
Since the oils tested have the same base oil viscosity, the
scuffing differentiation between the oils is a result of the way
oil chemistry handles the roughness features on the gear
tooth face. To activate oil chemistry, gear tooth temperature
must be an important factor. Another important factor is the
"tribologiccd" interaction at asperity (or grinding ridge) sites.
Tribologicai interaction involves normal load and tangential
strain at asperity sites. Asperity pressure and tangential
strain (sliding velocity) control the local temperature that activates oil chemistry. Oil chemistry is also influenced by activated iron surfaces, where the rubbing process removes surface films to expose material at a high energy state. What
makes the Ryder Geetr Test work then are two important fea-
100fun
of surface films that can control the initiation and progression of the scuffing front toward the pitch line. Temperature
is a key parameter that controls surface film formation. Surface temperature is also an important parameter for controlling the EHD film thickness. Two temperatures seem to be
important: (1) the tooth surface temperature, which controls
the inlet oil viscosity and possibly the out-of-contact surface
film formation, and (2) the total temperature within the contact (flash temperature plus out-of-contact surface temperature). The total temperature is frequently used as a scuff prediction criteria (flash temperature theory). The flash
temperature is the thermal response to frictional heating
within the contact. It is directly related to the traction coefficient, applied load, and sliding velocity. Flash temperature is
a calculated quantity with quite limited precision because of
heat partitioning and dissipation assumptions that have to be
made. Flash temperature in the Ryder test is difficult to estimate because the traction coefficient is not measured. It is
now possible to improve the calculated flash temperature in
the Ryder test by using the traction coefficients measured in
simulation tests for load capacity. The flash temperature that
is calculated is the global flash temperature associated with a
single heat source represented by the Hertzian contact. Since
we found much of the tribological action to occur at the
grinding ridges, it is likely that local asperity flash temperatures may be a more relevant quantity in the control of surface film formation. In this case, the precision of temperature
prediction depends on surface topography and local traction
coefficients at asperity sitesboth of which are not steady
state phenomenon. With regard to Ryder Gear simulation
tests, it is possible, and desirable, to be able to refine the calculation of the relevant temperatures due to frictional heating. Several temperatures are relevant. They range from the
bulk specimen temperatures to the asperity temperatures
within the contact. For now, we confine our thinking to the
two temperatures identified above.
From a practical viewpoint, with regard to Ryder test simulation, it is more important to focus on the out-of-contact
surface temperature. If the surface temperature is correct,
then the flash temperatures will take care of themselves provided the other contact parameters are appropriately simulated, such as: contact stress, sliding velocity, surface finish,
h/cr, and contact dimensions.
There does not seem to have been a detailed study of the
Ryder tooth surface temperatures. At the start of the first
load stage one can assume that the tooth surface temperature
is similar to the inlet oil temperature of 74''C (165F). Actually, from the above discussion on polishing wear and h/oduring the first load stage, the initial tooth temperature is
likely to be less than the oil supply temperature.
A second data point on the temperature profile for Ryder
Gear simulation can be derived from the "smoke point." The
smoke point is the temperature at which the surface immediately outside the contact area becomes hot enough to vaporize the oil to produce "smoke." In our Ryder Gear simulation tests we found ball temperatures in a few cases to be
sufficiently high to produce smoke. The measured ball temperatures that produce smoke are on the order of 200C
(392F) for typical MIL-L-23699 and DOD-L-85734 oils. The
Ryder tests frequently produce smoke, especially when the
percent scuff goes beyond 22.5%. It is assumed that the tooth
must also be the case for the narrow and wide gears used in
the Ryder test. A visual comparison of the simulation test
specimens and Ryder specimens is shown in Fig. 37.
The Wedeven Associates, Inc. WAM load capacity tests to
date have not addressed a precise simulation of the Ryder
tooth surface temperatures, which are still unknown quantities. If our assessment of the Ryder tooth temperatures is correct, simulation tests may have ball temperatures higher than
the narrow test gear temperatures and disk temperatures
lower than the wide gear of the Ryder.
Rolling and Sliding Velocities Across
the Tooth Face
The rolling and sliding velocities across the tooth face are directly linked to oil performance because they are key parameters that control lubrication and failure mechanisms. The
rolling (R) and sliding (S) velocities are defined as
R = 1/2 (Ui + U2)
S = (Ui - U2)
where Ui and U2 are the velocities of surfaces 1 and 2.
Note: Rolling velocity, R, is sometimes referred to as the
entraining velocity Ue, and sliding velocity, S, is sometimes
designated as Us.
The rolling, or entraining, velocity generates an EHD pressure in the inlet region that separates the surfaces in the
Hertzian region with an EHD film. The sliding velocity con-
zao
1'r
180
.0-0-0"
,-o-<^<^^'
.-o-o-O'
0 LtI
10
20
30
40
50
997
-I
60
lU
70
-1
80
90
i_
100
110
120
130
Loadt (lbs)
FIG. 36Simulated surface temperature profile for WAM3 tests based on estimated Ryder tootli surface
temperatures.
998
HANDBOOK
trols the rate of shear and heat generation within the
Hertzian region. A necessary condition for scuffing is that the
EHD film is sufficiently thin to cause the surfaces to interact
and that the shear and heat generation within the contact region is sufficiently great to cause the breakdown of microEHD and boundary film lubrication mechanisms.
The rolling and sliding velocities across the Ryder tooth
surface can be calculated from the geeir geometry and rotating speed. The calculated rolling and sliding velocities,
shown in Fig. 38, are plotted as a function of roll angle. For
reference, specific points are identified along the tooth face
using the following notations:
LPC
LPSTC
PD
HPSTC
OD
24
LPSTC
PD
HPSTC
OD
22 h
20
18
o
16 I14
o
^
8
6
4
2
0
12
14
16
18
20
22
24
26
28
30
32
34
36
LPC
18
u 16
(0
in
14
12
1
1
1
1 Entraining
1
Valoclty
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
o 10
<
8
6
4
2
1
1
1
1
1
>
OD
HPSTC
22
20
PD
LPSTC
999
12
14
\
\.
\
\
\
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1 \^
1
\
1
\
1
18
20
22
24
,^Sliding
/ Valoclty
/ \
1,
16
26
1
1
1
1
1.
28
30
32
34
36
HPSTC
I.PS1fC
Anticipated pragzeBsioa
t o 22,5% scuff.
yvc
FIG. 39Geometric positions across Ryder tooth face Including anticipated progression to 22.5% scuff.
1000
MANUAL
HANDBOOK
1000
2000
3000
STC). For the most part, one would expect the load on the area
being scuffed to be a portion of the total load that is shared between two pairs of teeth. Only under ideal conditions would we
find equal load sharing between two pairs of meshing teeth.
Because of practical geometric tolerances and dynamic loads,
the contact stresses that actually exist on the tooth face can be
m u c h higher thein that predicted under ideal conditions. For
this reason, the contact stress profile at the low point single
tooth contact (LPSTC) is used as a reference for simulation.
The contact stress profile on the tooth face at the LPSTC is
plotted in Fig. 40 as a function of tooth load in pounds per
inch (ppi). The relationship between the Ryder load oil pressure (psi) and the tooth load (ppi) is approximately ppi = 46
X (psi). The contact stress from the first to the ninth load
stage for the Ryder remges from 0.79 GPa (115 ksi) to 2.07
GPa (300 ksi). The load and stress profiles used in simulation
load capacity tests are similar. Thirty load stages are used
from 17.9 N (4 lbs) to 623 N (140 lbs) in order to provide a
contact stress from 0.73 GPa (106 ksi) to 2.4 GPa (348 ksi).
With a proper selection of sliding velocity, contact stress
protocol and degree of asperity interaction, as represented by
hJcr, the tribological mechanisms experienced in the Ryder
Gear Test Method (or any other gear operation), can be simulated. All that is needed is a test machine to cover these conditions and test specimens that replicate the material qualities of Ryder gears. Simulation tests with these conditions cire
described in the next section to illustrate how a tribology test
machine can simulate a high-speed gear machine.
4000
5000
6000
7000
8000
CHAPTER
The purpose of this section is to show h o w the Ryder Gear
Test Method can be simulated with respect to the lubrication
and failure mechanisms that control scuffing performance.
Simulation tests are different from correlation tests. The aim
of correlation tests is to rank oils like the Ryder Gear Test
Method. Simulation tests invoke lubrication a n d failure
mechanisms with test parameters that can be linked to the
gear test method. The development of a simulation test is
given in detail to illustrate the process of linking tribology
testing with a full-scale component, like a gear pair. This process is foundational to linking oil testing to field service
performance.
B a c k g r o u n d of Load Capacity Simulation Testing
The U.S. Navy has supported efforts [3,7,10] to provide
Ryder-like load capacity data of gas turbine and gearbox oils.
These efforts EJSO expand the scope of oil characterization beyond the perspective of a pass/fail or ranking of oils, with
scuffing performance being the only criteria. To provide continuity between Ryder Gear load capacity data and future oil
characterization methods, a "WAM Economical Load Capacity Screening Test" was developed to rank a wide range of engine and geEirbox oils similar to the Ryder Gear Test Method
[5]. This test method ranks oils with respect to a scuffing failure event. It also characterizes oils with respect to traction
(friction) behavior.
The introduction of high thermal stability (HTS) oils, and
particularly corrosion inhibited (CI) oils, has highlighted the
need for greater testing sensitivity for oils exhibiting lower
than average lubricating performance. Low lubricating performance, as evidenced in the Ryder test, reveals itself in the
form of a superficial form of scuffing ("micro-scuffing").
The test conditions selected highlight the load capacity performance features of oils that are submitted for qualification
under the MIL-PRF-23699 specification. Load capacity tests
are conducted with ball and disk specimens, which are operated u n d e r tribological contact conditions similar to the U.S.
Navy Ryder Gear Test Method. The WAM High Speed Load
Capacity Test Method has been approved by SAE E-34C for
incorporation into AIR4978 "Temporary Method for Assessing the Load Carrying Capacity of Aircraft Propulsion System
Lubricating Oils."
Failure Criteria in T e r m s o f Scuffing
a n d Micro-scuffing
The purpose of this test method is to evaluate oils according
to the Ryder Gear Test Method, with enhanced sensitivity for
lower than average lubricating performance. It is importcint
to recognize that the Ryder Gear performance criteria are
based upon the visucJ observations of "scuffing" damage on
Ryder geeir teeth. Since some scuffing features found on Ryder geEir teeth are superficial, a Ryder-like test method must
also invoke the same t5^e of surface deterioration mechanism. Micro-scuffing is a superficial form of scuffing, which
is confined to the surface topographical features of the gear
teeth. Micro-scuffing is generally associated with surface
damage at low load stages where contact stresses are too low
to cause "macro" scuffing. Scuffing, or "macro-scuffing," is
associated with the complete loss of surface integrity. Scuff-
36: BENCH
TEST MODELING
1001
ing involves gross failure of near-surface material, in addition to surface roughness features. When traction (friction) is
measured, micro-scuffing is generally detected by a rapid decline in traction coefficient. The decline in traction coefficient is associated with the removal of surface roughness features. While this action actually restores some of the EHD
fluid film separation between the surfaces, the rapid removal
of surface features by plastic flow and rapid polishing wear
reflects a failure of the oil to provide adequate surface films
for boundary lubrication. In contrast, macro-scuffing is associated with a sudden increase in traction coefficient resulting from massive adhesion and plastic flow of near surface
material. A sudden and massive scuffing failure requires high
contact stresses in the presence of high sliding velocities.
The observation of traction coefficient during a load capacity test is quite informative. High precision measurements of traction coefficient clearly identify "events" like
scuffing and micro-scuffing, as discussed above. Traction behavior also reflects the continual interactive process between
oil chemistry and the mating material pair within the contact. Subtle chatnges in topographical features due to wesir
are reflected in traction behavior.
Simulation Approach
The load capacity test protocol is conducted with a WAM test
facility shown in Fig. 4 1 . The test machine controls specimen
position, contact load, and motions of a single contact in
space. A computerized r u n file controls load and contact
kinematics between the specimens. Specimen temperatures
are recorded with trailing thermocouples. The high-speed
test protocol uses AISI 9310 bedl and disk specimens with
tight specifications for surface finish and hardness. To capture Ryder-like oil performance features, the following test
specimen specifications ctnd test conditions have evolved.
BaU
Disk
Ball vel.
Disk vel.
Orientation
Entraining vel.
Sliding vel.
Load
Test duration
Failure criteria
Performance
1002
MANUAL
HANDBOOK
TOP PLATE
A m BEAKING
BALL SPINDLE
BALL
DISC
SmE MOTION
TC INPUT
AC OUTPUT
Oil supply
Specimen temperatures controlled by frictional heating. Surface t e m p e r a t u r e s increase with load stage from a m b i e n t to
- 2 0 0 C.
Computer controlled peristaltic p u m p , approximately 1 drop/s. Oil flow rate is selected for adequate lubrication without significant cooling.
The entraining velocity (Ue) and sliding velocity (Us) are defined below:
Ue = l/2(Ub + Ud)
Us = (Ub - Ud)
where
1003
event are shown in Fig. 43. Micro-scuffing events, represented by momentary reductions in traction coefficient, reflect marginal oil chemistry to sustain surface films for protection against local adhesion and wear of surface features.
Some oils show multiple micro-scuffing events. Multiple micro-scuffs are characteristic of the non-formulated 4 cSt oil,
Herco-A. A macro-scuffing event is easily detected by a sudden increase in traction coefficient.
C D ' s l - C N J O C O C D ' ^ C N O O O O O
C M C s l C g C M T - T - T - T - T - O O C O - ^ C S I
0
00
"^
0
in
CO
"^
'is
0
0
10
T
*i
i
?s
ID
1^
djX
3
Q
CD.
CO
""
CJ
<a
m
II
5.^i,
(0
g
0
0
CM
0
10
0
^ /
/*^^
(0
a
B
<D
0
0
(0
C5>
(D
10
1^
1-
c
3
Q:
ix'
3.
CO II
OH
o"
3 : <-
tl
^13
c
CO
CO
Cvl
li.
a:
JO
ir> 00
( 0 o .. <
o a.
Q
CM
<X5
O
CO
O
O
O
CD
juapiyaoQ uogoBJi
CM
CD
CD
CM
O
CD
I
5
!
.K%
a:1
h- J CD Q
d>
0
0
CO
CD CO
0
0
CO
in
-^
1
r^
'
0.14
0.12
0.10
c
0)
o
200
180
\- 160
Ball
100x
Disc
lOOx
140
0.08
120
0.06
100
c
o
fs
o
S^
Traction Coefficient
0.04
80
Ball Temperature
: W^l^^^^M**w*H^^^
60
0.02
Vertical Load
0.02
400
500
600
Run T i m e (seconds)
E
h(0
D
CD
O
h 20
0
I
300
CD
3
0
Q.
40
Disc Temperature
0.00
O
O
900
800
700
FIG. 43Test terminated after tenth load stage to show micro-scuffing features.
220
Test: NA1333,NA1334,NA1335,NA1336
Lube: PE-5-L2053
Ball: 9310, Ra=10 |jin
Disc: 9-49b, 9310, Ra=6 pin.
Entraining Velocity: 225 in/sec.
Sliding Velocity: 346 in/sec.
Temperature: Ambient
Velocity Vector Angle (Z): 75
0.14
0.12
0.10
: 200
7 180
- 160
c
o
c
o
o
140
120
a>
a.
0.08
Ball Temperature
<D
O
NA1336
J
0.06
Traction Coefficient
h 100
80
0.04
60
0.02 Disc Temperature
40
0.00 -
20
Vertical Load
-0.02
'
I '
150
'
I '
300
'
I '
450
'
I '
600
'
I '
750
'
I '
900
'
I '
'
I '
'
I '
'
I '
'
I '
0
1800
in
o
CO
o
1005
O
o
a.
JD
I
-11
1 1 1 1 1 1 1 1 1 I
1 1 I 1 1 1 1 1 1 I 1 1 1 1 I 1 1 1 1 I I
r-
150 300 450 600 750 900 1050 1200 1350 1500 1650
1800
0.10
0.09
c
'o
0.08
i t 0.07
0
o 0.06
O
c
_o 0.05
"o
CO
CD
O)
CD
CD
>
<
-Scuff or micro-scuff
failure criteria
(avg. for all tests)
0.04
STD oil
high scuff
resistance
(3 of 4 tests
suspended)
0.03
0.02
^Cl oil with unacceptable wear
resistance and scuff resistance
(2 tests)
0.01
0.00
-11r~'''I
'
''I''f1''1'1'
'
I''I''I
Ir1'IIIII!'Ir1I'['IIIrr-
10 12 14 16 18 20 22 24 26 28 30 32
Load Stage
FIG. 46Scuffing and traction behavior of MIL-PRF-23699 type oils.
100 |m
1007
that the ball has reached compared to the disk (130C). The
reaction films are likely to have formed near the end of the
load capacity test where the specimen temperatures are high
and h/cr is small. Even with the presence of a significcint reaction film on the ball, there seems to be no perturbation in
traction coefficient.
The above tests show that the variation in traction behavior during a load capacity test does not seem to be affected by
bulk oil shear of an EHD film or perhaps even the presence
of boundary films. The traction behavior appears to be a
function of how oil chemistry affects the topographical features on the surfaces by way of polishing wear and scuffing.
The traction data with smooth surfaces and a standard
(STD) MIL-PRF-23699 oil provide a lower bound traction,
which is essentially unaffected by surface roughness features
and boundary lubrication. The lower bound traction is attributed to the shear behavior (traction) of the bulk oil. Interactions between surface topographical features do not
occur until late in the test protocol, when the contact temperatures are high and the EHD film is thin.
Performance Criteria
From all the load capacity traction data collected over time,
there seems to be a strong connection between traction coefficient and wear of surface finishing features. While fluid
temperature within the contact zilso affects traction, the rise
and fall of traction coefficient still reflects the process associated with how the physical and chemical properties of the
oil handle the intimate collisions of surface features within
the contact during a load capacity test. Since the WAM High
Speed Load Capacity Test protocol covers a large temperature range, we assume that the lubricating ability of the oil,
as reflected in traction, is also being tested over a large temperature range. If this is the case, the lubricating ability of the
test oils can be differentiated with respect to preservation of
surface topographical features, at least over a limited range
of temperature or contact severity. Additional investigations
are required to determine if subtle differences in traction
truly reflect variations in chemical activity for wear resistance in service hardware.
It can be postulated that the desired lubricating attributes
of oils are good wear resistance and scuffing resistance (and
surface fatigue resistance) "across-the-board" of temperature
and stress. The WAM High Speed Load Capacity Test protocol may be covering at least some of the desired performance
features and test conditions. For gear or other surfaces with
prominent roughness features one could argue that some
mild polishing wear is desired to topographically condition
the surfaces for low asperity stress to prevent early micro-pitting. If this were the case, good performance would be
associated with relatively low traction coefficient and high
scuffing load stages. Further tribology studies of service
hardware are needed to clarify the desired oil attributes and
testing conditions. Until this is done, we have to live with a
tenuous link between qualification testing and field performance. For now, the traction behavior and scuffing resistance of an oil, as determined with the present set of Ryderlike test conditions, can serve as an initial step toward full
characterization and clarification of performance criteria. In
the meantime, the collection of a database for test oils, along
1008
HANDBOOK
0.10
0.09
C
0
0.08
Failure criteria
(avg. of all tests)
iE 0.07
0
o
O 0.06
c
o 0.05
o
\ ,
\ I
CO
0.04
MIL-L-7808 Grade 4
TEL-0004
(4 tests)
(NA1368-NA1371)
0
CO
MIL-PRF-23699 CI
DLA 522
(4 tests)
0.03
0.02 -\
- Q-'
O'
e~^-o
0.01
0.00
-T1111IIIr-'I11111r
-ii11r-i1111I1r-
10 12 14 16 18 20 22 24 26 28 30 32
Load stage
FIG. 48Traction and scuffing failure characteristics of oils with known performance difficulties is specific military aircraft
hardware.
0.10
0.09
I Lower bound
{
I failure stage
|
I based on militaryi
hardware
I
experience
I
IProposed OEM
(scuffing limit
1009
I \ Scuffing or micro-scuffing
failure criteria
(avg, of all tests)
Oils DLA 522 and TEL-0004
have known deficiencies in
field service.
Oils DLA 562 and PE-5-L1859
failed the Ryder Gear test.
PE-5-L1874
4 tests)
DOD
DLA 511
(4 tests)
4 of 4 tests
suspended
DOD
PE-5-L2040
5> (4 tests)
3 of 4 tests
suspended
10 12 14 16 18 20 22 24 26 28 30 32
Load stage
FIG. 49^Traction and scuffing characteristics of qualified oils and oils with known performance deficiencies.
HANDBOOK
0.10
0.09
0.08
mended activity to sort out the significance of oil performance characteristics. This action is also an essential step
for the development of testing methods, which are truly
linked to service performance.
Applicability of WAM High Speed Load Capacity
Test Method
The WAM High Speed Load Capacity Test Method is a simulation of Ryder Gear Test ranking. The test conditions are
carefully selected to mtike the results correlate with the Ryder Gear Test. While the Ryder Gear Test operating conditions, in terms of rolling/sliding speeds, temperatures and
contact kinematics, are representative of helicopter gearbox
hardware, slight operational changes are likely to cause different rjinking. This is based on WAM load capacity tests conducted over a range of test conditions, which affect EHD film
generation and contact temperature. Load capacity tests over
a range of conditions are recommended. The conditions selected here are specific to Ryder ranking using a set of five
reference oils supplied by the U.S. Navy. In addition, there is
no confirmation that scuffing load capacity performance is in
any way connected with other prominent life-limiting performance criteria, expressed as surface distress (wear and micro-pitting). Additional tests for surface distress, or a complete simulation of specific hardware, are recommended to
supplement scuffing load capacity results.
260
Failure criteria
(avg. of all tests)
r 240
7 220
- 200
0.07
180
c
0)
160
PE-5-L2000
(4 tests)
;o 0.06
140
O 0.05
c
o
g 0.04
PE-5-L1823
(3 of 4 tests suspended)
OilB
(4 tests)
0)
CO
<D
100
80
60
0.03
..Q^.-eee--^*~^49-
40
20
0.01
0.00
a.
120 E
0)
0.02
0
6
10
12
14 16 18 20 22
Load Stage
Qualified STD MIL-PRF-23699 Oils
24
26
28
30
FIG. 50Average traction and scuffing stages for qualified Standard (STD) IVIIL-PRF-23699 oils.
32
0.10
0.09
0.08
1011
260
Failure criteria
(avg. of all tests)
I- 240
220
200 O
h 180
0.07 -_
c
PE-5-L1990
(4 tests)
0.06 -_
<u
o
O
c
o
SI
o
CD
0.05 -_
160
OilB
(4 tests)
Oil A
(4 tests)
(PWL14-PWL17)
0.04 ^
140
Q.
120
.0)
100
I
I
80
0.03 z
h 60
0.02 ^
-e&o-
~*G"^"'
40
0.01 -
20
0.00
10
12
14 16 18
Load Stage
20
22
24
26
28
30
32
HANDBOOK
0.10
Run File: naa.run
Ball: 9310, Ra = .25 urn (10 |jin)
Disc: 9310, Ra = .15 ^im (6 iJin)
Entraining Velocity: 5.72 m/s (225 in/sec)
Sliding Velocity: 8.78 m/s (346 in/sec)
Velocity Vector Angle (Z): 75
0.09
0.08
it 0.07
o
PE-5-L1997
(4 tests)
NAVAIR.00072
(4 tests)
0.06
c
o 0.05
o
03
NI
0.04
PE-5-L2001
tests)
O)
0.03
PE-5-L2002
(4 tests)
0.02
Lower bound reference,
polished surfaces, STD oil
0.01
0.00
10 12 14 16 18 20 22 24 26 28 30 32
Load Stage
Qualified CI MIL-PRF-23699 Oils
FIG. 52Average traction and scuffing stages for qualified Corrosion Inhibited (CI) MIL-PRF-23699 oils.
additive package. While both oils have good scuffing performance, their traction behavior reflects quite different
wear performance. Extensive testing with these oils reveals
significantly more chemical polishing wear with oil A compared to oil DLA 511. The lower traction coefficient with oil
A is consistent with lower oil out temperature, as measured
in Ryder Gear tests. While both oils have extensive field service, the noticeable difference in wear behavior, as reflected
in these tests, has not been investigated in field service
hardware.
Basestocks
S e l e c t e d U . S . Air F o r c e O i l s M I L - P R F - 7 8 0 8
Grade 3 and Grade 4
The U.S. Air Forces oils in Fig. 54 show the effect of oil viscosity during the initial load stages where temperatures are
relatively low. The markedly different traction behavior of
the two Grade 4 (4 cSt at 100C) oils indicates the strong role
oil chemistry has on wear and scuffing capacity. The Grade 3
MIL-PRF-7808 has higher load capacity t h a n the Grade 4
oils. Since viscosity differences at elevated temperatures are
insignificant, oil chemistry becomes the dominating factor in
scuffing and wear performance.
0.10
0.09
0.08
260
*^ 0.07
c
Failure criteria
(avg. of all tests)
b 240
220
200
180
160 I
DLA511
(4 tests)
(Na1251-Na1254)
<u
1 0.06
a>
O 0.05
c
g 0.04
0)
140 Q120 ^
100
CD
I-
80
0.03
CD
O
60
0.02
40
20
0.01
0.00
T"
"T
T"
"T
"T
10 12 14 16 18 20 22 24 26 28 30 32
Load Stage
Qualified DOD Oils, DOD-L-85734
FIG. 53Average traction and scuffing stages for qualified DOD-L-85734 oils.
0.10
0.09
0.08
c
0)
0.07
o
Scuffing or
micro-scuffing
failure criteria
(avg. of all tests)
O 0.06 :
c
o
0.05 o
Grade 3
MiL-PRF-7808L
(4 tests)
. Original
/^ 27502
Prototype
(4 tests)
CO
0.04
O)
CO
1-
0.03
0.02
Grade 4
H/IIL-PRF-7808
TEL-0004
(4 tests)
CD
6.5 cSt
e& o
0.01
0.00
10 12 14 16 18 20 22 24 26 28 30 32
Load Stage
U.S. Air Force Oils
FIG. 54Average traction and scuffing stages for U.S. Air Force oils.
1013
0.10
0.09
0.08
Failure criteria
(avg. of all tests)
PE-5-L1876
(4 tests)
(NA1306-NA1309)
0.07
PE-5-L1887
(4 tests)
(NA1300-NA1303)
(D
O
O 0.06
c
o
0.05
o
PE-5-L2039
(4 tests)
(NA1293-NA1296)
PE-5-L2056
(6 tests)
(NA1360-NA1385)
CO
0.04
(D
CD
0.03
PE-5-L2057
(4 tests)
(NA1364-NA1367)
PE-5-L1836
(4 tests)
(NA1287-NA1296)
0.02
Lower bound reference,
polished surfaces, STD oil
0.01
0.00 J
0
10 12 14 16 18 20 22 24 26 28 30 32
Load stage
Basestocks
FIG. 55Average traction and scuffing stages for basestocic oils.
0.10
0.09
0.08
c
o
o 0.07
JE
CD
O
CI Oils
MIL-PRF-23699
(4 oils)
Grade 4
MIL-PRF-7808
(2 oils)
HTS Oils
MIL-PRF-23699
(4 oils)
0.06 ]
STD Oils
MIL-PRF-23699
(5 oils)
c
o 0.05
o
CO
0.04 ]
D)
CO
0.03
DOD Oils
DOD-L-85734
(2 oils)
all tests suspended
0.02
0.01 0.00
)
10
12
14
16
18
20
22
24
26
28
Load Stage
Qualified product types and basestocks
FIG. 56IVIaster chart with average traction and scuffing stages for various oii types.
1014
30
32
1015
Acknowledgments
The author gratefully acknowledges support from the U.S.
Navy, U.S. Air Force, QinetiQ, and Pratt and Whitney, along
with several lubricant suppliers and bearing companies.
REFERENCES
[1] Wedeven, L. D., "Method and Apparatus for Comprehensive
Evaluation of Tribologlcal Materials," United States Patent
Number 5,679,883, Washington DC, 1997.
[2] Wedeven, L. D., Goodell, A. J., Black, W. F., Stimler, M. J., and
Ajayi, O. O., "Assessment of the Friction Characteristics and
Scuffing Performance of DOD-L-85734 Oils," University of Dayton Subcontract No. RI-21494X, U.S. Air Force Contract No.
F33615-92-C-2218, Feb. 11, 1994.
[3] "WAM3 Economical Load Capacity Test," U.S. Naval Research
Laboratory PO No. N00173-95-P-9981, September 11, 1995;
U.S. Navy PO No. N00421-95-M-0037, September 28, 1995.
[4] Ryder, E. A., "The Gear Rig as an Oil Tester," presented at the
ASLE Gear Symposium, Chicago, IL, 26-27 Jan. 1959.
[5] SAB AIR4978: Temporary Methods for Assessing the Load Carrying Capacity of Aircraft Propulsion System Lubricating Oils,
Society of Automotive Engineers, Warrendale, PA, 1997.
[6] Wedeven, L. D. and Hille, E., "Tribology Testing for Load Carrying Capacity of Aircraft Propulsion System Lubricating Oils,"
Bench Testing of Industrial Fluid Lubrication and Wear Properites
Used in Machinery Applications, ASTM STP1404, G. E. Totten, J.
R. Dickey, L. D. Wedeven, and M. Anderson, Eds., ASTM International, West Conshohocken, PA, 2001, pp. 318-332.
[7] Wedeven, L. D., "Tribologlcal Performance Measurement Research," U.S. Navy Contract No. N00140-92-C-BD32, August 2000.
[8] Wedeven, L. D. and D'Orazio A. J., "Technical Approach to Oil
Testing and Field Service Performance," Presented at the SAEE34 Propulsion Lubricants Technical Symposium, 22-23 Sept.
1999, Cardiff, Wales.
[9] Brown, S. C, Chin, H. A., Haluck, D. A., and Wedeven, L. D.,
"Linking Lubricants, Materials, Design and Tribology," Lubrication and Fluid Power, Vol. 2, No. 4, November 2001, pp. 7-21.
[10] "R&D Technique to Determine Scoring Load Capacity of Lubricants," U.S. Navy Contract No. N00140-88-C-1717, August 1988.
[11] Wedeven, L. D. and Hille, E., "Tribology Testing for Load Carrying Capacity of Aircraft Propulsion System Lubricating Oils,"
Bench Testing of Industrial Fluid Lubrication and Wear Properties Used in Machinery Applications, ASTM STP 1404, G. E. Totten, L. D. Wedeven, J. R. Dickey, md M. Anderson, Eds., ASTM
International, West Conshohocken, PA, 2001, pp. 118-332.
MNL37-EB/Jun. 2003
TION AND WEAR PROPERTIES of lubricants and materials. If friction and wear can be controlled then the engineer can select
materials and lubricants with a high degree of confidence.
Many laboratory tests are used to evaluate the interaction of
materials under a broad range of test conditions and controlled environments.
In this chapter, the following topics will be discussed:
History of tribology testing
Basic types of tribology test systems and reasons for their
use
Fundamentals in designing tribology tests
How to select a test device to simulate a field condition
Contact geometry used in bench tests
Standard and commonly used test devices
Designing special application bench tests
Common terminology relating to friction and wear testing
Even though m a n was employing simple engineering principles and lubrication for manufacturing, it wasn't until the
late 15th century, when Leonardo DiVinci first deduced laws
governing the motion of a block over a flat surface, that the
science of friction and lubrication was developed. During this
time, primitive testing devices were developed to measure the
force of one object moving against another. Scientist during
this time also realized that measured forces were less when a
material such as pig fat was introduced between sliding or
moving surfaces; hence, the study of lubrication had begun.
During the years that followed, friction, wear, and lubrication studies increased. As the industrial revolution brought
more advanced machines for transportation and power generation, engineering became part of the curriculum at universities. These studies included the fundamentals of friction,
lubrication, and wear. With new extraction techniques for
obtaining crude oil and the ability to refine this oil, lubricants
became m o r e commonplace. As lubricants became more
widely used, technology was needed to eveduate the differences in properties and in various applications. In 1927, the
first commercial tribomoter was introduced to blenders and
manufacturers of finished lubricants. This tester "Pin and
Vee Block test machine" provided suppliers with a method of
measuring anti-wear and extreme pressure properties of the
lubricants they were selling. Subsequently, tribometers such
as the Timken^ tester. Four Ball Wear and Four Ball EP,
Block-on-Ring, and others were introduced to evaluate lubricants and materials under a variety of test conditions. These
machines are described in this chapter.
Further developments in transportation, medicine, and
space exploration have provided impetus for the development of new lubricants and materials. With these technologies has come the development of test machine designs and
test methods to meet the challenges of these new applications. Today, over 225 commercial and independent testing
devices [2] have been developed.
1017
Copyright'
2003 by A S I M International
www.astm.org
BENCH TESTS
Test
tvDe
Relative
cost
Repeatabiltv
bench
component
$$$
***
field
FIG. 1Economic comparison of test types.
Accurate and precise indication of wear rates and performance properties given the test parameters under which
the test is conducted
Inexpensive and uniform consumable test pieces
Test pieces from a wide range of materials and conditions
Small volumes of test fluid
Controlled test environments and ambient conditions
Convenience of operation.
Commercial test devices offer significant benefits over
test equipment made in-house. Because commercial test
machines are made in quantity to the same manufacturing
specifications, they can offer better test result comparisons
between the laboratories using them. Commercial testers
are often used when developing standardized test methods
because of the availability of users willing to cooperate in
the development of precision statements. In most cases, the
test parameters are listed in standardized test methods.
However, they may not provide the user all the necessciry information for evaluating his materials. Therefore, standardized test methods can be suitable starting points, but the
user may need to modify the test parameters to achieve
meaningful test results [3,8]. Usually more data can be obtained throughout the test rather than just the final specified endpoint or reported test result. Many data occur during the course of a test, including but not limited to,
changes in lubricating mechanisms, changes in surface areas giving different contact pressures, development of lubricating films and surfaces, and so on. Therefore, the operator must identify these changes and develop test methods
that facilitate obtaining as much pertinent information as is
possible or required.
Commercial test devices provide the following benefits:
Established and known precision
Simplicity of test operation
Many meet ASTM, SAE, ISO and other standard test
methods
Flexible test procedures
Ability to compare results worldwide
Correlation with previously published field results
Support and assistance in operation and method development by the manufacturer
CHAPTER
of conclusions at the end of the test requires the user to analyze the data obtained with respect to actual field conditions. The user then draws the appropriate conclusions and
then may develop models for predicting wear of future applications involving similar materials and operating conditions [9].
When designing a laboratory test program, the basic steps
for successful testing are as follows:
Field Problem
1. Identify the location of the wear problem in the test system
2. Determine the failure mechanism
3. Identify the tribological conditions
Motion
Sliding, unidirectional
Sliding, bidirectional or reversing
Rolling
Fretting
Speed
Linear velocity
Rotational velocity
Contact Geometry
Point
Line
Area
Pressure/Load
Normal loads
Surface area of contact
Temperature
Bulk lubricant
Contact temperature
Type of Lubricant
Fluid
Solid
Semi-solid (grease)
Dry film
None
Lubricant Performance Properties
Anti-wear
Extreme pressure
Chemistry
Lubricating Mechanism
Enclosed chamber (flooded sump)
Constant circulation
Spray
Coated
Contacting Materials
External Operating Conditions
Ambient temperature
Atmosphere
Humidity
Vibration
Contaminants
B e n c h Test Selection
1.
2.
3.
4.
Experience
Standardized test methods
Available test equipment
Analytical methods such as Tribological Aspect Number
(TAN) [3]
37: LUBRICANT
FRICTION
AND WEAR
TESTING
1019
1020
MANUAL
HANDBOOK
All controlled laboratory testing yields test data that reflect what is happening in the test device under the selected
test conditions. If the test results do not correlate with the
field results, then either the test device is not representative
of the field application or an incorrect test procedure was
chosen. Therefore, it is of the utmost importance that the
user develops a meaningful test procedure and utilizes the
type of test equipment that best represents the field condition. There Eire many approaches that are used to select the
best test machine and the test parameters. This chapter will
reference and discuss a practical, analytical approach to selecting the best bench test for simulating a particular field
condition.
B e n c h Test
Bench Test, as used in this chapter, is the term used to describe laboratory test devices that are simple in design, yet
complex enough to rank a materiEil's performance for a specific property or to simulate an actual field condition. Unlike
component test stands, bench tests are designed to isolate
specific contacts, motions, loads, and geometric contacts.
These physical characteristics combined with the selected
test parameters give the researcher a means of easily evaluating materials for their effects in field applications or further
component testing. In a properly designed test, operating under a lubrication regime similar to the field condition, the asperities at the point of contact will react the same as they
would in the field condition that the bench test is represent-
CHAPTER
ing. Correlation has been shown by Faville [8] when using the
Pin and Vee Block for evaluating transmission and other
lubricants.
Component Test Design
Component testing, which includes, but is not limited to,
p u m p tests and engine test beds, uses actual parts or components from manufactured equipment. The test stand designer
must carefully select these parts to be within well-defined
manufacturing tolerances for dimensions, surface finish, and
hardness. The component fixturing is typically designed to
hold the components and test them in a manner that represents, as close as possible, the actual field conditions and environment while maintaining the desired test parameters.
The test device design should be sufficiently flexible to permit
a wide range of operating conditions.
To achieve reasonable repeatability and reproducibility
with the test results obtained from the test stand, close control of the test parameters must be maintained. In the actual
field condition it is virtually impossible to control all of the
a m b i e n t conditions, due to the wide fluctuations in surrounding conditions. These test parameters for a component
test stand should be selected to represent conditions that
might occur in actual applications. The selected parameters
must be closely controlled, and the test stand must be designed to provide provisions for monitoring the selected test
parameters. Monitoring the test parameters will provide the
operator with a recorded history indicating whether these parameters were maintained during the test. Often times controlled atmospheres, large sumps for test fluids, special air
and fluid filtration, temperature control, load control, and
other more specific systems must be designed into the test
stand to maintain test parameters or for better simulation of
field conditions. These test devices are designed to simulate a
particular aspect of actual operation and are valuable for the
development of additives and lubricant formulations [10]. In
engine test stands, for example, proper simulation of actual
driving conditions includes cycling of load, speed, and temperatures according to a designed test program. It is essential
to integrate the cyclic characteristics to simulate the actual
driving conditions on the laboratory test rig. The use of a
computer to control test parameters provides more consistent test operation and facilitates data acquisition
Monitoring test variables during the test sequence is critical. The computer, with its capability of acquiring and storing the test data, has offered considerable benefit to the test
operator by recording data throughout the test. This data will
advise the operator that the test has run within the selected
controlled parameters and that the test is operating as desired. It will also alert the operator to a change or failure in
any of the measured properties. Because ambient conditions
can also influence test results, it is important that these conditions such as t e m p e r a t u r e and relative humidity be
recorded. The computer may provide more rapid data collection when one or more of the variables exceed an alarm condition. This rapid data collection will give more detailed information of the test results when unusual conditions are
present. The computer can also activate the control function
of the test stand, eliminating the need for the operator to
make the control adjustments after the test has initiated. The
3 7: LUBRICANT
FRICTION
AND WEAR
TESTING
1021
computer can also cause the test to terminate if a predetermined set-point is exceeded or if a dangerous condition exists. And finally the computer can organize, calculate, and
present the data in tabulated or graphic format for ease of interpretation. This valuable tool is used in most component
test formats and for an increasing number of standard bench
tests stands.
With component tests, the parts chosen for the test fixturing must have some sensitivity to the materials under evaluation [11]. For example, p u m p s that are used to evaluate
wear of hydraulic fluids should be sensitive to formulated fluids that have sufficient anti-wear properties and those that do
not [12]. There should always be some check that the test device and selected test parameters and sequences are robust
enough to discriminate between materials with known poor
field performance and those with acceptable field performance. The user should prove that the component test has a n
acceptable degree of precision, both in repeatability and in
reproducibility. Repeatability is the closeness of the agreement of test data on back-to-back testing on the same test
stand, in the same laboratory, with the same operator, on the
same test materials or fluids, within a short time span. Reproducibility is the agreement of test results using the same
test materials or fluids but on different test stands, with different operators, in different laboratories, and run at different times.
When designing any laboratory test rig, the design should
provide for wide latitude of test parameters. This will assist
in discriminating between materials or components tested
with materials of varying performance properties. When a series of test parameters has been chosen that demonstrates
differences in materials of known field performances, the test
stand should successfully rank materials with unknown field
performance. Extreme care should be exercised when selecting existing manufactured parts for use as testing components, as these parts must have some guarantee of consistency of manufacture and known tolerances for dimensions
and materials. Nevertheless, successful testing has been developed and has given the test engineer considerable information on the performance of materials predicted from the
results of component testing under actual or near field conditions. Properly designed test stands should mimic the field
conditions as closely as possible so that the contacting materials will exhibit properties exactly as if they were in the actual field condition.
1022
MANUAL
HANDBOOK
Load
Load control must be considered when selecting a test. Test
load can be applied by a static or dead weight system, a pneumatic system, hydraulic system, or by fluid pressure. Consideration should be given to including an initial "break-in" or
"wear-in" at a lighter load representing partial EHD [13]. Inclusion of a break-in can form a more uniform surface rather
t h a n testing under machined conditions. This more uniform
surface can add to the consistency of test results.
It can be difficult to select test loads that will be representative of the loads encountered in the field, yet of a magnitude
large enough to challenge the test system without introducing any complex or other type wear mechanisms. Selecting
loads that are excessive could produce results that are not
representative of what is occurring in the actual field condition. If the operator chooses a test load that is low, he may encounter very long test duration before failures occur. Another
way to determine an appropriate test load is to conduct a step
load test and look for an erratic change in the torque or friction force as load is increased [8]. This variability of the
torque indicates a breakdown of the lubricant film, allowing
for metal to metal contact. The load immediately prior to the
load that corresponds to the erratic torque or friction force
can be looked at in terms of the threshold limit of the test system load. The operator can choose a test load at or below the
threshold load that should give a controlled amount of wear
in a reasonable time. Note that too light a test load may not
give enough weeir to discriminate between samples and too
heavy a load may yield too m u c h wear to discriminate. At this
point, it is basically an educated guess as to the best test load.
Several loads in this area may have to be tried in order to select the test load that gives the best discrimination with regards to the other test variable. Ideally, if materials with
known field data are being used to set u p the test procedure,
discrimination should be the focus. If discrimination is obtained, then this test load should be used as the starting point
for the tests, that is to say that at some point in the testing
with other materials, these test parameters may have to be
reevaluated.
Often times the load must be controlled to allow for cycling of test loads to simulate in-field conditions. Cycling
versus static load can better simulate the stresses encountered in the test system and is used to better maintain the
temperature of the test system in long-term endurance or
life tests.
Speed
If possible, select the linear test speed to be the same as the
field condition. This is done in rotational tests by taking
the speed of the field condition and dividing by diameter of
the point of contact or wear track, and by pi, msiking the appropriate conversions for distance units results in the corresponding rpm. Certain applications require very slow or very
fast test speeds. Test speeds have a profound effect on lubrication regime in the test system. The operator should consult
the Stribeck curve for general effects of the change in load or
speed on the coefficient of firiction and lubricating regime.
The Stribeck curve (Fig. 2) shows the relation of coefficient
of friction to the ratio of viscosity, speed, and the inverse of
load, known as the Sommerfeld N u m b e r [14] with respect to
coefficient of friction.
Sommerfeld Number = speed X viscosity/load
This fundamental curve gives an illustration of the effect of
changing viscosity, speed or load on the coefficient of friction
in the various lubrication regimes of boundary, elastohydrodynamic, mixed and hydrodynamic [15].
1. Hydrodynamic lubrication: the surfaces are separated by
the lubricant film resulting in low friction.
2. Mixed lubrication: the load is carried by the lubricant and
the interacting asperities
3. Boundary lubrication: the load is solely carried by the interacting asperities, resulting in high friction.
Although it may be impractical to construct the entire classic Stribeck curve, specific portions of the curve for vEirious
test systems can be determined as illustrated in the curves
listed. It should also be noted that different materials, geometries, and test systems can yield curves that are different
in shape than the classic Stribeck Curve. For example, certain
systems may not have a boundary lubrication region and may
rise directly to a very high friction value indicating severe
metal-to-metal contact.
The curve in Fig. 3 depicts Stribeck curves in the mixed lubrication region as a function of lubricant thickness [15]. By
changing speed and/or load in the Sommerfeld number, the
resulting change in coefficient of friction is determined and
plotted for each lubricant thickness. In the self-lubricated
speed X viscosity/ioad
FIG. 2Theoretical Stribeck Curve. Reprinted with
permission of STLE.
. . ... 1.00E-04
1.00E-05
1.00E-06
5.00E-07
3.00E-07
0.14
0.12
2.00E-07
^ ^ v
"~~-
\ ^ ^S-.-.--''>^
1.00E-07
8.00E-08
4.50E-08
*- 0.08
4.20E-08
%\.
-4.00E-08
3.90E-08
0.04
-3.80E-08
370E-08
0.02 -
3.65E-08
3.64E-08
3.63E-08
1023
3.60E-08
Materials
0.20
U 0.15
U-
p:
0.10-
o
O
0.05
c
<p
"o
N=0.2 N/cm2
Special Atmospheres
N=0.4 N/cm
N=1.0N/cm
N=0.8 N/cm
I
10"
IQ-
10 -6
10"
10"
10"
Sommerfeld Number
FIG. 4Coefficient of friction as a function of Sommerfeld
number for a plastic on a PMMA disk lubricated by a saline solution [14]. Reprinted with permission from the Society of Plastics Engineers.
condition, as illustrated in Fig. 4, changes in speed with constant loads are plotted against coefficient of friction determined by testing. Similarly, tests could be conducted by varying the load maintaining constant viscosity and speed.
Although it is possible to vary more than one variable in determining Sommerfeld numbers and their relation to coefficient of friction, it is more typically studied by varying just
one of the variable's affect on the coefficient of friction, as
illustrated in the above examples.
Duration
Test duration is also important. Often tests are conducted on
many different samples at the same predetermined test dura-
1024
HANDBOOK
duces the test fluid into the contact zone either by continuously changing the fluid in a flooded test chamber or by injecting or depositing a controlled volume of test fluid directly
into the contact zone.
Special Testing
Special testing is the addition of a test variable that is unique
to a situation to better understand certain phenomena. These
would include the introduction of abrasives or solid particles,
the testing of used oils or test fluids with known history, or
the addition of contaminants such as water or some other
solid or liquid. Special testing is generally used in the laboratory test program when the field condition typically contains
these special materials. Anything that can be done to better
simulate field results will improve the simulated laboratory
test results.
The basic design of the Pin and Vee Block consists of two
opposing Vee blocks loaded against a rotating journal pin
(Fig. 6). It conducts tests in four-line contact, unless optional
C-Blocks are used. C-Blocks give a conformal area contact.
The test is run with the pins and blocks submerged in the test
lubricant (D 2670, D 3233) (Fig. 7), with the test pieces coated
with a bonded film lubricant (D 2625), or with the lubricant
coating the test pieces (D 5620). Load is applied via a ratchet
wheel and eccentric pawl. Each turn of the motor will advance the ratchet wheel one tooth when the pawl is engaged.
Tests can be run at constant load (D 2670, D 2625 procedure
A) or at increasing load until failure (D 3233, D 2625 procedure B). In the increasing load test, failure is indicated by a
break in either the shear pin or test pin or in the inability of
COMMON TYPES OF B E N C H
TEST DEVICES
Pin and Vee Block
This Pin and Vee Block (Fig. 5) is the most widely used commercialized wear tester for evaluating lubricants [18] Also
known as the Falex'* Lubricant Tester, the Pin and Vee Block
test machine has been successfully used for evaluating lubricating and wear preventing properties of lubricants, both
fluid and solid, for over 75 yccirs. This tester is used for evaluating metalworking fluids, automotive and industrial lubricants, and bonded solid film lubricants [8].
'' Falex Corporation, Sugar Grove, IL
1025
1026
MANUAL
HANDBOOK
FIG. 8Falex Test Pieces [8]. A: Unused (new); B: After ASTM D 2670 wear test;
C: After ASTM D 3233 EP test, torque failure; D: After ASTM D 3233 EP test, weld
failure.
the test system to maintain test load. Careful monitoring of
the torque with respect to the test load can yield valuable information as to the lubricating properties of the test fluid as
it interacts with the selected test piece materials [8,19]
Changes in the slope of the torque curve can reveal changes
in the lubricating regime of the test system. Careful examination of the torque, load, and wear values gives information
on the anti-wear and extreme pressure properties of the tribology system.
Tests can be r u n at constant load for evaluating anti-wear
properties and also u n d e r increasing load conditions to evaluate lubricating effects at different load conditions. Although
the ASTM test m e t h o d s for evaluating extreme pressure
properties of lubricants directs the user to increase load u p to
the point where either the test or shear pin breaks, the information obtained during the entire test can provide important
data as to the performance of the lubricating properties. An
important p h e n o m e n o n described by Faville [8] and later
elaborated by Helmetag [19] is the occurrence of a sudden increase in the torque, also referred to as the torque "pop-up."
Anti-weld evaluations can be made only in the load range immediately following this initial seizure. Products lacking
anti-weld properties tear out metal, resulting in weld type
seizure (Fig. 8D), while some products develop high torque,
which result in twisting off the shear pin without any occurrence of scoring (Fig. 8C). The latter failures cire referred to
as torque seizures [20].
The ASTM test methods that relate to the Pin and Vee
Block test machine and their typical test results (Fig. 8) Eire:
ASTM D 2625, Endurance (Wear) Life and Load-Carrying
Capacity of Solid Film Lubricants (Falex Pin and Vee
Method)
ASTM D 2670, Measuring Wear Properties of Fluid Lubricants (Falex Pin and Vee Block Method)
ASTM D 3233, Measurement of Extreme Pressure Properties of Fluid Lubricants (Falex Pin a n d Vee Block
Methods)
ASTM D 5620, Evaluating Thin Film Fluid Lubricants in a
Drain and Dry Mode Using a Pin and V-Block Test Machine
Pin on Disk
Pin-on-Disk test is the simplest and most c o m m o n wear test
device [21]. It consists of a rotating disk upon which is loaded
a pin or ball (Figs. 9 and 10) In the simplest versions, the ball
rotates on the Scune wear scar. Other mechanisms can be incorporated such that the pin or ball comes in contact with a n
untouched portion of the rotating disk. This results in a spiral type of wear track. Pin-on-disk testing is used most widely
FIG. 9Pin-on-Disk.
1027
HANDBOOK
Four Ball EP
In the Four Ball EP test (D 2596, D 2783), the upper ball is allowed to rotate under load for 10 s, after which the resultant
wear scars are measured and averaged. In this test, a series of
test runs is performed at logarithmically increasing loads up
to the weld point. The weld point is the load at which the lubricant film breaks down and the temperature at the point of
contact is so high that it melts the metal, causing the test balls
to weld together, indicating that the extreme pressure level of
the lubricant has been exceeded. When the lubricant is performing as designed, the wear scars will be very smzdl, only
slightly larger than the corresponding theoretical Hertzian
scar diameters for the given materials, load, and radii of the
test balls. The Hertzian scar diameter is the average diameter
of an indentation caused by the deformation of the balls under static load (prior to test). The line that parallels the
Hertzian line is referred to as the compensation line. When
the lubricating film breaks down, metal-to-metal contact occurs and mild to severe incipient seizure occurs. This seizure
is evidenced by the disproportionate increase in the average
scar diameter. When incipient seizure is present, the test ball
scar diameter is no longer on the compensation line. The
highest test load that yields a scar diameter within 5% of the
compensation line value for the corresponding load is the last
non-seizure load. The ASTM D 2596 and D 2783 test methods
provide an index of the relative wear performance with respect to load for the lubricant under evaluation., which is
shown in a graph of the wear scar versus test load (Fig. 16).
This term is called the Load Wear Index (LWI).
Because of the wide range of test loads (8-1000 Kg) 2ind the
severe conditions that occur when a weld point is reached,
the Four Ball EP test machine (Fig. 17) is designed to be very
robust in construction. ASTM D 2266, D 4172, and D 5183
warn against using the Four Ball EP test machine for running
CHAPTER
37: LUBRICANT
FRICTION
AND WEAR
TESTING
1029
Block on Ring
The Block-on-Ring test machine (Fig. 19) is more of a research tool. It is primarily used to determine wear rates of
materials and to rank materials in pure sliding motion. The
tester is designed to accommodate different test fixtures to
effect point, line, ellipsoid, and area contact. The standard
block-on-ring test uses a rectangular block on a rotating ring
and starts as Hertzian line contact. As motion begins, a load
carrying bearing surface forms, allowing the formation of
anti-wear and/or EP films to form on the surface. The wear
scar width is measured and reported at the end of the test
(Fig. 20). The preferred method of reporting is volume loss;
however, if the same metals are being used, simply reporting
the wear scar diameter for comparative wear is acceptable. A
table in ASTM G 77 gives block scar volumes for measured
wccir scar widths. Oscillating drive mechanisms can be installed to effect reciprocating (back and forth) motion. This
motion is used in test methods for evaluating greases and
bonded film lubricants. Testing with a ball on ring combination results in initial high Hertzian point contact. After motion begins, the Hertzian point contact area develops into a
load carrying bearing surface. With increasing loads, moni-
RING a. BLDCK
BOTATIDN
ROTATION
FIG. 21High pressure (rectangular) block (left); Low pressure (conformal) block (right).
HANDBOOK
The Tapping Torque test machine (Fig. 25) is designed to perform actual metalworking applications in a laboratory environment. Originally designed to perform thread cutting and
thread forming, the Tapping Torque test machine can perform additional metalworking functions. There are two basic
metalworking applications: metal removal and metal deformation. Metal removal techniques remove material to
achieve the desired final shape, while metal deformation
techniques reshape or form the existing material into the desired shape. Under metal removal, there are thread cutting
(tapping), drilling, and reaming. Under metal deformation,
there are thread forming (tapping), roll forming, drawing,
and rolling mill simulation.
The tool rotates and descends at a rate determined by the
rotational speed and pitch of the lead screw of the tapping
head. The test machine measures the torque as the tool descends and enters the material to be machined (Fig. 26). The
piece to be machined will have various forms depending on
the test selected. It is most important to observe the tight tolerances required for the consumable test pieces. Even slight
variances can have an affect on the precision of the test results.
The ASTM standardized test method that uses the Tapping
Torque test machine is as follows:
ASTM D 5619, Comparing Metal Removal Fluids Using the
Tapping Torque Test Machine
Multi-Specimen/Multi-Purpose
(Thrust Washer Tester)
FIG. 23Timl<en
ring and block configuration.
T>pic4l OK
No Storing
1031
Improper Sclup
Scoring (failure)
FIG. 24Typical Timken test wear scars.
T I M E (RCJTATION)
FIG. 2BTapping Torque trace of tap entering test piece (insets show position of tap in specimen
blank).
R0TAT1C3N
TORQUE
FIG. 28Vaneon-disk.
LOAD
1033
FIG. 33SRV test machine. Reprinted with permission of Optimol Instruments Priiftechnik GmbH.
tanOtrii t p a c R w m
m<\
t-^^i^ -^Bjfijl^j
point
FIG. 31High speed linear reciprocating test
rig (TE77). Reprinted with permission from
Phoenix Tribology.
twm
am
FIG. 34Schematic of SRV test pieces. Reprinted with permission of Optimol Instruments Pruftechnilc GmbH.
1034
MANUAL
HANDBOOK
Type C gears are used for evaluating pitting and micro-pitting tendencies of industrial gear oils [38]. As with most
component tests, this gear tester uses actual parts, in this
case, gear sets.
A constant load test is used for evaluating anti-wear properties of tractor hydraulic oils (D 4998). The test gears are
weighed before and after the test. A load stage test of increasing test loads is used for evaluating industrial gear oils
for their ability to carry a load. After each test load, the gear
teeth are evaluated for signs of scoring (D 5182) (Figs. 37 and
PlBion
LodUng Pin
GMrWiietl
Oriva QitMm
UMd Clutch
TtmptnMm Stnser
Polishing
Scoring
Scuffing
CHAPTER
37: LUBRICANT
FRICTION
AND WEAR
TESTING
1035
CONCLUSION
3 |
Distress;
Pass
Scoring (15mm)
Scorinq (Smm)
Rating :
See 10.4.2
Rating
See 10.4.2
eBj
5 m
ASTM STANDARDS
Friction and Wear Properties
Distress:
Scoring (20mm)
Fail
7 M
See 10.4.2
No.
D1367
8 |M
D2266
Oistmss:
Rating :
[)istress:
Scuffing (20mm)
Rating :
Fail
D2271
D2625
Vickers P u m p Stand
The Vickers P u m p Stand is a controversial yet widely used
component bench test. Although u n d e r current scrutiny for
i m p r o v e m e n t of its precision, this test stand evaluates
hydraulic fluids for wear using an actual p u m p . The p u m p
parts are inspected metrologically a n d corrected, cleaned,
weighed, and assembled prior to beginning each test. The test
load is the fluid pressure, which can be either 1000 psi or
2000 psi depending on the test method. In some tests the
loaded pressure exceeds that pressure recommended for normal operation. This pressure is chosen to challenge the test
system in order to screen lubricants. At the end of the test, the
p u m p cartridge pieces are again inspected for damage,
cleaned, and weighed.
This test is undergoing considerable modifications. It is
recommended to review the latest draft prior to beginning
ciny test program using this tester.
The ASTM standardized test methods using the Vickers
P u m p Stand are as follows:
ASTM D 2271, Preliminary Examination of Hydraulic Fluids (Wear Test)
ASTM D 2882, Indicating the W e a r Characteristics of
Petroleum and Non-Petroleum Hydraulic Fluids in a Constant Volume Vane P u m p
D2670
D2714
D2882
D2981
D3336
D3704
Title
Standard Test Method for Lubricating Qualities of
Graphites (general laboratory test)
Standard Test Method for Wear Preventive Characteristics of Lubricating Grease (Four Ball
Method) (general laboratory test for wear of
greases in sliding contact)
Standard Test Method for Preliminziry Examination of Hydraulic Fluids (Wear Test) (general laboratory test for wear of hydraulic fluids under low
pressures in p u m p test)
Standard Test Method for Endurance (Wear) Life
and Load Carrying Capacity of Solid Film
Lubricants (Falex Pin and Vee Method) (genercil
laboratory tests for load carrying and wear
properties of solid lubricants)
Standard Test Method for Measuring Wear Properties of Fluid Lubricants (Fcdex Pin and Vee Block
Method) (general laboratory test for sliding wear)
Standard Test Method for Calibration and Operation of the Falex Block- on-Biing Friction and Wear
Testing Machine (generzJ laboratory test in sliding
motion)
S t a n d a r d Test Method for Indicating the Wear
ChEiracteristics of Petroleum a n d Non-Petroleum
Hydraulic Fluids in a Constant Volume Vane
Pump (general laboratory test, known as the Vickers p u m p stand test)
Standard Test Method for Wear Life of Solid Film
Lubricants in Oscillating Motion
(general laboratory test)
Standard Test Method for Life of Lubricating
Grease in Ball Bearings at Elevated Temperatures
(general laboratory test)
Standard Test Method for Wear Preventive Properties of Lubricating Greases Using the (Falex)
Block-on-Ring Test Machine in Oscillating Motion
(general laboratory test)
D 5183
D 5619
D 5620
D 5707
D 6078
D 6079
D 6425
G 77
G 83
G 99
G 115
G 118
G 133
HANDBOOK
Standard Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four Ball
Method) (general laboratory test)
Standard Practice for Sheet Metal Forming Lubricant Evaluation (general methodology for testing)
Standard Test Method for Evaluating Wear Characteristics of Tractor Hydraulic Fluids (general
laboratory test)
Standard Test Method for Measurement of Lubricity of Aviation Turbine Fuels by the Ball-onCylinder Lubricity Evaluator (BOCLE) (general
laboratory test)
Standard Test Method for Determination of the
Coefficient of Friction of Lubricants Using the
Four-Ball Wear Test Machine (general laboratory
test)
Standard Test Method for Comparing Metal Removal Fluids Using the Tapping Torque Test Machine (general laboratory test)
Standard Test Method for Evaluating Thin Film
Fluid Lubricants in a Drain and Dry Mode Using a
Pin and V-Block Test Machine (general laboratory
test)
Standard Test Method for Measuring Fiction and
Wear Properties of Lubricating Grease Using a
High-Frequency, Linear-Oscillation (SRV) Test
Machine (general laboratory test)
Standard Test Method for Evaluating Lubricity of
Diesel Fuels by the Scuffing Load Ball-on-Cylinder
Lubricity Evaluator (SLBOCLE) (general laboratory test)
Standard Test Method for Evaluating Lubricity of
Diesel Fuels by the High-Frequency Reciprocating
Rig (HFRR) (general laboratory test)
Standard Test Method for Measuring Friction and
Wear Properties of EP Lubricating Oils Using the
SRV Test Machine (general laboratory test)
Standard Test Method for Ranking Resistance of
Materials to Sliding Wear Using Block-on-Ring
Wear Test (general laboratory test)
Standard Test Method for Wear Testing with
a Crossed Cylinder Apparatus (general laboratory test)
Standard Test Method for Wear Testing With a
Pin-on-Disk Apparatus (general laboratory test)
Standard Guide for Measuring and Reporting
Friction Coefficients (guide for methodology)
Standard Guide for Recommended Data Format
for Sliding Wear Test (guide for methodology)
Standard Test Method for Linearly Reciprocating
Ball-on-Flat Sliding Wear (general laboratory test)
D 2509
D 2596
D 2782
D 2783
D 3233
D 5182
D 5706
OTHER STANDARDS
Friction and Wear Properties
DIN-Deutsches
No.
50280
Institut fur
Normung
Title
Running Test on Radial Plain Bearings; General
Plain Bearings; Testing of the Tribological Behavior of Plain Bearings with Hydrostatic and Mixed
Lubrication in Bearing Testing (General Laboratory Test for Sliding Wear of Bearings)
50281
Friction in Bearings; Definitions; Tjrpes; Conditions; Physical Quantities (definitions)
50320
Wear; Terms; System Analysis of Wear Processes;
Classification of Wear Phenomena
(definitions of wear terms and classifications)
5032l.G Wear Quantities (definitions of various wear
types)
50322
Wear; Wear Testing Categories (definitions of
scales of testing of all tjrpes of wear)
50323
Tribology; Terms (4 parts) (terms and definitions
of wear t5fpes)
50324
Tribology; Testing of Friction and Wear Model
Test for Sliding of Solids (Ball on Disc System)
51350
Testing in the Shell Four-Ball Tester (lubricant
characterization)
Determination of the Wearing Characteristics of
Liquids (Part 3);
Determination of the Wearing Characteristics
for Consistent Lubricants (Part 5);
Determination of Shear Stability of Lubricating
Oils Containing Polymers (Part 6)
51354
Mechanical Testing of Lubricants in the FZG Gear
Rig Test (gear lubricant classification in
sliding/rolling contact)
51389
51509
51834
ISO-International
7148/1
TR6281
Standards
Organization
Testing of the Friction and Wear Behavior of Bearing Material / Mating Material / Oil Combinations
under Conditions of Boundary Lubrication (bearings, friction and wear tests)
Testing Under Conditions of Hydrodynamic and
Mixed Lubrication in Test Rigs-Guidelines (guidelines for bearings in sliding wear)
334
166
239
240
326
and
IP - Institute
281
Science
of
Petroleum-UK
1037
REFERENCES
[1] Dowson, D., History ofTribology, Professional Engineering Publishing Limited, London, UK, 1998.
[2] Benzing, R., Goldblatt, I., Hopkins, V., Jamison, W., Mecklenburg, K., and Peterson, M., Friction and Wear Devices, STLE,
Park Ridge, IL, 1976.
[3] Voitik, R. M., "Realizing Bench Test Solutions to Field Tribology
Problems," Tribology: Wear Test Selection for Design and Application, ASTM STP 1199, A. W. Ruff, and Raymond G. Bayer,
Eds., ASTM International, West Conshohocken, PA, 1993.
[4] Sture, H. and Staffan, J., "Hints and Guidelines for Tribotesting
and Evaluation," Lubrication Engineering, Vol. 48, No. 5, 1991,
pp. 401-409.
[5] Neale, M. J. and Gee, M., Guide to Wear Problems and Testing for
Industry, y^ ed., Williams Andrew Publishing, Norwich, NY,
2001.
[6] Calabrese, S. J. and Muray, S. F., "Methods of Evaluating Materials for Icebreaker Hull Coatings," Selection and Use of Wear
Tests for Coatings, ASTM STP 769, R. G. Bayer, Ed., ASTM International, West Conshohocken, PA, 1982, pp. 157-173.
[7] Banniak E. A. and Fein R. S., "Precision of Four Ball and
Timken Tests and Their Relation to Service Performance," NLGI
Spokesman, January 1973.
[8] Faville, F. and Faville, W., "Falex Procedures for Evaluating Lubricants," Journal of the American Society of Lubrication Engineers, STLE, Park Ridge, IL, August 1968.
[9] Bayer R. G., Shalkey A. T., and Wayson A. R., "Designing for
Zero," Machine Design, IBM Corporation, Endicott, NY, 1969.
[10] Wei D.-P., "Future Directions of Fundamental Research in Additive Tribochemistry," Lubrication Sciences, Vol. 7, April 1995.
[11] Mizuhara K. and Tsuya Y., "Investigation of a Method for Evaluating Fire-Resistant Hydraulic Fluids by Means of an Oil-Testing Machine," JSLE International Tribology Conference, Tokyo,
Japan, 8-10 July 1985.
[12] Feldman, D. G. and Kessler, M., "Development of a New Application-RelatedTest Procedure for Mechanical Testing of Hydraulic Fluids," Hydraulic Failure Analysis: Fluids, Components
and System Effects, STP 1339, G. E. Totten, D. K. Wills, and D.
G. Feldman, Eds., ASTM International, West Conshohocken,
PA, 2001, pp. 75-89.
[13] De Gee, A. W. J., "Characterization of Five High-Performance
Lubricants in Terms of IRG Transition Diagram Data," Proceedings of the IMechE, International Conference on Tribology-Friction. Lubrication, and Wear, Fifty Years On, London, Mechsinical
Engineering Publications Lmtd., Bury St. Edmunds, 1987, Vol.
1, pp. 427-436.
[14] Vaim, J. A. and Jising, T.-B, "Measurement of the Friction and
Lubricity Properties of Contact Lenses," Proceedings of the ANTEC1995, Boston, MA, May 7-11, 1995.
[15] Schipper, D. J. and Faraon, I. C, "Stribeck Curves for Starved
Line Contacts," University of Twente, The Netherlands, Report
number TROl-2227, 2001.
[16] Sanvordenker, K. S., "Lubrication by Oil-RefrigerEint Mixtures:
Behavior in the Falex Tester," ASHRAE Transactions, KC-84-14,
No. 3, pp. 799-805.
[17] Anderson, M., "The Use of Tribological Aspect Numbers in
Bench Test Selection-A Review Update," Bench Testing of In-
APPENDIX
Terminology Related to Fuels
and Lubricants Testing
abrasive wear, nwear due to hard peirticles or hard protuberances forced against and moving cdong a solid surface.
additive, na material added to another, usueJly in small
amounts, to impart or enhance desirable properties or to suppress undesirable properties.
adhesive wear, nwear due to localized bonding between
contacting solid surfaces leading to material transfer between the two surfaces or loss from either surface.
apparent area of contact, nin tribology, the area of contact
between two solid surfaces defined by the boundaries of their
macroscopic interface. (Contrast with real a r e a of contact.)
asperity, nin tribology, a protuberance in the small-scale
topographical irregularities of a solid surface.
break-in, nin tribology, an initicJ transition process occurring in newly established weEuing contacts, often accompanied by transients in coefficient of friction or wear rate, or
both, which are uncharacteristic of the given tribological system's long-term behavior.
catastrophic vwear, nrapidly occurring or accelerating
surface damage, deterioration, or change of shape caused by
wear to such a degree that the service life of a part is appreciably shortened or its function is destroyed.
coefficient of friction, fi or f, nin tribology, the dimensionless ratio of the friction force (F) between two bodies to
the normal force {N) pressing these two bodies together.
/x or f = (F/N)
Discussiona distinction is often made between static coefficient of friction and kinetic coefficient of friction.
corrosive wear, n^wear in which chemical or electrochemical reaction with the environment is significEuit.
debris, nin tribology, pjirticles that have become detached
in a wear or erosion process.
dry solid film lubricants, ndry coatings consisting of lubricating powders in a solid matrix bonded to one or both
surfaces to be lubricated.
extreme pressure (EP) additive, nin a lubricant, a substcince that minimizes damage to metcil surfaces in contact
under high stress rubbing conditions (D 4175).
fatigue wear, n^wear of a solid surface caused by fracture
arising from material fatigue.
fretting wear, na form of attiitive wear caused by vibratory or oscillatory motion of limited amplitude characterized
1039
HANDBOOK
scuff, scuffing, nin lubrication, damage caused by instantaneous localized welding between surfaces in relative motion, which does not result in immobilization of the parts.
scuffingn, a form of wear occurring in inadequately lubricated tribosystems that is characterized by macroscopiccJlyobservable changes in surface texture, with features related
to the direction of relative motion.
Discussionfeatures characteristic of scuffing include
scratches, plastic deformation, and transferred material. (Related terms: galling, scoring.)
seizure, nin lubrication, welding between surfaces in relative motion that results in immobilization of the parts. Localized fusion of metal between the rubbing surfaces of the
test pieces (D 5707). DiscussionSeizure is usually indicated
by an increase in coefficient of friction, wear, or unusual
noise and vibration. In this test method, increase in coefficient of friction is displayed on the chart recorder as rise in
the coefficient of friction from a steady state value.
sliding wear, nwear due to the relative motion in the tangential plane of contact between two solid bodies.
speilling, nin tribology, the separation of macroscopic particles from a surface in the form of flakes or chips, usually associated with rolling element bearings and gear teeth, but
also resulting from impact events.
standard test, na test on a calibrated test stand, using the
prescribed equipment according to the requirements in the
test method, and conducted according to the specified operating conditions. Discussionthe specified operating conditions in some test methods include requirements for determining a test's operational validity. These requirements are
applied after a test is completed, and can include (1) midlimit ranges for the average values of primary and secondary
parameters that are narrower than the specified control
ranges for the individual values, (2) allowable deviations for
individual primary and secondary parameters from the specified control ranges, (3) downtime limitations, and (4) special
parameter limitations.
static coefficient of friction, nthe coefficient of friction
corresponding to the maximum friction force that must
be overcome to initiate macroscopic motion between two
bodies.
stick-slip, nin tribology, a cyclic fluctuation in the magnitudes of friction force and relative velocity between two
elements in sliding contact, usually associated with a relaxation oscillation dependent on elasticity in the tribosystem
and on a decrease of the coefficient of friction with onset of
sliding or with increase of sliding velocity.
DiscussionClassical or true stick-slip, in which each cycle
consists of a stage of actual stick followed by a stage of overshoot "slip," requires that the kinetic coefficient of friction is
lower than the static coefficient. A modified form of relaxation oscillation, with near-harmonic fluctuation in motion,
can occur when the kinetic coefficient of friction decreases
gradually with increasing velocity within a certain velocity
range. A third t5^e of stick-slip can be due to spatial periodicity of the friction coefficient along the path of contact. Random variations in friction force measurement do not constitute stick-slip.
test oil, nany oil subjected to evaluation in an established
procedure.
1041
MNL37-EB/Jun. 2003
1043
Copyright'
2003 by A S I M International
www.astm.org
HANDBOOK
QUALITY ASSURANCE
measurement process
environment
operator
equipment
measurement process
antftfonment
[" operator 1
OF MEASUREMENT
PROCESSES
FOR
PETROLEUM
based on collaborative expeiimental work under the auspices of a scientific or engineering group (E456).
true value, nfor practical purposes, the value towards
which the average of single results obtained by N laboratories tends, when N becomes veiy large. Consequently, such
a true value is associated with the particular test method
employed (D 3244).
The term true value as defined above, is also referred to as
a consensus value as described by item (3) under the definition of accepted reference value (ARV).
Hence, if an average was calculated from N results obtained for the same material, from a single measurement process, under site precision conditions, AND, if the material has
an accepted reference value, then, for large values of N
(greater than 30), any statistically significant difference between this average and the ARV of the material is referred to
as bias. Bias provides a quantitative measure of how well the
actual process outcome agrees with an expected value.
accuracy, nthe closeness of agreement between a test result and an accepted reference value.
Note: The term accuracy, when applied to a set of test
results, involves a combination of a random component and of a common systematic error or bias component (E 456).
Hence, precision and bias are quantitative measures of different attributes of the measurement process. The combined
effect of both attributes affects the accuracy of the results.
M E A S U R E M E N T P R O C E S S QUALITY
A S S U R A N C E (QA) P R O G R A M
pj^^^i^.
B
not allowed to vary by design
measurement process
May or may not vary
environment
operator
material
FIG. 1a) ASTM reproducibility conditions; b) ASTM repeatability conditions; c) site precision conditions.
1046
MANUAL
HANDBOOK
Einalysis in accordcince with industry-accepted rules to ascertain the statistical control status of the measurement process.
Any out-of-control data should trigger a n investigation for
root causes in a timely manner. Pending on outcome of this
investigation, remedial action may be required.
Selection,
Preparation,
Control Material
Testing
The testing should b e CEurried out under site precision conditions, with participation of as many operators as practical,
and test time during the day should be randomized to avoid
any unknown systematic effects. Test frequency should be
designed in accordance with the business needs, taking into
considerations the following factors:
frequency of use of measurement process
criticality of the parameter being measured
measurement process stability and precision performance
based on historical data
business economics
regulatory, contractual, or test method requirements.
The sample treatment and testing of quality control materials should emulate the processing of day-to-day samples.
Application of special treatment to the quality control sample
in order to get a better result is discouraged, as this would undermine the integrity of the data in providing a valid estimate
of the long-term measurement process precision under normal production conditions. TypicEilly, for automated large
batch analyses commonly practiced in testing using autosamplers, it is good practice to include a quality control sample in the beginning, middle, emd end of batch run. Periodic
re-submission of quality control samples, disguised as normal samples, provides data to test the authenticity of precision established using known quality control samples as truly
representative of the test m e t h o d precision u n d e r n o r m a l
testing conditions.
Testing multiple aliquots of quality control samples as a
batch, under repeatability conditions, is not appropriate for
estimating the m e a s u r e m e n t process long t e r m precision.
The bulk of the total long term measurement process vari-
Treatment
The most practical and technically applicable tool for recording and assessing quality control sjimple data is the control
chart. Quality control test results should be plotted on control charts as soon as they cire generated and the chart should
be interpreted immediately to assess the acceptability of process performance. For measurement processes where there is
n o issue with quality control sample homogeneity among
aliquots prepeired from one batch of materieJ, the Individual
(I) cind Moving Range of 2 (MR2) are the appropriate charts.
These charts have been the basic workhorses in the statistical
process control (SPC) discipline for over half a century, primarily deployed in the discrete component manufacturing
sector. They are also known as "Shewart" charts, a tribute to
Dr. Walter Shewhart, one of the early quality pioneers w h o
preached the use of these charts for manufacturing process
monitoring and control.
Designed with simplicity in mind, the I chart is not as effective in detecting small process shifts as it is for large shifts.
To address this shortcoming, its use is often augmented with
a set of r u n rules, often referred to as the "Western Electric"
r u n rules, a tribute to the company that pioneered their use.
More advanced statistical techniques such as the Exponentially Weighted Moving Average (EWMA), or Cumulative
Sum (CUSUM) can be deployed in lieu of the r u n rules with
equivalent effectiveness. The EWMA is recommended due to
ease of deployment, a n d its close emulation to detection
power of the r u n rules [6]. An abridged summeiry description
of these cheirts and the r u n rules can be found in the Annex
under the section on Control Charts.
Hence, a combination of the I chart with the run rules, or
augmented with EWMA, should be used for the detection of
both large and small shifts of the location value simultcineously. The MR2 chart tracks the total process variation (precision) over multiple operators cind time.
In order to deploy control chcirts for regular use, control
limits and center values need to be CEilculated. These values
can be obtained initially after a veJid test equipment calibration from a m i n i m u m of 15 valid quality control test results
(for the same batch of qucJity control samples), then periodically updated as new data arrive. Prior to calculating the initial values, the following screening steps should be CEirried
out:
1. Screen for suspicious resultsResults should first be visually screened for unusual values, such as those that could
have been caused by transcription errors. Results flagged
as suspicious should be investigated. Discard of any data
at this stage must be supported by evidence that the discarding is due to special causes that Eire not part of the normal testing process.
2. Screen for unusual patterns^The next step is t o plot the results in chronological order. In SPC terminology, this is
known as a r u n chart. The chart should be examined for
non-random patterns such as continuous trending in either
direction, unusual clustering, eind cycles. Several of the
non-random patterns described in control chart literature
QUALITY ASSURANCE
can be used as guides at this step [8]. Detection of any nonrandom pattern should trigger investigation for causes.
3. Test distribution assumptionsIf, after removal of appropriate results, there is a minimum of 15 observations remaining, the normal distribution assumption for the control chart needs to be validated, as this assumption is used
to predict the behavior of the measurement process under
statistical control. For a small number of observations
(15-25), the tool of choice is the normal probability, or
quantile-quantile plot, since it tends to provide better information regarding the "goodness-of-fit" of the data to the
assumed model than the more commonly known histogram, which generally requires 40 or more data points to
be effective. A plot indicating a departure from the assumed model may reveal abnormal conditions not discovered by previous screening steps.
4. Assess process stabilityIf no obvious non-random patterns are detected from the run charts, and the normal
probability plot reveals no unusual pattern, proceed with
detail calculations of control limits. Use the control chart
rules (or EWMA), in conjunction with the control limits, to
determine if the measurement process is under the influence of common causes variation only (in statistical control). Out-of-control points should be investigated in detail. For those associated with special causes, their
exclusion from further data analysis is warranted only if
the special causes are deemed not part of the normal process. These control limits should be viewed as starting values only, with appropriate reassessment and/or updating
as more data become available.
The initial control chart limit established above should be
re-assessed based on a minimum number (15) of new data
points. Update calculations should be preceded by an appropriate statistical test to assess if the precision of the new data
is essentially the same as previous data. If the test is not significant, a new estimate of the total process precision should
be re-estimated using data from both periods. A significant
test outcome should trigger an investigation for root causes.
When the total number of data points used to estimate process precision exceeds 100, a re-estimate of the site precision
when additional data becomes available reaches the point of
diminishing return. The value based on 100 data points is a
fairly accurate representation of the long term site precision.
Batch Change of Quality Control Material
Due to inherent variation of the manufacturing process and
different operation targets, differences may exist between
batches of materials extracted at different times for quality
control use. Since control limit calculations for the I chart require a center value usually established by the process itself,
a special procedure is required to ensure that the center line
for a new batch of QC material is established with a process
that is in statistical control. This procedure can be designed
as follows:
Collect and prepare a new batch of QC material as the current supply is close to depletion.
Start a new set of I, MR2 charts for the new material. Commence collection of data for the new material each time a
current quality control sample is tested. The new data is
deemed valid if the process in-control status is established
by the current QC material.
OF MEASUREMENT
PROCESSES
FOR
PETROLEUM
Use the control limits for the current MR2 chart or a previous MR2 chart where the matericil is at nominally similar
property level, for the new MR2 chart.
After a minimum of 5 in-control data points are collected
on the new material, calculate a temporary center line for
the new I chart.
Calculate the control limits for the new I chart using the
new center and MR-BAR value from previous MR2 chart.
Assess subsequent data points for new material against the
new control limits. Temporatrily suspend the run rules.
After 15 data points have been accrued, re-calculate the
new I-chart center line. Assess the precision of the new
dataset against the previously established precision for
equivalency. Combine and re-estimate the precision if
necessary.
Deploy the new control chart and activate all run rules.
The reason for the temporary center line is to minimize the
commissioning period for the new QC material. The suspension of run rules is to avoid false alarms due to a less precise
estimate of the center line using five data points. With an effective QC material inventory management program, the calculation and transfer of control chart limits between batches
of quality control materials should be seamless.
When the System is in statistical-control, i.e. no assignable
cause is present, the expected outcome when switching QC
material are:
fluctuation between I-chart center line values for different
QC batches; it represents material difference only;
no statisticcdly significant difference is expected for the MR
chart control limits for different batches of QC material at
similar nominal levels.
For detailed instructions on how to execute the aforementioned calculations and techniques, refer to the Appendix at
the end of this chapter.
1048
MANUAL
and
HANDBOOK
ARV
Calibration
It is a well-known fact (Deming Funnel Experiment) that frequent and unnecessary adjustment to any process will result
in the inflation of the c o m m o n cause variation of the process.
Therefore, equipment calibration should only be done when
there is evidence, supported by quality control testing data,
suggesting that the process requires adjustment as the calibration process itself is subject to c o m m o n cause variation. A
c o m m o n and frequently overlooked source of calibrationinduced variation is the calibration s t a n d a r d preparation
process, a n d / o r c o m m o n cause composition variation of
commercial standards themselves.
QUALITY ASSURANCE
OF MEASUREMENT
PROCESSES
FOR
PETROLEUM
Crosscheck Program (I.L.C.P); ASTM-D02.01 National Exchange Group(N.E.G.); ASTM D02.01.A Regional Exchange
Programs; Alberta Research Council -International Cooperative Exchange Testing Programs) all use outliers treatment to
generate exchange statistics.
With regular and meaningful participation in these exchanges, an industry benefit is the availability of an on-going
estimate of the achievable precision in executing the standard test methods. The test method custodian (e.g., ASTM
subcommittee member) can regularly compare this information to the published precision to identify the need for
method improvement, and/or revisions to published precision figures. For example, the cetane method (ASTM D 613)
precision was revised based on historical exchange data, primary from the NEG (National Exchange Group), with data
from exchanges such as IP in the UK also considered.
Technical
Resist the temptation of being seduced by computer automation technology: Computers can't think. People do.
Make the paper system work first before making any attempt at automation. When designing for automation, do
not settle for partial charts or text entries without the pictorial information and the capability to directly annotate
on the chart. Insist on the fuU features and functionalities
to include as a minimum:
instant access to a pictorial representation of at least 16
previous points
direct emnotation features on cheirt
1050
MANUAL
HANDBOOK
CONCLUSION
In summary, proficiency in executing standardized measurement protocol for product quality testing is a key mutual expectation between suppliers and customers. Proficiency assurance requires data to demonstrate:
m e a n a n d precision of measurement process in statistical
control, i.e., the process is stable, (hence predictable), and,
the total magnitude of c o m m o n cause variation is
quantifiable
precision metrics obtained on samples compositionally
representative of product routinely tested cire acceptable
relative to standards
measurement process is non-biased when testing materials
that have ARVs (check standards) assigned by the standard
measurement protocol.
An effective quality management system that ensures the
timely and proper collection of the required data, documentation, and review of performance statistics will provide the
assurance of measurement proficiency, as well as continued
improvement of the measurement processes.
ASTM STANDARDS
No.
D 3244
D 6299
D 6300
E 456
E 69
E 178
Title
Standard Practice for Utilization of Test Data
to Determine Conformance with Specifications
Standard Practice for Applying Statistical
Quality Assurance Techniques to Evaluate Analytical Measurement System Performance
Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for
Petroleum Products a n d Lubricants
Standard Terminology for Relating to Quality
and Statistics
Standard Practice for Conducting an Interlaboratory Study to Determine the Precision of a
Test Method
Standard Practice for Dealing with Outlying
Observations
APPENDIX
Statistical Quality Control Tools
Purpose
of this
Appendix
of Test
ISO 5725
Title
Determination a n d Application of Precision
Data in Relation to Methods of Test
Accuracy (Trueness and Precision) of Measurement Methods and Results
REFERENCES
[1] ASTM E 456: Standard Terminology for Relating to Quality and
Statistics, Annual Book of ASTM Standards, ASTM International,
West Conshohocken, PA, 1997.
[2] ASTM E 69: Standard Practice for Conducting an Interlaboratory
Study to Determine the Precision of a Test Method, Annual Book
of ASTM Standards, ASTM International, West Conshohocken,
PA, 2000.
[Al]
/; = Yu
OTHER STANDARDS
No.
ISO 4259
Results
/,- = Yi-
[A2]
Xi
TABLE Al
Sequence
Number
I
QC/Check
Standard Result
1
2
3
4
5
6
7
8
9
10
11
12
13
55.3
55.8
56.3
56.1
55.8
55.5
55.3
55.4
56.6
56.1
55.0
55.5
55.5
Yi = Ii
Sequence
Number
I
QC/Check
Standard Result
14
15
16
17
18
19
20
21
22
23
24
25
55.2
56.5
55.7
55.6
55.2
55.7
56.1
56.3
55.2
55.4
55.4
55.6
Yi = Ii
QUALITY ASSURANCE
TABLE A2
Sequence
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Difference
Result - ARV
(Yi)
Accepted Reference
Value
(ARV = Xi)
55.3
55.8
56.3
56.1
55.8
55.5
55.3
55.4
56.6
56.1
55.0
55.5
55.5
55.2
56.5
55.7
55.6
55.2
55.7
56.1
56.3
55.2
55.4
55.4
55.6
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
55.88
-0.58
-0.08
0.42
0.22
-0.08
-0.38
-0.58
-0.48
0.72
0.22
-0.88
-0.38
-0.38
-0.68
Check Standard
Result
li
0.62
-0.18
-0.28
-0.68
-0.18
0.22
0.42
-0.68
-0.48
-0.48
-0.28
[A3]
where D, are estimates of the reproducibility standard deviation of the measurement process at levels [Xi].
Table A3 shows an example of results for multiple check
standards where the precision of the measurement system is
level dependent.
OF MEASUREMENT
PROCESSES
FOR
PETROLEUM
TABLE A3
Result
Sequence
Number, i
Raw
Result
Yi
XI
Raw
Difference
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
71.0
65.8
70.3
66.2
93.8
102.9
102.2
103.2
71.4
64.9
70.2
67.7
93.4
104.0
101.8
103.9
99.8
71.5
76.4
61.8
43.9
69.7
59.19
98.87
95.21
103.94
96.7
100.65
84.15
83.75
65.93
68.0
-0.40
0.90
0.10
-1.50
0.40
-1.10
0.40
-0.70
0.20
0.10
0.30
-0.60
0.20
0.01
0.31
0.76
-1.51
-0.17
-0.52
-0.95
0,17
-0.46
-0.77
0.19
100
71.6
76.7
61.2
44.1
69.71
59.5
99.63
93.7
103.77
96.18
99.7
84.32
83.29
65.16
68.19
ARV
Preprocessed
Result
li
1.14
1.10
1.13
1.11
1.26
1.33
1.31
1.32
1.30
1.14
1.16
1.08
0.98
1.13
1.06
1.30
1.27
1.32
1.28
1.31
1.21
1.21
1.10
1.12
-0.35
0.82
0.09
-1.35
0.32
-0.83
0.30
-0.53
0.15
0.09
0.26
-0.56
0.20
0.01
0.29
0.59
-1.19
-0.13
-0.41
-0.73
0.14
-0.38
-0.70
0.17
10
15
20
30
10
15
10
Anderson-Darling
Statistic
The Anderson-Darling Statistic is used to test for normality.
The test involves the following steps:
Order the non-outlying results such that Xi X2 ^ . . . . Xn
Obtain standardized variate from the Xj's as follows:
15
Wi = {xi -
[A4]
x)/s
TABLE A4z-values.
n
Order
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
-1.83
-1.28
-0.97
-0.73
-0.52
-0.34
-0.17
0.00
0.17
0.34
0.52
0.73
0.97
1.28
1.83
-1.86
-1.32
-1.01
-0.78
-0.58
-0.40
-0.24
-0.08
0.08
0.24
0.40
0.58
0.78
1.01
1.32
1.86
-1.89
-1.35
-1.05
-0.82
-0.63
-0.46
-0.30
-0.15
0.00
0.15
0.30
0.46
0.63
0.82
1.05
1.35
1.89
-1.91
-1.38
-1.09
-0.86
-0.67
-0.51
-0.36
-0.21
-0.07
0.07
0.21
0.36
0.51
0.67
0.86
1.09
1.38
1.91
-1.94
-1.41
-1.12
-0.90
-0.72
-0.55
-0.41
-0.27
-0.13
0.00
0.13
0.27
0.41
0.55
0.72
0.90
1.12
1.41
1.94
-1.96
-1.44
-1.15
-0.93
-0.76
-0.60
-0.45
-0.32
-0.19
-0.06
0.06
0.19
0.32
0.45
0.60
0.76
0.93
1.15
1.44
1.96
-1.98
-1.47
-1.18
-0.97
-0.79
-0.64
-0.50
-0.37
-0.24
-0.12
0.00
0.12
0.24
0.37
0.50
0.64
0.79
0.97
1.18
1.47
1.98
-2.00
-1.49
-1.21
-1.00
-0.83
-0.67
-0.54
-0.41
-0.29
-0.17
-0.06
0.06
0.17
0.29
0.41
0.54
0.67
0.83
1.00
1.21
1.49
2.00
-2.02
-1.51
-1.23
-1.03
-0.86
-0.71
-0.58
-0.45
-0.33
-0.22
-0.11
0.00
0.11
0.22
0.33
0.45
0.58
0.71
0.86
1.03
1.23
1.51
2.02
-2.04
-1.53
-1.26
-1.05
-0.89
-0.74
-0.61
-0.49
-0.37
-0.26
-0.16
-0.05
0.05
0.16
0.26
0.37
0.49
0.61
0.74
0.89
1.05
1.26
1.53
2.04
-2.05
-1.55
-1.28
-1.08
-0.92
-0.77
-0.64
-0.52
-0.41
-0.31
-0,20
-0.10
0.00
0.10
0.20
0.31
0.41
0.52
0.64
0.77
0.92
1.08
1.28
1.55
2.05
-2.07
-1.57
-1.30
-1.10
-0.94
-0.80
-0.67
-0.56
-0.45
-0.34
-0.24
-0.15
-0.05
0.05
0.15
0.24
0.34
0.45
0.56
0.67
0.80
0.94
1.10
1.30
1.57
2.07
-2.09
-1.59
-1.32
-1.13
-0.97
-0.83
-0.70
-0.59
-0.48
-0.38
-0.28
-0.19
-0.09
0.00
0.09
0.19
0.28
0.38
0.48
0.59
0.70
0.83
0.97
1.13
1.32
1.59
2.09
-2.10
-1.61
-1.35
-1.15
-0.99
-0.85
-0.73
-0.62
-0.51
-0.41
-0.32
-0.23
-0.13
-0.04
0.04
0.13
0.23
0.32
0.41
0.51
0.62
0.73
0.85
0.99
1.15
1.35
1.61
2.10
-2.11
-1.63
-1.36
-1.17
-1.01
-0.88
-0.76
-0.65
-0.54
-0.45
-0.35
-0.26
-0.17
-0.09
0.00
0.09
0.17
0.26
0.35
0.45
0.54
0.65
0.76
0.88
1.01
1.17
1.36
1.63
2.11
-2.13
-1.64
-1.38
-1.19
-1.04
-0.90
-0.78
-0.67
-0.57
-0.48
-0.39
-0.30
-0.21
-0.13
-0.04
0.04
0.13
0.21
0.30
0.39
0.48
0.57
0.67
0.78
0.90
1.04
1.19
1.38
1.64
2.13
-2.14
-1.66
-1.40
-1.21
-1.06
-0.93
-0.81
-0.70
-0.60
-0.51
-0.42
-0.33
-0.25
-0.16
-0.08
0.00
0.08
0.16
0.25
0.33
0.42
0.51
0.60
0.70
0.81
0.93
1.06
1.21
1.40
1.66
2.14
-2.15
-1.68
-1.42
-1.23
-1.08
-0.95
-0.83
-0.72
-0.63
-0.53
-0.45
-0.36
-0.28
-0.20
-0.12
-0.04
0.04
0.12
0.20
0.28
0.36
0.45
0.53
0.63
0.72
0.83
0.95
1.08
1.23
1.42
1.68
2.15
QUALITY ASSURANCE
OF MEASUREMENT
PROCESSES
FOR
PETROLEUM
Table A4 (cont.)
n
Order
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
-2.17
-1.69
-1.43
-1.25
-1.10
-0.97
-0.85
-0.75
-0.65
-0.56
-0.47
-0.39
-0.31
-0.23
-0.15
-0.08
0.00
0.08
0.15
0.23
0.31
0.39
0.47
0.56
0.65
0.75
0.85
0.97
1.10
1.25
1.43
1.69
2.17
-2.18
-1.70
-1.45
-1.26
-1.12
-0.99
-0.87
-0.77
-0.67
-0.58
-0.50
-0.42
-0.34
-0.26
-0.19
-0.11
-0.04
0.04
0.11
0.19
0.26
0.34
0.42
0.50
0.58
0.67
0.77
0.87
0.99
1.12
1.26
1.45
1.70
2.18
-2.19
-1.72
-1.47
-1.28
-1.13
-1.01
-0.89
-0.79
-0.70
-0.61
-0.52
-0.44
-0.37
-0.29
-0.22
-0.14
-0.07
0.00
0.07
0.14
0.22
0.29
0.37
0.44
0.52
0.61
0.70
0.79
0.89
1.01
1.13
1.28
1.47
1.72
2.19
-2.20
-1.73
-1.48
-1.30
-1.15
-1.02
-0.91
-0.81
-0.72
-0.63
-0.55
-0.47
-0.39
-0.32
-0.25
-0.17
-0.10
-0.03
0.03
0.10
0.17
0.25
0.32
0.39
0.47
0.55
0.63
0.72
0.81
0.91
1.02
1.15
1.30
1.48
1.73
2.20
-2.21
-1.74
-1.49
-1.31
-1.17
-1.04
-0.93
-0.83
-0.74
-0.65
-0.57
-0.49
-0.42
-0.35
-0.27
-0.20
-0.14
-0.07
0.00
0.07
0.14
0.20
0.27
0.35
0.42
0.49
0.57
0.65
0.74
0.83
0.93
1.04
1.17
1.31
1.49
1.74
2.21
-2.22
-1.76
-1.51
-1.33
-1.18
-1.06
-0.95
-0.85
-0.76
-0.67
-0.59
-0.52
-0.44
-0.37
-0.30
-0.23
-0.17
-0.10
-0.03
0.03
0.10
0.17
0.23
0.30
0.37
0.44
0.52
0.59
0.67
0.76
0.85
0.95
1.06
1.18
1.33
1.51
1.76
2.22
-2.23
-1.77
-1.52
-1.34
-1.20
-1.08
-0.97
-0.87
-0.78
-0.69
-0.62
-0.54
-0.47
-0.40
-0.33
-0.26
-0.19
-0.13
-0.06
0.00
0.06
0.13
0.19
0.26
0.33
0.40
0.47
0.54
0.62
0.69
0.78
0.87
0.97
1.08
1.20
1.34
1.52
1.77
2.23
-2.24
-1.78
-1.53
-1.36
-1.21
-1.09
-0.98
-0.89
-0.80
-0.71
-0.64
-0.56
-0.49
-0.42
-0.35
-0.29
-0.22
-0.16
-0.09
-0.03
0.03
0.09
0.16
0.22
0.29
0.35
0.42
0.49
0.56
0.64
0.71
0.80
0.89
0.98
1,09
1.21
1.36
1.53
1.78
2.24
-2.25
-1.79
-1.55
-1.37
-1.23
-1.11
-1.00
-0.90
-0.82
-0.73
-0.66
-0.58
-0.51
-0.44
-0.38
-0.31
-0.25
-0.18
-0.12
-0.06
0.00
0.06
0.12
0.18
0.25
0.31
0.38
0.44
0.51
0.58
0.66
0.73
0.82
0.90
1.00
1.11
1.23
1.37
1.55
1.79
2.25
-2.26
-1.80
-1.56
-1.38
-1.24
-1.12
-1.02
-0.92
-0.83
-0.75
-0.67
-0.60
-0.53
-0.46
-0.40
-0.33
-0.27
-0.21
-0.15
-0.09
-0.03
0.03
0.09
0.15
0.21
0.27
0.33
0.40
0.46
0.53
0.60
0.67
0.75
0.83
0.92
1.02
1.12
1.24
1.38
1.56
1.80
2.26
-2.27
-1.81
-1.57
-1.40
-1.26
-1.14
-1.03
-0.94
-0.85
-0.77
-0.69
-0.62
-0.55
-0.48
-0.42
-0.36
-0.30
-0.24
-0.18
-0.12
-0.06
0.00
0.06
0.12
0.18
0.24
0.30
0.36
0.42
0.48
0.55
0.62
0.69
0.77
0.85
0.94
1.03
1.14
1.26
1.40
1.57
1.81
2.27
-2.28
-1.82
-1.58
-1.41
-1.27
-1.15
-1.05
-0.95
-0.87
-0.79
-0.71
-0.64
-0.57
-0.50
-0.44
-0.38
-0.32
-0.26
-0.20
-0.14
-0.09
-0.03
0.03
0.09
0.14
0.20
0.26
0.32
0.38
0.44
0.50
0.57
0.64
0.71
0.79
0.87
0.95
1.05
1.15
1.27
1.41
1.58
1.82
2.28
-2.29
-1.83
-1.59
-1.42
-1.28
-1.16
-1.06
-0.97
-0.88
-0.80
-0.73
-0.66
-0.59
-0.52
-0.46
-0.40
-0.34
-0.28
-0.22
-0.17
-0.11
-0.06
0.00
0.06
0.11
0.17
0.22
0.28
0.34
0.40
0.46
0.52
0.59
0.66
0.73
0.80
0.88
0.97
1.06
1.16
1.28
1.42
1.59
1.83
2.29
-2.29
-1.84
-1.60
-1.43
-1.29
-1.18
-1.07
-0.98
-0.90
-0.82
-0.74
-0.67
-0.61
-0.54
-0.48
-0.42
-0.36
-0.30
-0.25
-0.19
-0.14
-0.08
-0.03
0.03
0.08
0.14
0.19
0.25
0.30
0.36
0.42
0.48
0.54
0.61
0.67
0.74
0.82
0.90
0.98
1.07
1.18
1.29
1.43
1.60
1.84
2.29
-2.30
-1.85
-1.61
-1.44
-1.31
-1.19
-1.09
-1.00
-0.91
-0.83
-0.76
-0.69
-0.63
-0.56
-0.50
-0.44
-0.38
-0.33
-0.27
-0.21
-0.16
-0.11
-0.05
0.00
0.05
0.11
0.16
0.21
0.27
0.33
0.38
0.44
0.50
0.56
0.63
0.69
0.76
0.83
0.91
1.00
1.09
1.19
1.31
1.44
1.61
1.85
2.30
-2.31
-1.86
-1.62
-1.45
-1.32
-1.20
-1.10
-1.01
-0.93
-0.85
-0.78
-0.71
-0.64
-0.58
-0.52
-0.46
-0.40
-0.35
-0.29
-0.24
-0.18
-0.13
-0.08
-0.03
0.03
0.08
0.13
0.18
0.24
0.29
0.35
0.40
0.46
0.52
0.58
0.64
0.71
0.78
0.85
0.93
1.01
1.10
1.20
1.32
1.45
1.62
1.86
2.31
-2.32
-1.87
-1.64
-1.47
-1.33
-1.21
-1.11
-1.02
-0.94
-0.86
-0.79
-0.72
-0.66
-0.60
-0.54
-0.48
-0.42
-0.37
-0.31
-0.26
-0.21
-0.15
-0.10
-0.05
0.00
0.05
0.10
0.15
0.21
0.26
0.31
0.37
0,42
0.48
0.54
0.60
0.66
0.72
0.79
0.86
0.94
1.02
1.11
1.21
1.33
1.47
1.64
1.87
2.32
-2.33
-1.88
-1.64
-1.48
-1.34
-1.23
-1.13
-1.04
-0.95
-0.88
-0.81
-0.74
-0.67
-0.61
-0.55
-0.50
-0.44
-0.39
-0.33
-0.28
-0.23
-0.18
-0.13
-0.08
-0.03
0.03
0.08
0.13
0.18
0.23
0.28
0.33
0.39
0.44
0.50
0.55
0.61
0.67
0.74
0.81
0.88
0.95
1.04
1.13
1.23
1.34
1.48
1.64
1.88
2.33
[A5]
Compute A as
( 2 i - l)[ln(p;) + ln(l - p + i - 0
12 _ i s l _
- n
[A6]
Compute A^* as
A^ I +
0.75 I 2.25
n
n^
[A7]
If the computed value of A^* exceeds 0.752, then the hypothesis of normality is rejected for a 5% level test.
Example of Normal Probability Plot for QC ResultsOnce
15 results have been obtained (Table Al), they are sorted in
TABLE A5Pi values. Probability ( z < wj) where w, is the sum of the number in the left column and top row.
-0.09
-0.08
-0.07
-0.06
-0.05
-0.04
-0.03
-0.02
-0.01
0.00
0.0
0.0002
0.0002
0.0003
0.0005
0.0007
0.0010
0.0014
0.0019
0.0026
0.0036
0.0048
0.0064
0.0084
0.0110
0.0143
0.0183
0.0233
0.0294
0.0367
0.0455
0.0559
0.0681
0.0823
0.0985
0.1170
0.1379
0.1611
0.1867
0.2148
0.2451
0.2776
0.3121
0.3483
0.3859
0.4247
0.4641
0.0002
0.0003
0.0004
0.0005
0.0007
0.0010
0.0014
0.0020
0.0027
0.0037
0.0049
0.0066
0.0087
0.0113
0.0146
0.0188
0.0239
0.0301
0.0375
0.0465
0.0571
0.0694
0.0838
0.1003
0.1190
0.1401
0.1635
0.1894
0.2177
0.2483
0.2810
0.3156
0.3520
0.3897
0.4286
0.4681
0.0002
0.0003
0.0004
0.0005
0.0008
0.0011
0.0015
0.0021
0.0028
0.0038
0.0051
0.0068
0.0089
0.0116
0.0150
0.0192
0.0244
0.0307
0.0384
0.0475
0.0582
0.0708
0.0853
0.1020
0.1210
0.1423
0.1660
0.1922
0.2206
0.2514
0.2843
0.3192
0.3557
0.3936
0.4325
0.4721
0.0002
0.0003
0.0004
0.0006
0.0008
0.0011
0.0015
0.0021
0.0029
0.0039
0.0052
0.0069
0.0091
0.0119
0.0154
0.0197
0.0250
0.0314
0.0392
0.0485
0.0594
0.0721
0.0869
0.1038
0.1230
0.1446
0.1685
0.1949
0.2236
0.2546
0.2877
0.3228
0.3594
0.3974
0.4364
0.4761
0.0002
0.0003
0.0004
0.0006
0.0008
0.0011
0.0016
0.0022
0.0030
0.0040
0.0054
0.0071
0.0094
0.0122
0.0158
0.0202
0.0256
0.0322
0.0401
0.0495
0.0606
0.0735
0.0885
0.1056
0.1251
0.1469
0.1711
0.1977
0.2266
0.2578
0.2912
0.3264
0.3632
0.4013
0.4404
0.4801
0.0002
0.0003
0.0004
0.0006
0.0008
0.0012
0.0016
0.0023
0.0031
0.0041
0.0055
0.0073
0.0096
0.0125
0.0162
0.0207
0.0262
0.0329
0.0409
0.0505
0.0618
0.0749
0.0901
0.1075
0.1271
0.1492
0.1736
0.2005
0.2296
0.2611
0.2946
0.3300
0.3669
0.4052
0.4443
0.4840
0.0002
0.0003
0.0004
0.0006
0.0009
0.0012
0.0017
0.0023
0.0032
0.0043
0.0057
0.0075
0.0099
0.0129
0.0166
0.0212
0.0268
0.0336
0.0418
0.0516
0.0630
0.0764
0.0918
0.1093
0.1292
0.1515
0.1762
0.2033
0.2327
0.2643
0.2981
0.3336
0.3707
0.4090
0.4483
0.4880
0.0002
0.0003
0.0005
0.0006
0.0009
0.0013
0.0018
0.0024
0.0033
0.0044
0.0059
0.0078
0.0102
0.0132
0.0170
0.0217
0.0274
0.0344
0.0427
0.0526
0.0643
0.0778
0.0934
0.1112
0.1314
0.1539
0.1788
0.2061
0.2358
0.2676
0.3015
0.3372
0.3745
0.4129
0.4522
0.4920
0.0002
0.0003
0.0005
0.0007
0.0009
0.0013
0.0018
0.0025
0.0034
0.0045
0.0060
0.0080
0.0104
0.0136
0.0174
0.0222
0.0281
0.0351
0.0436
0.0537
0.0655
0.0793
0.0951
0.1131
0.1335
0.1562
0.1814
0.2090
0.2389
0.2709
0.3050
0.3409
0.3783
0.4168
0.4562
0.4960
0.0002
0.0003
0.0005
0.0007
0.0010
0.0013
0.0019
0.0026
0.0035
0.0047
0.0062
0.0082
0.0107
0.0139
0.0179
0.0228
0.0287
0.0359
0.0446
0.0548
0.0668
0.0808
0.0968
0.1151
0.1357
0.1587
0.1841
0.2119
0.2420
0.2743
0.3085
0.3446
0.3821
0.4207
0.4602
0.5000
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
3.2
3.3
3.4
3.5
0.5000
0.5398
0.5793
0.6179
0.6554
0.6915
0.7257
0.7580
0.7881
0.8159
0.8413
0.8643
0.8849
0.9032
0.9192
0.9332
0.9452
0.9554
0.9641
0.9713
0.9772
0.9821
0.9861
0.9893
0.9918
0.9938
0.9953
0.9965
0.9974
0.9981
0.9987
0.9990
0.9993
0.9995
0.9997
0.9998
0.5040
0.5438
0.5832
0.6217
0.6591
0.6950
0.7291
0.7611
0.7910
0.8186
0.8438
0.8665
0.8869
0.9049
0.9207
0.9345
0.9463
0.9564
0.9649
0.9719
0.9778
0.9826
0.9864
0.9896
0.9920
0.9940
0.9955
0.9966
0.9975
0.9982
0.9987
0.9991
0.9993
0.9995
0.9997
0.9998
0.5080
0.5478
0.5871
0.6255
0.6628
0.6985
0.7324
0.7642
0.7939
0.8212
0.8461
0.8686
0.8888
0.9066
0.9222
0.9357
0.9474
0.9573
0.9656
0.9726
0.9783
0.9830
0.9868
0.9898
0.9922
0.9941
0.9956
0.9967
0.9976
0.9982
0.9987
0.9991
0.9994
0.9995
0.9997
0.9998
0.5120
0.5517
0.5910
0.6293
0.6664
0.7019
0.7357
0.7673
0.7967
0.8238
0.8485
0.8708
0.8907
0.9082
0.9236
0.9370
0.9484
0.9582
0.9664
0.9732
0.9788
0.9834
0.9871
0.9901
0.9925
0.9943
0.9957
0.9968
0.9977
0.9983
0.9988
0.9991
0.9994
0.9996
0.9997
0.9998
0.5160
0.5557
0.5948
0.6331
0.6700
0.7054
0.7389
0.7704
0.7995
0.8264
0.8508
0.8729
0.8925
0.9099
0.9251
0.9382
0.9495
0.9591
0.9671
0.9738
0.9793
0.9838
0.9875
0.9904
0.9927
0.9945
0.9959
0.9969
0.9977
0.9984
0.9988
0.9992
0.9994
0.9996
0.9997
0.9998
0.5199
0.5596
0.5987
0.6368
0.6736
0.7088
0.7422
0.7734
0.8023
0.8289
0.8531
0.8749
0.8944
0.9115
0.9265
0.9394
0.9505
0.9599
0.9678
0.9744
0.9798
0.9842
0.9878
0.9906
0.9929
0.9946
0.9960
0.9970
0.9978
0.9984
0.9989
0.9992
0.9994
0.9996
0.9997
0.9998
0.5239
0.5636
0.6026
0.6406
0.6772
0.7123
0.7454
0.7764
0.8051
0.8315
0.8554
0.8770
0.8962
0.9131
0.9279
0.9406
0.9515
0.9608
0.9686
0.9750
0.9803
0.9846
0.9881
0.9909
0.9931
0.9948
0.9961
0.9971
0.9979
0.9985
0.9989
0.9992
0.9994
0.9996
0.9997
0.9998
0.5279
0.5675
0.6064
0.6443
0.6808
0.7157
0.7486
0.7794
0.8078
0.8340
0.8577
0.8790
0.8980
0.9147
0.9292
0.9418
0.9525
0.9616
0.9693
0.9756
0.9808
0.9850
0.9884
0.9911
0.9932
0.9949
0.9962
0.9972
0.9979
0.9985
0.9989
0.9992
0.9995
0.9996
0.9997
0.9998
0.5319
0.5714
0.6103
0.6480
0.6844
0.7190
0.7517
0.7823
0.8106
0.8365
0.8599
0.8810
0.8997
0.9162
0.9306
0.9429
0.9535
0.9625
0.9699
0.9761
0.9812
0.9854
0.9887
0.9913
0.9934
0.9951
0.9963
0.9973
0.9980
0.9986
0.9990
0.9993
0.9995
0.9996
0.9997
0.9998
0.5359
0.5753
0.6141
0.6517
0.6879
0.7224
0.7549
0.7852
0.8133
0.8389
0.8621
0.8830
0.9015
0.9177
0.9319
0.9441
0.9545
0.9633
0.9706
0.9767
0.9817
0.9857
0.9890
0.9916
0.9936
0.9952
0.9964
0.9974
0.9981
0.9986
0.9990
0.9993
0.9995
0.9997
0.9998
0.9998
-3.5
-3.4
-3.3
-3.2
-3.1
-3.0
-2.9
-2.8
-2.7
-2.6
-2.5
-2.4
-2.3
-2.2
-2.1
-2.0
-1.9
-1.8
-1.7
-1.6
-1.5
-1.4
-1.3
-1.2
-1.1
-1
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
Original
Sequence #, I
11
14
1
7
8
6
12
13
2
5
10
4
3
15
9
zvalue
1.83
-1.28
-0.97
-0.73
-0.52
-0.34
-0.17
0.00
0.17
0.34
0.52
0.73
0.97
1.28
1.83
TABLE A6
Sorted
Result
55.0
55.2
55.3
55.3
55.4
55.5
55.5
55.5
55.8
55.8
56.1
56.1
56.3
56.5
56.6
-1.47
-1.07
-0.86
-0.86
-0.66
-0.46
-0.46
-0.46
0.15
0.15
0.76
0.76
1.16
1.57
1.77
0.07
0.14
0.19
0.19
0.25
0.32
0.32
0.32
0.56
0.56
0.78
0.78
0.88
0.94
0.96
i^Term
in [A6]
-5.91
-14.35
-18.70
-21.94
-25.77
-21.44
-25.34
-22.80
-16.52
-18.46
-11.50
-10.80
-8.65
-5.79
-3.25
FIG. A5Example of a normal probability plot for multiple results from a single check standard.
Sort*
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Original
Sequence #
11
14
1
7
8
6
12
13
2
5
10
4
3
15
9
TABLE A8
Sorted
Result
z-value
1.83
1.28
0.97
0.73
0.52
0.34
0.17
0
0.17
0.34
0.52
0.73
0.97
1.28
1.83
-1.35
-0.83
-0.56
-0.53
-0.35
0.01
0.09
0.09
0.15
0.2
0.26
0.29
0.3
0.32
0.82
i* Temi
in [A6]
-3.12
-1.94
-1.32
-1.25
-0.84
-0.02
0.16
0.16
0.30
0.41
0.55
0.62
0.64
0.69
1.83
0.00
0.03
0.09
0.11
0.20
0.49
0.56
0.56
0.62
0.66
0.71
0.73
0.74
0.75
0.97
-10.41
-15.11
-18.58
-24.98
-25.59
-19.68
-19.93
-21.05
-22.33
-20.75
-11.91
-9.73
-9.99
-8.34
-1.02
z-values
Original
Sequence *
11
14
1
7
8
6
12
13
2
5
10
4
3
15
9
Sorted
Result
-0.88
-0.68
-0.58
-0.58
-0.48
-0.38
-0.38
-0.38
-0.08
-0.08
0.22
0.22
0.42
0.62
0.72
zvalue
-1.83
-1.28
-0.97
-0.73
-0.52
-0.34
-0.17
0
0.17
0.34
0.52
0.73
0.97
1.28
1.83
Pi
-1.47
-1.07
-0.86
-0.86
-0.66
-0.46
-0.46
-0.46
0.15
0.15
0.76
0.76
1.16
1.57
1.77
0.07
0.14
0.19
0.19
0.25
0.32
0.32
0.32
0.56
0.56
0.78
0.78
0.88
0.94
0.96
i* Tenn
in [A6]
-5.91
-14.35
-18.70
-21.94
-25.77
-21.44
-25.34
-22.80
-16.52
-18.46
-11.50
-10.80
-8.65
-5.79
-3.25
1056
MANUAL
37: FUELS
AND LUBRICANTS
HANDBOOK
several statistical techniques that can be used for this purpose, this practice advocates use of an MR (Moving Range of
Two) chart for its simplicity axid robustness to outliers.
Produce an /-Chart only after a m i n i m u m of 15 preprocessed results have been obtained from the measurement system, and the data have been screened (8.3.1 and 8.3.2) and
tested for normality (A3).
A horizontal center line is added at the level of the mean of
eJl the results, / :
lli
(A8)
Upper and lower control limits are added, also, computed
from the average moving range of two:
equation:
EWMAi = h
EWMAi = (1
A)WMA;-i + \Ii
(A15)
S|/.-..
MR =
(A14)
UCLx = 1 + 2.66MR
(A16)
LCLx = / -
(A17)
(AlO)
(All)
2.66MR
E x a m p l e s o f C o n t r o l C h a r t s f o r QC
and Check Standard Results
Example of an MR Chart for QC ResultsMRi values for the
data from Table Al are calculated and plotted in sequence.
After 15 results are obtained, the MR = 0.500 value is calculated and added to the plot. Computations are shown in Table
A9. A UCLMR=
1.64 is a d d e d to produce the MR Chart
(Fig. A7).
Example of I Chart and EWMA Overlay for QC ResultsThe
average of the first 15 QC results (Table A9, Column 2) is calculated and plotted on the r u n chart as 7 = 55.73. The upper
TABLE A9
MR-Chart
Sequence Number,
I
(A12)
= 3.27
AIR.
(A13)
MR-chait.
EWMA-Overlay
A EWMA overlay is a trend line constructed from Exponentially Weighted Moving Average {EWMA) values calculated
using the I-values. The EWMA trend line is typically overlaid
on the /-chart to enhance its sensitivity in detecting m e a n
shifts that are small relative to the measurement system precision. Each EWMA value is a weighted average of the current result and previous results, with the weights decreasing
exponentially with the age of the reading.
A sequence of values, EWMA,, are calculated, and overlaid
on the /-chart and connected. Use the following recursion
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Average
16
17
18
19
20
21
22
23
24
25
QC Result
(Y, = li)
55.3
55.8
56.3
56.1
55.8
55.5
55.3
55.4
56.6
56.1
55
55.5
55.5
55.2
56.5
Moving Range
MRi
0.5
0.5
0.2
0.3
0.3
0.2
0.1
1.2
0.5
1.1
0.5
0.0
0.3
1.3
55.73
0.500
55.7
55.6
55.2
55.7
56.1
56.3
55.2
55.4
55.4
55.6
0.8
0.1
0.4
0.5
0.4
0.2
1.1
0.2
0.0
0.2
EWMAi
55.3
55.50
55.82
55.93
55.88
55.73
55.56
55.49
55.94
56.00
55.60
55.56
55.54
55.40
55.84
55.78
55.71
55.51
55.58
55.79
55.99
55.68
55.57
55.50
55.54
10
15
10
20
57.5
20
o Result Value
EWMA Value
acL,
57
56.5
^
15
UCL,
VCL,
acLEtna
56
LCL,
(0 55.5
LCL'EtmA
55
54.5
LCL-,
10
LCL,
15
20
30
10
15
20
25
30
FIG. AlOExample of an l-Chart with EWMA overlay for multiple results from a single check standard.
TABLE AlO
Sequence Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Average
16
17
18
19
20
21
22
23
24
25
Check Standard
Result (li)
Moving Range
MRi
-0.58
-0.08
0.42
0.22
-0.08
-0.38
-0.58
-0.48
0.72
0.22
-0.88
-0.38
-0.38
-0.68
0.62
0.5
0.5
0.2
0.3
0.3
0.2
0.1
1.2
0.5
1.1
0.5
0.0
0.3
1.3
-0.153
0.500
-0.18
-0.28
-0.68
-0.18
0.22
0.42
-0.68
-0.48
-0.48
-0.28
0.8
0.1
0.4
0.5
0.4
0.2
1.1
0.2
0.0
0.2
EWMAi
-0.58
-0.38
-0.06
0.05
-0.00
-0.15
-0.32
-0.39
0.06
0.12
-0.28
-0.32
-0.34
-0.48
-0.04
-0.10
-0.17
-0.37
-0.30
-0.09
0.11
-0.20
-0.31
-0.38
-0.34
1058
MANUAL
HANDBOOK
Result Value
. EWMA Value
DCL,
CC 1
PCi,
*(D
-LCL,
10
15
20
25
30
FIG. A12Example of an l-Chart with EWMA overlay for results from multiple check standards.
TABLEAU
Result Sequence
Number, i
Preprocessed Result
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
T-Test
Moving Range
MRi
EWMAi
-0.35
0.82
0.09
-1.35
0.32
-0.83
0.30
-0.53
0.15
0.09
0.26
-0.56
0.20
0.01
0.29
1.17
0.73
1.44
1.67
1.15
1.13
0.83
0.68
0.06
0.17
0.82
0.76
0.19
0.28
-0.35
0.12
0.11
-0.48
-0.16
-0.43
-0.14
-0.29
-0.12
-0.03
0.08
-0.17
-0.02
-0.01
0.11
erage
-0.073
0.791
16
17
18
19
20
21
22
23
24
0.59
-1.19
-0.13
-0.41
-0.73
0.14
-0.38
-0.7
0.17
0.3
li
1.78
1.06
0.28
0.32
0.87
0.52
0.32
0.87
0.30
-0.29
-0.23
-0.30
-0.47
-0.23
-0.29
-0.45
-0.20
[A18]
2. The t vEilue is calculated as:
t = V ^ | 7 , - iJLoVs,,
[A19]
M'(MR/l.n8),
[A20]
30
10
15
20
QUALITY ASSURANCE
OF MEASUREMENT
PROCESSES
FOR
PETROLEUM
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Degrees
of Freedom
Degrees
of Freedom
Degrees
of Freedom
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
12.7062
4.3027
3.1824
2.7764
2.5706
2.4469
2.3646
2.3060
2.2622
2.2281
2.2010
2.1788
2.1604
2.1448
2.1314
2.1199
2.1098
2.1009
2.0930
2.0860
2.0796
2.0739
2.0687
2.0639
2.0595
2.0555
2.0518
2.0484
2.0452
2.0423
2.0395
2.0369
2.0345
2.0322
2.0301
2.0281
2.0262
2.0244
2.0227
2.0211
lyzed are the difference relative to the ARV, (IQ is 0. The standard deviation of the first 15 preprocessed resuUs is 0.493, and
the t vaJue is 1.2034. The t value is less than the critical value
for 14 degrees of freedom (t^ = 2.1448), so the average difference between the check standard results and the accepted
reference value is statistically indistinguishable from zero.
Example oft test applied to results from multiple check standards - For the first 15 preprocessed results in column 6 of
Table A3, 7 is 0.0719. Since the results being analyzed are
the difference relative to the ARV, ^o is 0. The standard deviation of the first 15 preprocessed results is 0.550, and the t
value is 0.506. The t value is less than the critical value for 14
degrees of freedom (fis = 2.1448), so the average difference
between the check standard results and the accepted reference value is statistically indistinguishable from zero.
Approximate Chi-Square Test
The chi-square (x^) test is used to compare the estimated site
reproducibility to a published reproducibility value, as instructed in section 9.1.2.
Compute the Chi-Square
Statistic
.2_{n-\)R'
X-
n2
2R^
[A21]
Degrees
of Freedom
41
42
43
44
45
46
47
48
49
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
2.0195
2.0181
2.0167
2.0154
2.0141
2.0129
2.0117
2.0106
2.0096
2.0086
2.0040
2.0003
1.9971
1.9944
1.9921
1.99006
1.98827
1.98667
1.98525
1.98397
1.98282
1.98177
1.98081
1.97993
1.97912
1.97838
1.97769
1.97705
1.97646
1.97591
1.97539
1.97490
1.97445
1.97402
1.97361
1.97323
1.97287
1.97253
1.97220
1.97190
Degrees
Freedom
Degrees
Freedom
7
8
9
10
11
12
13
14
15
16
14.1
15.5
16.9
18.3
19.7
21.0
22.4
23.7
25.0
26.3
17
18
19
20
21
22
23
24
25
26
27.6
28.9
30.1
31.4
32.7
33.9
35.2
36.4
37.7
38.9
27
28
30
35
40
45
50
60
70
80
40.1
41.3
43.8
49.8
55.8
61.7
67.5
79.1
90.5
101.9
[A22]
1060
MANUAL
HANDBOOK
Denom
d.f.
7
8
9
10
11
12
13
14
15
16
17
18
19
20
25
30
35
40
45
50
60
70
80
90
100
10
12
14
16
18
20
25
30
40
50
100
4.99
4.53
4.20
3.95
3.76
3.61
3.48
3.38
3.29
3.22
3.16
3.10
3.05
3.01
2.85
2.75
2.68
2.62
2.58
2.55
2.51
2.47
2.45
2.43
2.42
4.90
4.43
4.10
3.85
3.66
3.51
3.39
3.29
3.20
3.12
3.06
3.01
2.96
2.91
2.75
2.65
2.58
2.53
2.49
2.46
2.41
2.38
2.35
2.34
2.32
4.82
4.36
4.03
3.78
3.59
3.44
3.31
3.21
3.12
3.05
2.98
2.93
2.88
2.84
2.68
2.57
2.50
2.45
2.41
2.38
2.33
2.30
2.28
2.26
2.24
4.76
4.30
3.96
3.72
3.53
3.37
3.25
3.15
3.06
2.99
2.92
2.87
2.82
2.77
2.61
2.51
2.44
2.39
2.35
2.32
2.27
2.24
2.21
2.19
2.18
4.67
4.20
3.87
3.62
3.43
3.28
3.15
3.05
2.96
2.89
2.82
2.77
2.72
2.68
2.51
2.41
2.34
2.29
2.25
2.22
2.17
2.14
2.11
2.09
2.08
4.60
4.13
3.80
3.55
3.36
3.21
3.08
2.98
2.89
2.82
2.75
2.70
2.65
2.60
2.44
2.34
2.27
2.21
2.17
2.14
2.09
2.06
2.03
2.02
2.00
4.54
4.08
3.74
3.50
3.30
3.15
3.03
2.92
2.84
2.76
2.70
2.64
2.59
2.55
2.38
2.28
2.21
2.15
2.11
2.08
2.03
2.00
1.97
1.95
1.94
4.50
4.03
3.70
3.45
3.26
3.11
2.98
2.88
2.79
2.72
2.65
2.60
2.55
2.50
2.34
2.23
2.16
2.11
2.07
2.03
1.98
1.95
1.92
1.91
1.89
4.47
4.00
3.67
3.42
3.23
3.07
2.95
2.84
2.76
2.68
2.62
2.56
2.51
2.46
2.30
2.20
2.12
2.07
2.03
1.99
1.94
1.91
1.88
1.86
1.85
4.40
3.94
3.60
3.35
3.16
3.01
2.88
2.78
2.69
2.61
2.55
2.49
2.44
2.40
2.23
2.12
2.05
1.99
1.95
1.92
1.87
1.83
1.81
1.79
1.77
4.36
3.89
3.56
3.31
3.12
2.96
2.84
2.73
2.64
2.57
2.50
2.44
2.39
2.35
2.18
2.07
2.00
1.94
1.90
1.87
1.82
1.78
1.75
1.73
1.71
4.31
3.84
3.51
3.26
3.06
2.91
2.78
2.67
2.59
2.51
2.44
2.38
2.33
2.29
2.12
2.01
1.93
1.88
1.83
1.80
1.74
1.71
1.68
1.66
1.64
4.28
3.81
3.47
3.22
3.03
2.87
2.74
2.64
2.55
2.47
2.41
2.35
2.30
2.25
2.08
1.97
1.89
1.83
1.79
1.75
1.70
1.66
1.63
1.61
1.59
4.21
3.74
3.40
3.15
2.96
2.80
2.67
2.56
2.47
2.40
2.33
2.27
2.22
2.17
2.00
1.88
1.80
1.74
1.69
1.66
1.60
1.56
1.53
1.50
1.48
(fij - 1) MRi +
(M2
- 1) MR2
Ml + W2 2
[A23]
TABLE A15
Sequence Number
QC Result
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
54,2
56.1
55.2
54.1
53.7
54
54.3
54.8
53.9
53.2
52.5
52.8
54.3
52.7
53.4
53.1
54
53.2
52.8
53.2
53.1
53.3
52.8
MR
1.9
0.9
1.1
0.4
0.3
0.3
0.5
0.9
0.7
0.7
0.3
1.5
1.6
0.7
0.3
0.9
0.8
0.4
0.4
0.1
0.2
0.5
55.15
55.17
54.90
54.66
54.55
54.51
54.55
54.48
54.35
54.18
54.07
54.08
53.99
53.95
53.89
53.90
53.86
53.81
53.78
53.74
53.72
53.68
LCL
UCL
54.21
54.08
53.75
53.47
53.34
53.28
53.31
53.22
53.09
52.91
52.79
52.81
52.70
52.66
52.61
52.61
52.57
52.51
52.48
52.44
52.42
52.38
56.09
56.25
56.05
55.85
55.76
55.75
55.79
55.73
55.61
55.45
55.34
55.36
55.27
55.23
55.18
55.19
55.15
55.10
55.07
55.04
55.02
54.98
MNL37-EB/Jun. 2003
Index
olefin-based polymers, 224-226
performance package, 200-201
performance testing, 235-242
engine oils, 237-239
finished formulations, 235-236
gear oils, 239-240
greases, 242
hydraulic fluids, 240-241
individual additives, 235
machine tests, 236
metalworking fluids, 241
miscellaneous industrial oils, 241-242
physical tests, 236
ttansmission fluids, 239
viscosity tests, 237
polymeric, 223-233
pour point depressants, 230-232, 373
primary fimctions, 200
refrigeration lubricants, 418-420
rust and corrosion inhibitors, 218, 220-223, 318-320
stabilizers/deposit control agents, 201-211
standard, 243-246
for turbines, 312-323
antifoams, 321-323
antioxidants, 312-318
antiwear and extreme-pressure, 319-321
rust and corrosion inhibitors, 318-320
viscosity modifiers, 223-224
see also Antifoam additives; Antiwear additives;
Antioxidants; Corrosion inhibitors
Adhesion, friction due to, 911
Adhesives, viscosity, 870-872
Adhesive wear, 435, 923, 927-930, 979-982
resistance ranking, 980-981
testing, oil evaluation, 981-982
test method, 979
traction test plots, 980
Adiabatic flame temperature, gasoline, 84
Adiabatic operation, 384
Adipic acids, synthesis, 276, 279
Adsorption, environmental characteristics, 888
Adsorption efficiency, steric hinderance, 952-953
Adsorption isotherms, 953-954
Aeration, hydraulic fluids, 366-367
Aero-derivative gas turbines, 301-302
Aerospace, engine thermodynamics, 730-732
Aerospace fuels, 729-756
air dilution, 742
bouyancy in air, 732
calorific values, 739-740
combustion emissions, 743
density, 735-736
flame stabilization, 742
2003 by A S I M International
www.astm.org
1062
flammability, 738
fueling fire safety, 744
future trends, 747-748
handling characteristics, 743-747
health issues in handling, 747
ignition, 741
lubricity, 744-745
maximum combustion temperature, 735, 740-741
molecular structure, 732-734
oxidation heat release, 735
performance of rocket fuels and oxidants, 731
physical state, 733
preparation and mixing, 741
properties, 735-736
reformation, 747
smoke tendency, 741
solidification, 737-738
specifications, 748
specific impulse, 742-743
spontaneous ignitability, 733-734, 738
standards, 749
stoichiometry, 734-735, 738-739
storage stability, 732, 745
substitute fuels, 748
supplemental fuels, 747
surface tension, 738
thermal stability, 745-746
turbine entry temperature distribution, 742
viscosity, 737
volatility, 736-737
water content, 746-747
Aging, Baader aging test, 821-822
Air conditioning lubricants, 484
Aircraft, sumpingprocedure. 111
Aircraft range, aviation fuels, 100-101
Air-fuel ratio, octane number requirement, 76
Airport
fuel systems, 106
quality control, 110-111
Air release
compressor lubricants, 398
gear lubricants, 460
turbine lubricating oils and hydraulic fluids, 332-334
Alcohol bonds, environmentally friendly oils, 271-272
Alcohols
hydrogen bond, 270
for lubricants, 271-273
Algae, acute toxicity tests, 901-902
Alkalinity agents
automotive lubricants, 474-475
metalworking and machining fluids, 516
Alkanes
lattice transition, 534
physical properties, 532
Alkenylsuccinates, synthesis, 206
Alkylated cyclopentanes, 260
Alkylation, 15-17
HANDBOOK
Alkylbenzene
compressor lubricants, 395
refrigeration lubricants, 415
Alkyl lead
history, 62
phasedown, 63
Alkyl lead content, 68
ASTMD4814, 82
Alkylphenols, 209
Alkyl phosphates, synthesis, 216, 218
Alkyl phosphites, synthesis, 216-217
Alternative fuels, diesel engines, 138-139
Aluminum, production, carbon anodes, 781-782
Aluminum beaker oxidation test, 810, 813
Aluminum complex soap greases, 559
Aluminum soap greases, 558
Ammonia, in LPG, 50
Amonton's Law, 383
Aniline point, hydrocarbon base oil, 181
"Anti-dumping" provisions, 65
Antifoam additives, 233-234
gear lubricants, 441
hydraulic fluids, 367
metalworking and machining fluids, 518
refrigeration lubricants, 419-420
for turbines, 321-323
Anti Knock Index, 73-74
ASTMD4814, 78
Antimicrobial agents, metalworking and machining fluids,
517-518
Anti-misting agents, metalworking and machining fluids,
516
Antioxidants, 201-202, 793-796
arylamine, 795
gasoline, 69, 82-83
gear lubricants, 441,445
hindered phenols, 794
hydraulic fluids, 356-358
metalworking and machining fluids, 518-519
refrigeration lubricants, 419
structures, 314
synergistic combination, 315
turbine lubricating oils and hydraulic fluids, 312-318
zinc dialkyl dithiophosphate, 794
Antiseize additives, 218
Antiwear additives, 69, 213-216, 955-956
gear lubricants, 440,444
hydraulic fluids, 363
refrigeration lubricants, 419
surface reactions, 954-955
turbines, 319-321
Antiwear performance testing, hydraulic fluids, 361-364
Antiwear properties, compressor lubricants, 402-406
API CF oils, 473
API CG-4 oils, 473-474
API CH-4 oils, 474
API gravity
INDEX
1063
1064
water related, 95
lubricity, 102-103
manufacturing, 103-104
metering, 99-100
oxidation
stability, 813
standards, 823
quality control, 106-111
aviation gasoline, 107
contaminants, 106
contamination detection equipment, 109-110
contamination removal equipment, 107-109
jet fuel, 107
procedures, 110-111
standards, 112-113
static electricity, 103
storage stability, 102
transportation, 105-106
volatility and flammability, 98-99
Aviation gas turbine oils
basestocks, 1012, 1014
corrosion inhibited MIL-PRF-23699 oils, 1011
gear testing, 988
high load-carrying DOD-L-85734 oils, 1011- 1012
high thermal stability MIL-PRF-23699 oils, 1011
load capacity database, 1011-1015
master chart, 1012, 1014
selected MIL-PRF-7808 grade 3 and grade 4 oils, 10121013
standard MIL-PRF-23699 oils, 1011
Aviation turbine fuels, thermal oxidation stability, 815-816
Avogadro's Law, 383
Axle lubricants, 483
B
Baader aging test, 821-822
Backpressure control, 164-165
Bainite, 587
Ball bearings, greases, at elevated temperatures, 565-566
Ball on Cylinder Lubrication Evaluator, 102
Ball rust test, 472-473
Band area methods, infrared spectroscopy, 668
Barus equation, 917-918
Base number, gear lubricants, 458
Base oil, see Hydrocarbon base oil
Bearing contacts, performance maps and, 972-973
Beer-Lambert law, 667
Beer's law, 661
Beeswax, 525-526
Bench test, 1020-1021
Block-on-Ring test, 1029-1030
four ball extreme pressure test, 1028-1029
four ball tests, 1026-1027
four ball wear test, 1027-1028
linear reciprocation, 1031 -1033
multi-specimen test machine, 1030-1031
pin and vee block tester, 1025-1026
HANDBOOK
Pin-on-Disk test, 1026
selection, 1019
tapping torque test, 1030
Timken extreme pressure test machine, 1030-1031
Bench test modeling, see Ryder gear; Systematic tribology
Bending-beam rheometer, 870, 872
Benzene, 28
Benzene Emission Number, 66
Bessemer Gas Engine Company, 37
Bias
measurement process, 1044-1045
monitoring, 1047-1048
Bioaccumulation factor, 894-895
Biocides, marine petroleum fuels, 154
Bioconcentration factor, 894-895
Biodegradability
diesters, 252
environmental characteristics, 890-894
hydrocarbon base oil, 182
polyolesters, 252
synthetic lubricants, 263
Biodegradable lubricants, oxidation
standards, 823
testing, 820-822
Biodiesel, 138-139
Biological properties, hydrocarbon base oil, 181-182
Biological stability, polymer quenchants, 620-623
Biota-sediment accumulation factor, 894-895
Bituminous materials, viscosity, 870-872
Black deposits, LPG, 49-50
Black penetration, lubricating greases, 561
"Blaugas", 35-36
Blending
marine fuel oils, 147-148
petroleum oil, 28
Blocking point, petroleum waxes, 552-553
Block-on-Ring test, 1029-1030
Boeing 747-400 fuel tankage, 93
Boiling point, 28
Boiling range, synthetic hydrocarbons, 195
Bomb combustion methods, elemental analysis, 709
Bomb oxidation test, lubricating greases, 565
Bonded fuel, aviation fuels, 106
Boost systems, diesel fuel system, 164
Borsoff effect, 936
Boundary lubrication, 214, 498, 949
Bouyancy, aerospace fuels, 732
Brake fluids, 483
standards, 493
Brayton cycle, 730-731
Broomwade 2050H Compressor Rig Test, 403
Brush drag of latex paints, 868
Btx recovery, 14-15
Bubble tubes, 868
Bulk material properties, flow properties, 921-922, 925-926
Bunsen Coefficient, 406
Bureau of Mines Correlation Index, 186
INDEX
Butadiene
analysis, 193
production, 190-192
purity, 193
Butane, 46
Butane-butene mixtures, chlorides in, 194
Butylene
analysis, 193
production, 190-192
1065
1066
HANDBOOK
detection equipment, aviation fuels, 109-110
gasoline, 69
lubricating greases, 568-569
quench oils, 610-614
removal equipment, aviation fuels, 107-109
Continuous cooling transformation diagrams, 589
Control chart, 1055-1056
Conventional Oxidation Catalyst, 63-64
Coolants, secondary, 574
Coolant separability, hydraulic fluids, 370-371
Cooling curve analysis, polymer quenchants, 621-623
Copper corrosion, 826
aviation fuels, 101-102
compressor lubricants, 398
lubricating greases, 567-568
Copper corrosion inhibitors, 69
Copper corrosion test, ASTM D 4814, 82
Copper deactivation, 221
Copper passivators, 221-222
Copper strip corrosion, diesel fuel, 134-135
Copper strip tarnish test, 827-828
gear lubricants, 454, 456
Corrosion, 825-832
compressor lubricants, 398-399
in LPG, 49
specifications, 827
Corrosion behavior, turbine lubricating oils and hydraulic
fluids, 340-341
Corrosion inhibitors, 218, 220-223
gear lubricants, 441
hydraulic fluids, 369-370
metalworking and machining fluids, 516-517
polymer quenchants, 619-620
surface activity, 826-827
for turbines, 318-320
Corrosion protection, hydraulic fluids, 368-370
Corrosion tests, 827-832
automotive engine oils, 828-829
aviation gasolines, 828
diesel fiiel oils, 828
gear oils, 829
greases, 831-832
lubricants, 827-828, 829-831
Corrosion wear, 931-932
Corrosivity
aviation fuels, 101-102
diesel engine oil, 475
Coupling agents, metalworking and machining fluids, 513
Cracking, crude oil, 146-148
Critical pressure, 384
Critical temperature, 384
Crude oil gases, 3
disposition, 5
Crude oils, 6-7, 145-148
classification, 526-527, 575-576
cracking, 146-148
distillation, 146-147
INDEX
distillation, 696-698
preparation and separation, 9-10
refinery blending and storage, 147-148
refining, 528-529
vapor pressure, 702
waxy, 527-528
Crystalline structure, petroleum coke, 775-776
Crystallization, esters, 289-291
Cyclic durability test, gear lubricants, 458
Cyclohexane derivatives, 260
D
Dalton's Law, 383
Defoamers, see Antifoam additives
Deformation, friction due to, 911
Degree of overbasing, 208
De-icers, 68
Delamination wear, 937-938
Delayed coking, 21-23
Demulsibility
compressor lubricants, 397-398
gear lubricants, 457-458
hydraulic fluids, 366
Demulsifiers, 232-233
gear lubricants, 441
marine petroleum fuels, 154
Density
aerospace fuels, 735-736
crude oil, 6
dieselfuel, 117-118
marine petroleum fuels, 149
petroleum coke, 775
petroleum pitch, 768
refrigeration lubricants, 421
turbine lubricating oils and hydraulic fluids, 332
Deposit control additives, 69-70
Desorption, environmental characteristics, 888
Detergents, 208-211
gear lubricants, 440, 444
hydraulic fluids, 358
micellar structure, 210-211
synthesis, 210
Dewaxing, hydrocarbon base oil, 171-172
Dewaxing process variables, 530-531
Dew Point test, 47-48
Dialkyl dithiophosphoric acid derivatives, synthesis, 215
Dibasic acid esters, refrigeration lubricants, 416
Diesel engines
alternative fuels, 138-139
history, 115-116
Diesel fuel oils, 9
API gravity, 117-118
aromatics, 131-132
ash, 135
carbon residue, 135-136
cetane index, 119-120
cetane number, 119
cleanliness, 124-125
Cloud Point, 121-122
Cold Filter Plugging Point, 123-124
composition/performance correlations, 178-179
copper strip corrosion, 134-135
corrosion tests, 829
corrosiveness, 475
density, 117-118
distillation, 120-121
dyed, 135-137
Flashpoint, 128-129
formation of insolubles, 125
grades, 116-117
heat content, 132-134
heat of combustion, 132-134
ignition and combustion characteristics, 118-119
low-sulfur, 135-137
Low-Temperature Flow Test, 123
lubricity, 129-131
oxidation stability, 126-127
performance categories, 473-474
Pour Point, 122-123
premium, 137-138
requirements, 118
specifications, 116-117
stability, 125-126
storage stability, 127-128
thermal stability, 126
total sulfur, 134
viscosity, 121
volatility, 120-121
World Wide Fuel Charter, 137
Diesel fuel combustion, 717-727
combustion process, 718-719
emissions, 719-721
fuel injection, 717-718
ignition, 718
Diesel fuel oils
cetane number, 721-723
corrosion tests, 828
CVCA/IQT method, 724-727
ignition quality, 721-727
proposed alternatives to ASTM D 613, 723-724
specifications, 718
standards, 727
Diesel fuel system, 161, 163-165
back pressure control, 164-165
boost systems and deaeration, 164
centrifuges, 161, 163
emulsifiers, 165
filters and strainers, 163-164
fuel final filter, 164
fuel service heaters, 164
fuel supply flowmeter, 164
homogenizer, 165
viscosity control, 164
waste heat economizers, 165
1067
1068
HANDBOOK
Elastohydrodynamic film-forming capability, engine oil,
983-987
optical thickness measurement, 984-985
pressure-viscosity coefficients, 985-987
Elastohydrodynamic lubrication, 413, 968
film thickness, 1007
measurements by interferometry, 947-948
mixed film lubrication, 949
non-Newtonian, 948-949
Reynolds equation, 948
Elastomeric seals, see Seal compatibility
Elastomers, turbine lubricating oils and hydraulic fluids
compatibility, 344
Electric-arc furnaces, graphic electrodes, 782
Electrochemical corrosion, 218, 220
Electrostatic stabilization, 204-205
Elemental analysis, 707-716
ASTM proficiency testing, 714
atomic absorption specttometry, 709
bomb combustion methods, 709
classical wet chemistry methods, 709
D02 test methods, 709-710
future developments, 715-716
graphite furnace atomic absorption spectrometry, 709-711
inductively coupled plasma-atomic emission spectrometry,
711-712
inductively coupled plasma-mass spectrometry, 712
international test methods harmonization, 714-715
ion chromatography, 712
microelemental analysis methods, 712
neutron activation analysis, 712-713
sample preparation, 707
standard reference materials, 714
wear metals in used oils, 707-709
X-ray fluorescence spectrometry, 713
Elemental content, gear lubricants, 458
Emissions
aerospace fuels, 743
diesel fuel combustion, 719-721
Emulsifiers, 232-233
diesel fuel system, 165
gear lubricants, 441-442
Emulsion promoters, metalworking and machining fluids,
512-513
Energy conserving characteristics, 471
Energy content, gasoline, 72
Energy equation, 756
Engine deposits, effect on octane number requirement, 77
Engine management systems, 71
Engine oils
adhesive wear testing, 981-982
elastohydrodynamic film-forming capability, 983-987
hydraulic fluids, 374
oxidation
standards, 823
testing, 807-811
performance tests, 237-239
INDEX
standards, 485-488
thermo oxidation engine oil simulation test, 808-812
traction and scuffing failure characteristics, 1008-1009
traction characteristics, 1003, 1005
WAM high speed load capacity test method, 1010
Engine spark timing, octane number requirement, 76-77
Engine tests, engine oils, 823
Entraining velocity, 966-967
Environmental acceptability, synthetic lubricants, 262-263
Environmental characteristics, 885-906
abiotic degradation, 889-890
accumulation processes, 894-895
acute toxicity tests, 894, 901-902
adsorption, 888
biodegradation, 890-894
chemical structure and, 886-887
chronic and subchronic tests, 894, 903-904
complex mixture toxicity, 900-901
desorption, 888
dissociation constant, 888
exposures, 895-896, 900-901
hazard and risk, 904
Henry's Law Constant, 888
low solubility materials, 900
noo-aquatic toxicity tests, 903-904
octanol/water partition coefficient, 887
rationale for standardized testing, 885-886
standardized tests, 895-899
terminology, 904-906
transformation processes, 889
transport processes, 888-889
vapor pressure, 888
volatility, 896, 900
water solubility, 887
Environmental considerations, marine petroleum fuels, 156
Environmental impact, 234
Environmentally acceptable hydraulic fluids, 377-378
Environmentally friendly oils, 267-294
alcohol bonds, 271-272
carboxylic acids, 272-273
chemical properties, 273-276
crystallizing, 289-291
ecologically toxic properties, 289, 291-292
esterification, 270-271
functional groups and elementary compound, 269-270
functions and requirements, 267-268
future developments, 291-293
hydrolysis, 274
low temperature properties, 289-291
native esters, 275, 277-278
oxidation stability, 274-275
standards, 293-294
synthetic esters, 276, 278-279
viscosity, 273, 289-290
see also Pressure media
Equation-of-state approach, 423, 535-539
Equipment line sizing, refrigeration lubricants, 426
1069
1070
HANDBOOK
viscometer geometries, 835-836
wear maps, 942-945
wear surfaces, 911-913
see also Cold flow properties; Viscosity
Fluid biodeterioration, polymer quenchants, 620-621
Fluid catalytic cracking, 9-12
yields, 11
Fluid coking, 770
Fluidized bed hydrocracking, 24-25
Fluid oxidation, compressor lubricants, 400-401
Foaming
automotive lubricants, 471
compressor lubricants, 398
gear lubricants, 456-457
hydraulic fluids, 366-367
turbine lubricating oils and hydraulic fluids, 332-334
Foam inhibitors, see Antifoam additives
Foam testing, polymer quenchants, 620
Four ball extreme pressure test, 457, 1028-1029
compressor lubricants, 402
lubricating greases, 566-567
Four ball tests, 1026-1027
Four ball wear test, 457, 1027-1028
Fourier transform infrared spectroscopy, 667
Free water, 639-640, 646
in aviation fuels, 109-110
Fretting wear, 567, 934-936
Friction, 909-911
area of true contact, 909-911
due to adhesion, 911
due to deformation, 911
due to ploughing, 911-912
standards, 1035-1037
types of, 497
Friction coefficient, 945
effect of hydrocarbon chain length, 954
Friction modifiers, 211-213, 949, 951-952
gear lubricants, 441
F-test, 1059-1060
Fuel additives, marine petroleum fuels, 153-154
Fuel-injection system, 115-116
Fuel injector shear stability test, 852
standards, 875
Fuel oils, 8, 757-762
API gravity, 758-759
ash, 761-762
carbon residue, 761
compatibility of blended, 762
distillation, 761
flashpoint, 761
heating value, 759-760
instability, 762
pour point, 761
specifications and applications, 757-759
sulfiir content, 762
viscosity, 760-761
Fuels, oxidation testing, 811, 813, 815-818
INDEX
1071
1072
demulsibility, 457-458
demulsifiers, 441
detergents, 440, 444
dispersants, 440-441, 445
dynamic seals test, 460
early, 431-432
elemental content, 458
emulsifiers, 441-442
extreme pressure, 439
oxidation, 458
extreme pressure agents, 440, 444
fire point, 454
flash point, 454
foam characteristics, 456-457
foam inhibitors, 441
four ball EP, 457
four ball wear, 457
friction modifiers, 441
function, 431
future trends, 460-461
FZG Pits C 180 TS, 459
FZG scuffing test, 458
gear corrosion test, 460
gear scoring test, 459-460
GFC oxidation, 459
greases, 439
high temperature foam inhibition, 459
insolubles in used oils, 457
kinematic viscosity, 456
low speed high torque hypoid test, 459
low temperature Brookfield viscosity, 458
MIL-PRF-2105E, 451-452
nitrogen level, 458
OEM specifications, 451, 453
open gear compounds, 439
oxidation inhibitors, 441, 445
phosphorus level, 457
polymeric thickeners, 441-442
pour point, 454
pour point depressants, 441
precipitation number, 453
rust and oxidation inhibited, 439
rust inhibition, 456
Ryder gear test conditions, 988-990
SAE 3306 viscosity classification, 449-451
scuffing
front, propagation, 992-993
initiation, 990-992
seal compatibility, 459
shear stability, 459
standards, 461-462, 493
standard tests, 482-483
storage solubility, 460
sulfur level, 457
synchronizer SSP 180 test, 459
systematic tribology, 988-996
thermal and oxidation test, 458
HANDBOOK
Timken EP Tester, 457
fribological features, microscopic examination, 991-992
fribological processes, 993-996
types, 437,439
viscosity index, 457
water content, 457
Gear oils
corrosion tests, 829
oxidation, standards, 822
oxidation testing, 802-804
performance testing, 239-240
Gears
failure modes, 434-436
lubrication, 434, 436-438
types, 432-434
Gear scoring test, gear lubricants, 459-460
Gear testing, aviation gas turbine oil, 988
GFC oxidation, gear lubricants, 459
Glass capillary vacuum viscometers, 870-871
Gloss retention, petroleum waxes, 549
GM quenchometer cooling times, 604-606
Graphic electrodes, for elecfric-arc furnaces, 782
Graphite furnace atomic absorption spectrometry, elemental
analysis, 709-711
Greases, see Lubricating greases
Grossmann hardenability, 592-593
Gum content, gasolines and fuels, 811, 813, 815
H
Halocarbons, in LPG, 50
Hardenability, steel, 589-591
measurement, 591-593
Hardness, petroleum waxes, 547-548
Hazard, environmental characteristics, 904
Health effects, LPG exposure, 54-55
Health issues, aerospace fuels handling, 747
Heat capacity, gasoline, 84
Heat content, diesel fuel, 132-134
Heating value
fiiel oils, 759-760
marine petroleum fuels, 149-150
Heat of adsorption, wear reduction and, 954
Heat of combustion, 72
diesel fuel, 132-134
gasoline, 84
Heat of vaporization, gasoline, 84
Heat resistance, lubricating greases, 563-565
Heat transfer
efficiency, compressor lubricants, 408-409
hydraulic fluids, 353-354
Heat fransfer coefficient, 573-575
Heat transfer fluids, see Mineral oil heat transfer fluids
Heat transfer fluid system, design and construction, 583-584
HEES fluids, 377
Henry's Law Constant,;
HEPG fluids, 378
HEPR type fluids, 378
INDEX
1073
1074
HANDBOOK
terminology, 5-6
see also Synthetic hydrocarbons
Hydrocracked basestocks, turbines, 307-308
Hydrocracking
fixed bed, 24
fluidized bed, 24-25
hydrocarbon base oil, 171
Hydrodynamic film region, 963
Hydrodynamic lubrication, 214, 413,498, 949
Hydrofinishing hydrocarbon base oil, 172
Hydrogen
in petroleum fractions, 195
classification in organic molecules, 788
Hydrogen production, 25-26
Hydrogen refining, hydrocarbon base oil, 171
Hydrolysis
environmental characteristics, 889-890
environmentally friendly oils, 274
pressure media, 279-281
Hydrolytic stability
compressor lubricants, 398
diesters, 251-252
polyolesters, 251-252
pressure media
laboratory aging, 285-287
test stand aging, 287-289
turbine lubricating oils and hydraulic fluids, 339-340
Hydrolytic stability testing, hydraulic fluids, 365-366
Hydroperoxide
decomposers, 791-792
decomposition, 790, 793
oxidation rate and, 790
Hydroprocessing
options, 19
terminology, 18
Hydrostatic tank gauges, 645
Hydrotteated basestocks, turbines, 307-308
Hyfinishing, hydrocarbon base oil, 172
I
/-Chart, 1055-1056
Icing, in LPG systems, 45
Ideal Gas Law, 383
Ignition quality, marine petroleum ftiels, 149-150
Indiana Stirring Oxidation Test, compressor lubricants, 401
Induction Period Method, 813, 815-817
Inductively coupled plasma-atomic emission spectrometry,
elemental analysis, 711-712
Inductively coupled plasma-mass spectrometry, elemental
analysis, 712
Industrial gear lubricants, 453-456
perfr)rmance testing, 240
Indusfrial hydraulic fluids, performance testing, 241
Industrial lubricants, base oil effects, 179-180
Infrared specfroscopy, 665-671
achieving reproducible baselines, 668
analysis of multicomponent solutions, 667-668
INDEX
Laboratory aging
hydrolysis stability, 285-287
oxidation stability, 281-283
Lambda values, 912-913
Lattice transition, alkanes, 534
Lead corrosion, 221
Leakage, lubricating greases, from wheel bearings, 565
Leidenfrost temperature, 593
"Liedenfrost effect", 53
Light hydrocarbons
high temperature vapor pressure, 32
low-temperature vapor pressures, 33
Linear reciprocation, 1031-1033
Liquid chromatography
fluorescent indicator adsorption, 659
hydrocarbon analysis, 657-660
principles, 657-658
standards, 660
super critical fluid chromatography, 659-660
Liquid Heptane Washing Test, compressor lubricants, 401402
Liquified petroleum gas, 31-56
auto propane, 51-52
exposure, 54-55
flammability, 52
gas hydrates, 44-46
handling, 52-54
history, 31-32, 35-38
industry, 32, 35
use, 35-37
odorization, 55
properties and thermodynamics, history, 37-38
sample cylinder approvals, 54
specifications, 38-50
composition, 40
contaminants, 49-50
density, 40
dryness of propane, 42-49
history of ASTM standards, 38-39
naturally occurring radioactive materials, 50
octane, 40
olefins, 40-41
residual matter, 49
sampling, 39-40
sulfiir content, 49
vapor pressure, 40-42
volatility residue, 42
uses, 56
vapor, 53
vapor pressure, 703-704
volume correction factors, 50-51
water in, 47-49
LISCIC/NANMAC quench probe, 623-625
1075
1076
HANDBOOK
aviation fuels, 102-103
dieselfiiel, 129-131
gasoline, 85
Lubricity additives, 69
Luminometer, 98
M
MacCoull equation, 854
MacCoull-Walther equation, 919
Macroemulsions, metalworking and machining fluids, 503
Magnetic quenchometer method, quench oils, 614-615
Magnetic residues, LPG, 49-50
Manifold, air temperature and pressure, octane number
requirement and, 76
Mannich products, synthesis, 206-207
Marine petroleum fuels, 145-167
ash, 150
ash modifiers, 154
biocides, 154
carbon residue, 151-152
cat fines, 150
compatibility, 152
demulsiflers, 154
density, 149
diesel plant fuel system, 161-162
environmental considerations, 156
flashpoint, 150
fuel additives, 153-154
heating value, 149-150
ignition quality, 149-150
impact on exhaust emissions, 154
on board testing, 157
oxidation, 152
pour point, 150
sampling, 156
sediment, 152-153
shore side analysis, 156
sodium in, 152-153
specifications, 154-156
stabilizers and dispersants, 153
standards, 167
steam plant fuel service system, 157, 161
storage systems, 157-160
sulfiir, 151
toxicity, 154
transfer systems, 157
vanadium and nickel in, 152
viscosity, 148-149
water in, 151
Marine transport, aviation fuels, 105-106
Mass spectrometry, 662-665
hydrocarbon analysis, 664-665
instrumentation, 663-664
standards, 665
theory, 662-663
Master chart, aviation gas turbine oils, 1012, 1014
McMillan/Murphy pumpability apparatus, 848
INDEX
Measurement process
bias, 1044-1045
manufacturing process control, 1043
precision, 1044-1045
product property conformance to specification, 10431044
self-monitoring, 1044
see also Quality assurance
Melting point, petroleum waxes, 542-545
Mercaptan odorants, 55
Metal content, mineral oil heat transfer fluids, 580-581
Metal deactivators, 795-796
Metal forming fluids, 509, 520
Metal passivators, 319-320, 369-370
Metal preservatives, 830
Metal protecting fluids, 510
Metal ratio, 208
Metal removal fluids, 505-509, 519
Metals
crude oil, 6
oxidation potentials, 220
significance in petroleum products, 707-708
Metal treating fluids, 510
Metalworking and machining fluids, 234, 497-524
additives, 511-519
alkalinity agents, 516
antimicrobial agents, 517-518
anti-misting agents, 516
corrosion inhibitors, 516-517
coupling agents, 513
dispersants, 516
dyes, 519
emulsion promoters, 512-513
film-forming agents, 513-515
foam inhibitors, 518-519
inorganic/organic solids, 519
odor control agents, 519
base fluid, 510-511
classification based on end-use, 505-510
formulations, 519-521
metal forming fluids, 509
metal protecting fluids, 510
metal treating fluids, 510
oil-based, 501
performance testing, 241
semisynthetic fluids, 504-505
slideway lubricants, 510
solid dispersions, 505
soluble oils, 503
synthetic fluids, 503-504
tests, 521-523
used, recycling, 521-522, 524
water-based, 501-503
classification, 503-505
Metering, aviation fiiels, 99-100
Methane, structure, 732
Methanol
Kill
1078
HANDBOOK
INDEX
1079
1080
HANDBOOK
application and performance characteristics, 255-256
chemical characteristics, 254-255
chemistry, 253
compressor lubricants, 392-393
physical properties, 254
refrigeration lubricants, 417-418
synthesis, 253-254
Polyalphaolefins, 257-258
compressor lubricants, 393-394
refrigeration lubricants, 415-416
for turbines, 308-309
Poly(ethylene) waxes, 525
Polymer, viscosity, 869
loss due to degradation, 228-230
Polymer-containing oils, shear stability, 851-853
Polymeric additives, 223-233
Polymeric thickeners, gear lubricants, 441-442
Polymer molecular weight analysis, polymer quenchants,
620
Polymer quenchants
appearance, 616
biological stability, 620-623
cloud point, 619
conductance, 618-619
cooling curve analysis, 621-623
corrosion inhibitor, 619-620
fluid biodeterioration, 620-621
foam testing, 620
pH determination, 617-618
polymer molecular weight analysis, 620
refractive index, 616-617
viscosity, 617-618
water content, 617
Polyolesters, 249-252
application and performance characteristics, 252
biodegradability, 252
chemical characteristics, 251
chemistry and manufacturing, 249-251
manufacturing technology, 250-251
physical properties, 251
refrigeration lubricants, 416-417
Polyphenyl ethers, 259-260
Polyurea greases, 559-560
Polyvinylethers, refrigeration lubricants, 418
Potential Residue Method, 815
Pour point, 879-880
compressor lubricants, 397
diesel fuel, 122-123
effect of double bonds, 273
esters, 273
fuel oils, 761
gear lubricants, 454
marine pefroleum fuels, 150
petroleum waxes, 545
standards, 874
turbine lubricating oils and hydraulic fluids, 329
Pour point depressants, 205, 230-232
INDEX
1081
1082
HANDBOOK
applicability of WAM high speed load capacity test
method, 1010
backgroimd of load capacity testing, 1001
contact stress simulation, 997-1000
data processing and traction behavior, 1003, 1004-1007
failure criteria in terms of scuffing and micro-scuffing,
1001
link to service performance, 1008-1009
OEM proposed criteria, 1009-1010
oil evaluation, 1000-1010
performance criteria, 1007-1008
procedure, 1003
rolling and sliding velocities across tooth face, 997-1000
simulation approach, 1001-1003
surface film formation, 1007
test description, 1003-1005
tooth temperatures, 996-997
Ryder gear scuffing
criteria, 995-996
effect of oil chemistry, 992-994
effect of load stage, 993-994
initiation, 990-992
Ryder Gear Test, 320-321
simulation conditions, 996-1000
test conditions, 988-990
INDEX
1083
1084
hardenability, 589-591
measurement, 591-593
hardening capability, 599
shock film boiling, 599-602
transformation, 587-589
wetting kinetics, 593-596
Steel quenching
acoustical measurements, 600-602
bath maintenance, 607-608
process analysis example, 626-629
Steric stabilization, 204-205
Stoichiometry, aerospace fuels, 734-735, 738-739
Storage stability
aerospace fuels, 732
aviation fuels, 102
diesel fuel, 127-128
distillate fuel, 817-818
gear lubricants, 460
low temperature, 329
Stormer viscometer, 868
Strainers, diesel fuel system, 163-164
Stribeck curve, 945-946, 949, 1022-1023
Styrene-diene polymers, 225
Subsurface region, 964-965
Sulfur content, 19, 28-29
ASTMD4814, 82
diesel fuel, 134
crude oil, 6
fuel oils, 762
gear lubricants, 457
impact on base oil chemistry, 176-177
LPG, 49
marine petroleum fuels, 151
petroleum coke, 775
petroleum gas, 194-195
petroleum pitch, 768
Sulfur recovery, 26-27
Super critical fluid chromatography, hydrocarbon analysis,
659-660
Surface analysis, methods, 950-951
Surface conformity, 914-916
Surface distress testing
other types, 976-978
imder incipient sliding, 974-975
Surface energy, 922
Surface fatigue, impact of oil attributes, 972, 974
Surface film region, 963-964
Surface films, 919, 921-923
Surface roughness, 911-913
data analysis, 913-916
Surface tension, aerospace fuels, 738
Surfacewax, 549, 551
Synchronizer SSP 180 test, gear lubricants, 459
Synthetic basestocks, compressor lubricants, 392
Synthetic ester fluids, for turbines, 309-311
Synthetic fluids, metalworking and machining fluids, 503504
HANDBOOK
Synthetic hydrocarbons, 185-196
analytical test methods, 192
basestocks, 185-186
boiling range, 195
butylene and butadiene production, 190-192
C-4 product, characterization, 193-194
ethylene, 186-190, 192
propylene, 190, 192-193
standards, 195-196
Synthetic lubricants, 249-264
alkylated cyclopentanes, 260
biodegradability, 263
classes, 249
cyclohexane derivatives, 260
environmental acceptability, 262-263
FDA incidental food contact approval, 263
lubrication, 261-262
perfluoroalkyl ethers, 259
polyalkylene glycols, 252-256
polyalphaolefins, 257-258
polyphenyl ethers, 259-260
raw materials, 249-250
relative cost, 263
silicones, 258-259
standards, 263-264
Synthetic waxes, 525
System operational envelope, refrigeration lubricants, 427
INDEX
1085
1086
HANDBOOK
Vapor pressure, 697-704
automatic method, 701
crude oils, 702
environmental characteristics, 888
evacuated chamber method, 703
gasoline, 699, 701
gasoline-oxygenate blends, 699, 701
liquified petroleum gas, 40-42, 703-704
mini-method, 701-702
mini-method-atmospheric, 702
Reid method, 698-700
triple-expansion method, 702-703
vapor-liquid ratio
Vegetable waxes, 525
Vehicle emission standards, history, 63
Vickers pump stand, 1035
Visbreaking, 20-21
Viscometer geometries, 835-836
Viscosity, 500-501
absolute, water, 863-864
adhesives, 870-872
aerospace fuels, 737
apparent, lubricating greases, 562-563
automotive lubricants, 475-476
bituminous materials, 870-872
bubble tubes, 868
coatings, 867
diesel fuel, 121
diesters, 251
dip cups, 867-868
environmentally friendly oils, 273, 289-290
falling needle, 868-869
fuel oils, 760-761
gas/liquid mixtures under pressure, 408
gasoline, 84-85
greases, 479-480
hydraulic fluids, 359-360
jet fuel, 94
loss
due to polymer degradation, 228-230
shear-related, 225, 227-228
marine petroleum fuels, 148-149
mineral oil heat transfer fluids, 579, 582-583
paints, 867
petroleum pitch, 764-765
petroleum waxes, 546-547
plastics, 869-870
polymer quenchants, 617-618
polyolesters, 251
refrigeration lubricants, 420-422
rubber, 872
standards, 864-867, 872-875
temperature measurement considerations, 866-867
tests, 237
turbine lubricating oils and hydraulic fluids, 326-330
visualization, 835
see also Kinematic viscosity
INDEX
1087