How to Select and Service Turbine Oils

James B. Hannon, ExxonMobil
The question “How long will this turbine oil last?” should be answered with the sound
engineering response of “it depends.”
Turbine oil suppliers can give fairly wide-ranging estimates, say 5 to 15 years, in gas turbine
applications. Any attempt to create a more exact estimate requires consideration of so
many variables that it becomes somewhat useless. Water, heat, contamination, operating
hours and maintenance practices will have a significant impact on
turbine oil longevity.
There is no denying that properly tested and maintained, higher quality
turbine oils will provide longer life than poorly tested and maintained,
lower quality products. Following is a discussion of new turbine oil
performance characteristics that will promote longer, trouble-free
service.
More than 100 tons of steel, rotating at 3600 rpm, is supported by plain
bearings on a cushion of oil that is thinner than a human hair. In power
plants around the world, the same fluid dynamics take place day-in and
day-out without much notice.
Lost revenue at seasonal peaks can be counted in millions of dollars.
An average utility sells electricity for about $50/MW hr during nonpeak
periods, and as much as $1,000/MW hr during peak periods. Poor
selection and maintenance of turbine oil can result in production losses exceeding $500,000
per day.
When selecting a turbine oil for steam, gas, hydro and aero-derivative turbines, oil supplier
services and commitment to the customer should be evaluated as part of the selection
process.

Have the Right Tool for the Job

It is important to have an understanding of the physical and chemical characteristics of
turbine oils compared to other lubricating oils before embarking upon the selection process.
Steam, gas and hydro turbines operate on a family of lubricating oils known as R&O oils
(Rust & Oxidation inhibited oil). Turbine equipment geometry, operating cycles,
maintenance practices, operating temperatures and potential for system contamination
present unique lubricating oil demands versus other lubricating oils like gasoline and diesel
engine applications.
Utility steam and gas turbine sump capacities can range in size from 1,000 to 20,000
gallons, which drives the economic incentive for a long-life lubricating oil. Low turbine oil
makeup rates (approximately five percent per year) also contribute to the need for high-
quality, long-life lubricants. Without significant oil contamination issues, turbine oil life is
primarily dictated by oxidation stability.
Oxidation stability is adversely affected by heat, water, aeration and particulate
contamination. Antioxidants, rust inhibitors and demulsibility additives are blended with
premium quality base stock oil to extend oil life. Lube oil coolers, water removal systems
and filters are installed in turbine lubrication systems for the same purpose.
Unlike most gasoline and diesel engine oil applications, turbine oil is formulated to shed
water and allow solid particles to settle where they can be removed through sump drains or
kidney loop filtration systems during operation. To aid in contaminant separation, most
turbine oils are not additized with high levels of detergents or dispersants that clean and
carry away contaminants. Turbine oils are not exposed to fuel or soot and therefore do not
need to be drained and replaced on a frequent basis.

Recommended Performance
Characteristics of Turbine Oil Vary by
Application Steam Turbines
A well-maintained steam turbine oil with moderate makeup rates should last 20 to 30 years.
When a steam turbine oil fails early through oxidation, it is often due to water contamination.
Water reduces oxidation stability and supports rust formation, which among other negative
effects, acts as an oxidation catalyst.
Varying amounts of water will constantly be introduced to the steam turbine lubrication
systems through gland seal leakage. Because the turbine shaft passes through the turbine
casing, low-pressure steam seals are needed to minimize steam leakage or air ingress
leakage to the vacuum condenser.
Water or condensed steam is generally channeled away from the lubrication system but
inevitably, some water will penetrate the casing and enter the lube oil system. Gland seal
condition, gland sealing steam pressure and the condition of the gland seal exhauster will
impact the amount of water introduced to the lubrication system.

Typically, vapor extraction systems and high-velocity downward flowing oil create a vacuum
which can draw steam past shaft seals into the bearing and oil system. Water can also be
introduced through lube oil cooler failures, improper powerhouse cleaning practices, water
contamination of makeup oil and condensed ambient moisture.
In many cases, the impact of poor oil-water separation can be offset with the right
combination and quality of additives including antioxidants, rust inhibitors and demulsibility
improvers.
Excess water may also be removed on a continuous basis through the use of water traps,
centrifuges, coalescers, tank headspace dehydrators and/or vacuum dehydrators. If turbine
oil demulsibility has failed, exposure to water-related lube oil oxidation is then tied to the
performance of water separation systems.
Heat will also cause reduced turbine oil life through increased oxidation. In utility steam
turbine applications, it is common to experience bearing temperatures of 120ºF to 160ºF
(49ºC to 71ºC) and lube oil sump temperatures of 120ºF (49ºC). The impact of heat is
generally understood to double the oxidation rate for every 18 degrees above 140ºF (10
degrees above 60ºC).
A conventional mineral oil will start to rapidly oxidize at temperatures above 180ºF (82ºC).
Most tin-babbited journal bearings will begin to fail at 250ºF (121ºC), which is well above the
temperature limit of conventional turbine oils. High-quality antioxidants can delay thermal
oxidation but excess heat and water must be minimized to gain long turbine oil life.

Gas Turbines
For most large gas turbine frame units, high operating temperature is the leading cause of
premature turbine oil failure. The drive for higher turbine efficiencies and firing temperatures
in gas turbines has been the main incentive for the trend toward more thermally robust
turbine oils. Today’s large frame units operate with bearing temperatures in the range of
160ºF to 250ºF (71ºC to 121ºC).
Next-generation frame units are reported to operate at even higher temperatures. Gas
turbine OEMs have increased their suggested limits on RPVOT - ASTM D2272 (Rotation
Pressure Vessel Oxidation Test) and TOST - ASTM D943 (Turbine Oil Oxidation Stability)
performance to meet these higher operating temperatures.
As new-generation gas turbines are introduced into the utility market, changes in operating
cycles are also introducing new lubrication hurdles. Lubrication issues specific to gas
turbines that operate in cyclic service started to appear in the mid-1990s. Higher bearing
temperatures and cyclic operation lead to fouling of system hydraulics that delayed
equipment start-up.
Properly formulated hydrocracked turbine oils were developed to remedy this problem and
to extend gas turbine oil drain intervals. Products such as Exxon Teresstic GTC and Mobil
DTE 832 have demonstrated excellent performance for almost five years of service life in
cyclically operated gas turbines where conventional mineral oils often failed in one to two
years.

Hydro Turbines
Hydro turbines typically use ISO 46 or 68 R&O oils. Demulsibility and hydrolytic stability are
the key performance parameters that impact turbine oil life due to the constant presence of
water. Ambient temperature swings in hydroelectric service also make viscosity stability, as
measured by viscosity index, an important performance criterion.

Aero-Derivative Gas Turbines

Aero-derivative gas turbines present unique turbine oil challenges that call for oils with
much higher oxidation stability. Of primary concern is the fact that the lube oil in aero-
derivative turbines is in direct contact with metal surfaces ranging from 400ºF to 600ºF
(204ºC to 316ºC). Sump lube oil temperatures can range from 160ºF to 250ºF (71ºC to
121ºC).
These compact gas turbines utilize the oil to lubricate and to transfer heat back to the lube
oil sump. In addition, their cyclical operation imparts significant thermal and oxidative stress
on the lubricating oil. These most challenging conditions dictate the use of high purity
synthetic lubricating oils. Average lube oil makeup rates of .15 gallons per hour will help
rejuvenate the turbo oil under these difficult conditions.
Current technology turbine oils for land-based power generation turbines are described as 5
cSt turbo oils. Aero-derivative turbines operate with much smaller lube oil sumps, typically
50 gallons or less. The turbine rotor is run at higher speeds, 8,000 to 20,000 rpm, and is
supported by rolling element bearings.
Synthetic turbo oils are formulated to meet the demands of military aircraft gas turbo
engines identified in Military Specification format. These MIL specifications are written to
ensure that similar quality and fully compatible oils are available throughout the world and
as referenced in OEM lubrication specifications.
Type II turbo oils were commercialized in the early 1960s to meet demands from the U.S.
Navy for improved performance, which created MIL - L (PRF) - 23699. The majority of aero-
derivatives in power generation today deploy these Type II, MIL - L (PRF) - 23699, polyol
ester base stock, synthetic turbo oils. These Type II oils offer significant performance
advantages over the earlier Type I diester-based synthetic turbo oils.
Enhanced Type II turbo oils were commercialized in the early 1980s to meet the demands
from the U.S. Navy for better high-temperature stability. This led to the creation of the new
specification MIL - L (PRF) - 23699 HTS. In 1993, Mobil JetOil 291 was commercialized as
the first fourth-generation turbo oil to satisfy present and advanced high temperature and
high load conditions of jet oils. Improvements continue to be made in turbo oil lubricant
technology.
Generator bearing sets typically use an ISO 32 R&O or hydraulic oil. The lower pour points
of a hydraulic vs. an R&O oil may dictate the use of a hydraulic oil in cold environments.

Writing a Turbine Oil Procurement

Standard
Steam, gas and hydro turbine oils are a blend of highly refined or hydroprocessed
petroleum base oils, usually ISO VG 32 and 46 or 68. Lubricant suppliers have developed
turbine oils to meet the varying demands of turbines in propulsion and power generation
applications.
These formulations were developed to meet turbine OEM specifications. Many turbine
OEMs have moved away from specific turbine oil brand name approvals due to enhanced
technologies in their turbines and corresponding improvements in turbine oils. OEMs have
identified suggested or recommended lube oil performance test criteria and typically
stipulate that an oil known to perform successfully in the field may still be used even if all
recommended values have not been satisfied.
Industry standard lube oil bench tests can provide great insight into the performance and life
expectancy of turbine oils. However, turbine OEMs and oil
suppliers generally agree that past successful performance
of a particular oil under similar conditions is the best overall
representation of quality and performance.
Regardless of the type or service of a turbine oil, the quality
of the base stocks and additive chemistry will be a major
factor in its longevity. High-quality base stocks are
characterized by higher percentage saturates, lower
percentage aromatics, and lower sulfur and nitrogen levels.
The performance of additives must be extensively tested.
They must also be blended into the oil in a tightly controlled
process.
The key to a superior turbine oil is property retention. Some turbine oil formulations have
been found to present good lab test data, but can experience premature oxidation because
of additive dropout and base stock oxidation.
Again, lube oil laboratory analysis can support your efforts to determine turbine oil longevity,
but direct field experience should take precedence. Note, turbine oil suppliers will offer
typical lube oil analysis data to help assess predicted performance. Typical data is used
because lubricating oils vary slightly from batch to batch because of minor base stock
variations.
Utility steam and gas turbine oils can be either conventional mineral-based (Group 1) or
hydroprocessed (Group 2). High-quality conventional mineral-based oils have performed
well in both steam and gas turbine service for more than 30 years. The trend toward higher
efficiency, cyclically operated gas turbines has spurred the development of hydroprocessed,
Group 2, turbine oils.
Most hydroprocessed turbine oils will have better initial RPVOT and TOST performance
than conventional turbine oils. This oxidation stability performance advantage is suited for
heavy-duty gas turbine applications.
The oxidation performance advantages of a hydroprocessed turbine oil may not be
necessary in many less demanding steam and gas turbine applications. Conventional
mineral-based oils are known to have better solvency than hydroprocessed oils which can
provide better additive package retention and increased ability to dissolve oxidation
products that could otherwise potentially lead to varnish and sludge.
Compatibility testing between turbine oil brands should also be addressed when writing a
turbine oil specification for systems not available for a complete drain and flush. Clashing
additive chemistries or poor in-service oil quality may prohibit the mixing of different and
incompatible turbine oils. Your oil supplier should provide compatibility testing to confirm
suitability for continued service.
This testing should address the condition of the in-service oil compared to various possible
blends with the proposed new oil. The in-service oil should be tested for suitability for
continued service. Then a 50/50 blend should be tested for oxidation stability (RPVOT
ASTM D2272), demulsibility (ASTM D1401), foam (ASTM D892, Sequence 2) and the
absence of additive package dropout as witnessed in a seven-day storage compatibility
test.

Turbine Lube Oil System Flushing

Turbine lube oil system flushing and initial filtration should be addressed in conjunction with
the selection of the turbine oil. Lubrication system flushing may be either a displacement
flush after a drain and fill, or a high velocity flush for initial turbine oil fills. A displacement
flush is performed concurrently during turbine oil replacement and a high velocity flush is
designed to remove contaminants entering from transport and commissioning a new
turbine.
Displacement flushes using a separate flush oil are done to remove residual oil oxidation
product that is not removed by draining or vacuum. A displacement flush is conducted by
utilizing lubrication system circulation pumps without any modification to normal oil
circulation flow paths, except for potential kidney loop filtration.
This flush is typically done based on a time interval vs. cleanliness (particle levels) to
facilitate the removal of soluble and insoluble contaminants that would not typically be
removed by system filters.
Most turbine OEMs offer high velocity flushing and filtering guidelines. Some contractors
and oil suppliers also offer flushing and filtering guidelines. Often during turbine
commissioning, these guidelines are scaled back to reduce cost and time. There are
common elements of a high-velocity flush that are generally supported by interested parties.
There are also some procedural concerns that may differ and should be addressed on a risk
vs. reward basis.
Common elements of mutual agreement in high-velocity flushing are as follows:
 Supply and storage tanks should be clean, dry and odor-free. Diesel flushing is not
acceptable.
 Two to three times normal fluid velocity achieved with external high-volume pumps
or by sequential segmentation flushing through bearing jumpers.
 Removal of oil after flush is completed to inspect and manually clean (lint-free rags)
turbine lube oil system internal surfaces.
 High-efficiency by-pass system hydraulics to eliminate the risk of fine particle
damage.
Possible supplemental or alternative elements of a high-velocity flush are as follows:
 Use of a separate flush oil to remove oil soluble contaminants that can impact foam,
demulsibility and oxidation stability
 Need to filter the initial oil charge at a level consistent with the filtration specification
 Thermal cycling of oil during the flush
 Pipe line vibrators and the use of rubber mallets at pipe elbows
 Installing special cleanliness test strainers and sampling ports
 Desired cleanliness criteria for flush buy-off
 Lab ISO 17/16/14 to 16/14/11 acceptable particulate range
 Use of on-site optical particle counters
 100-mesh strainer, no particles detectable by naked eye
 Millipore patch test
Up-front planning and meetings with construction, start-up, oil supplier and the end user
should be scheduled in advance to build consensus on these flushing procedures.
A good practice for turbine oil performance documentation is to take a 1-gallon sample from
the supply tank and then a second gallon sample from the turbine reservoir after 24 hours of
operation. The recommended testing is consistent with turbine oil condition assessment
testing:

 Suitability for Continued Use (Annual)

 Viscosity ASTM D445
 RPVOT ASTM D2272
 Water by Karl Fischer Titration ASTM D1744
 Acid Number ASTM D664
 ISO Cleanliness Code 4406
 Rust ASTM D665 A
 Demulsibility ASTM D1401
 Foam ASTM D892 Sequence 2
 ICP Metals

Past experience, turbine OEM recommendations, customer testimonials and oil supplier
reputation are key elements to be considered in the selection of a turbine oil. Proper initial
selection of turbine oil and continued conditioned-based maintenance should set the stage
for years of trouble-free service. In many plants, Murphy’s Law strikes at the worst time.
This is when you will truly appreciate a turbine oil with superior performance characteristics
and an oil supplier with extensive technical support.
References
1. AISE Association of Iron and Steel Engineers. (1996). The Lubrication Engineers Manual
- Second Edition. Pittsburgh, PA.
2. Bloch, H. P. (2000). Practical Lubrication for Industrial Facilities. Lithburn, GA: The
Fairmont Press.
3. Exxon Mobil Corporation. Turbine Inspection Manual. Fairfax, VA.
4. Swift, S.T., Butler D.K., and Dewald W. (2001).
Turbine Oil Quality and Field Applications Requirements. Turbine Lubrication in the 21st
Century ASTM STP 1407. West Conshohocken, PA.
5. ASTM. (1997). Standard Practice for In-Service Monitoring of Mineral Turbine Oils for
Steam and Gas Turbines ASTM D4378-97. Annual Book of ASTM Standards Vol. 05.01.

ISO Viscosity Grades

Noria Corporation

Through the years, lubricant users have been treated to a number of ways to designate
viscosity grades of the lubricants used in manufacturing. There are SAE (Society of
Automotive Engineers) grades for gear oils and crankcases (engines), AGMA (American
Gear Manufacturers Association) grades for gear oils, SUS (Saybolt Universal Seconds),
cSt (kinematic viscosity in centistokes), and absolute viscosity.
To add to the confusion, two measures of temperature (Fahrenheit and Celsius) can be
applied to most of these, not to mention that viscosity might be presented at either 40°C
(104°F) or 100°C (212°F).
While all of these have served useful purposes to one degree or another, most lubrication
practitioners settle on and use one method as a basis for selecting products. To the new
entrant into the lubrication field, the number of options can be confusing, particularly if the
primary lubricant supplier does not associate one of the prominent viscosity systems to the
product label.
To complicate matters, machinery designers must define the lubricant viscosity in such a
way that the equipment user understands clearly what is needed without having to consult
outside advice.
This points to the need for a universally accepted viscosity designation - one that can be
used by lubrication practitioners, lubricant suppliers and machinery design engineers
simultaneously with minimal confusion.
In 1975, the International Standards Organization (ISO), in unison with American Society for
Testing and Materials (ASTM), Society for Tribologists and Lubrication Engineers (STLE),
British Standards Institute (BSI), and Deutsches Institute for Normung (DIN) settled upon an
approach to minimize the confusion. It is known as the International Standards Organization
Viscosity Grade, ISO VG for short.
You don’t have to listen very long in this field before someone
says that viscosity is the most important physical property of a
fluid when determining lubrication requirements.

What is Viscosity?
Viscosity is the measure of the oil’s resistance to flow (shear
stress) under certain conditions. To simplify, the oil’s viscosity
represents the measure for which the oil wants to stay put when
pushed (sheared) by moving mechanical components.
Think of a water-skier cutting through the water. Water has a
viscosity measured in centistokes of 1. That is at the bottom of
the cSt scale. We can see how much water a professional skier
displaces when he runs through a ski course.
If the skier was skiing on a lake of SAE 90/ISO 220 gear oil and
all of the other conditions were exactly the same, then the
amount of spray generated would be considerably less because
the fluid would resist the force of the ski to a much greater
degree.
There are two viewpoints of the resistance to flow that the machine designer is interested in.
One is the measure of how the fluid behaves under pressure, such as a pressurized
hydraulic line. This property is called absolute viscosity (also known as dynamic viscosity)
and is measured in centipoises (cP).
The other consideration is how the fluid behaves only under the force of gravity. This is
called centistokes, which we have already noted. The two are related through the specific
gravity of the fluid. To determine the centipoise of a fluid it is necessary to multiply the
viscosity of the fluid times the specific gravity of the fluid, or measure it directly using an
absolute viscometer. For the practitioner of industrial lubrication, the centistoke is the
measure that will occupy most of our attention.
On a side note, if you are using in-service oils, it is probably worth measuring the viscosity
in absolute units. The measure in centistokes can be misleading because the specific
gravity of lubricants changes with age, generally moving up. It is possible to find yourself
exceeding an absolute viscosity limit for a machine but still have a kinematic measure that
indicates you are OK.
So, viscosity is a measure of the fluid’s resistance to flow. Water has a low viscosity of
1 cSt and honey has a very high viscosity, lets say 1,000 cSt. If a machine is heavily loaded
then the machine designer will use a lubricant that resists being pushed around, which
would be heavy like honey. If the machine runs very fast then the machine designer will
specify a lubricant that can get out of the way, and back into the way just as quickly.
Generally, machines will have either one or the other to be concerned about; sometimes
both at the same time.

Viscosities are defined or assigned using a laboratory device called a viscometer. For
lubricating oils, viscometers tend to operate by gravity rather than pressure. Think of a
kinematic viscometer as a long glass tube that holds a volume of oil. The measure of the
fluid’s viscosity is the measure of the amount of time that it takes for the designated amount
of oil to flow through the tube under very specific conditions.
Because the conditions are repeatable, it is now possible to measure the amount of time
that it takes for the fluid to flow through the tube, and it should be nearly the same each
time. This is similar to the amount of time it takes a specific volume of fluid at a specific
temperature to drain through a funnel. As the fluid gets thicker - a function of its increasing
resistance to flow - then it takes progressively longer to move through the tube (funnel).
Water goes through in one second. The same amount of honey takes a thousand seconds
(hypothetically).
We know that if we raise and lower the temperature of a fluid, there is often a correlating
change in the fluid’s resistance to flow. The fluid gets thicker at lower temperatures and it
gets thinner at higher temperatures.
Given all of these variables and details, several organizations decided to come up with a
way to characterize lubricating oils so that members of their respective organizations would
have a uniform and simple way to communicate, educate and ultimately protect their
interests.

Purpose of the ISO VG System

The purpose of the ISO system of classifying viscosity grades is to establish a viscosity
measurement method so that lubricant suppliers, equipment designers and users will have
a common (standardized) basis for designating or selecting industrial liquid lubricants.
Different approaches were thoroughly considered before the ISO Technical Committee
(TC23) settled on an approach that is logical and easy to use. There were a few important
criteria to keep in mind from the beginning, such as:
 Referencing the lubricants at a nominal temperature for industrial systems.
 Using a pattern that conforms to uncertainties imposed by dimensional
manufacturing tolerances.
 Using a pattern that had some sense of repeatability up and down the scale.
 Using a pattern that used a small, easily manageable number of viscosity grades.
The reference temperature for the classification should be reasonably close to average
industrial service experience. It should also relate closely to other selected temperatures
used to define properties such as viscosity index (VI), which can aid in defining a lubricant.
A study of possible temperatures indicated that 40ºC (104ºF) was suitable for the industrial-
lubricant classification as well as for the lubricant-definition properties mentioned above.
This ISO viscosity classification is consequently based on kinematic viscosity at 40ºC
(104ºF).
For the classification to be used directly in engineering design calculations in which the
kinematic viscosity of the lubricant is only one of the parameters, it was necessary that the
viscosity grade width (range of tolerance) be no more than 10 percent on either side of the
nominal value. This would reflect an order of (center point) uncertainty in calculations similar
to that imposed by dimensional manufacturing tolerances.
This limitation, coupled with the requirement that the number of viscosity grades should not
be too large, led to the adoption of a system with gaps between the viscosity grades.
This classification defines 20 viscosity grades in the range of 2 to 3200 square millimeters
per second (1 mm2/s = equals 1 cSt) at 40ºC (104ºF). For petroleum-based liquids, this
covers approximately the range from kerosene to cylinder oils.
Each viscosity grade is designated by the nearest whole number to its midpoint kinematic
viscosity in mm2/s at 40ºC (104ºF), and a range of +/- 10 percent of this value is permitted.
The 20 viscosity grades with the limits appropriate to each are listed in Table 1.
The classification is based on the principle that the midpoint (nominal) kinematic viscosity of
each grade should be approximately 50 percent greater than that of the preceding one. The
division of each decade into six equal logarithmic steps provides such a system and permits
a uniform progression from decade to decade.
The logarithmic series has been rounded off for the sake of simplicity. Even so, the
maximum deviation for the midpoint viscosities from the logarithmic series is 2.2 percent.
Table 2 pulls together some popular viscosity measurement methods into one table. If the
practitioner is comfortable with one particular measure but would like to see the correlating
viscosity range in another measure, all he must to do is place a straight horizontal line
through his chosen viscosity type and see its correlation within the other types of measures.
While it is true that some viscosity grades will be left out of the mix as companies move
toward adopting the ISO designation, it is not necessary that the users of those products
have to move away from them. Further, there is no intention to offer quality definition of
lubricants with this scale. That a product has an ISO VG number associated with it has no
bearing on its performance characteristics.
The ISO designation has been under development since 1975. The most recent release in
1992 (ISO 3448) contains 20 gradients. This covers nearly every type of application that the
lubricant practitioner can expect to encounter. The lubricant manufacturing community has
accepted the recommended ISO gradients and has devoted appreciable effort and energy
to conform to the new grading approach with old and new products.
It is unlikely that all of us who learned about the use of oil from our mentors or friends under
the hood of a car will ever abandon the SAE grading system. We don’t have to. At least for
automotive oils, we can expect to continue to see the 10- 20- 30- 40- 50- values used. It is
likely, however, that in the industrial lubrication world there will be more ISO dependence in
the future.
Don't Ignore Viscosity Index When
Selecting a Lubricant
Jim Fitch, Noria Corporation
Too often the viscosity index (VI) is disregarded as a lubricant selection parameter. One
reason is simply because it is poorly understood. Some people think the viscosity index is
incorporated in the ISO Viscosity Grade, but it is not. It stands alone as an independent
lubricant performance differentiator.
We all know that viscosity is the single most important physical property of a lubricant. It is a
crude measure of a lubricant’s molecular constitution from the standpoint of hydrocarbon
chain size. Viscosity is determined by creating friction between the molecules from fluid
movement. The higher the intermolecular friction (longer molecular chains), the higher the
viscosity.
thickness and film strength in machines. It also influences other important factors such as
those in the table below.

The Effects of Viscosity

However, a lubricant’s viscosity is meaningless unless the temperature is noted, i.e., the
temperature at which viscosity is measured. Conversely, machines don’t care about
temperature as it relates to viscosity (loosely speaking).
Minimum, maximum and optimum viscosity requirements demanded by machines don’t take
temperature into account. Instead, a machine’s viscosity requirement is based on such
things as component design (e.g., bearing), loads and speeds. You may recall that the well-
known Stribeck curve doesn’t have a temperature variable.
That said, because machines require a certain viscosity, and temperature is known to have
a dramatic influence on viscosity, it is imperative that you take the average operating
temperature and temperature range into account when selecting viscosity.
Remember, the ISO Viscosity Grade system only reports viscosity at a single temperature:
40 degrees C. Most importantly, for any candidate oil, you need to know how viscosity
changes relative to a change in temperature.
The viscosity index was developed for this purpose (ASTM D2270) by E. Dean and G.
Davis in 1929. It is an empirically derived, unitless number. Based on the methodology,
Pennsylvania crude (paraffinic) was set as a benchmark at one extreme, representing low
viscosity changeability relative to temperature.
At the other extreme was Texas Gulf crudes (naphthenic). If a lubricant was similar to the
Pennsylvania crude, it was assigned a VI of 100. If it was similar to Texas Gulf crude, it was
assigned a VI of 0. Halfway in between was a VI of 50, and so forth. The higher the VI, the
more stable the viscosity across a range of temperatures (more desirable). The
temperatures used to determine the VI are 40 degrees C to 100 degrees C.

An Internet search on “viscosity index calculator” will direct you to several Web pages. You
can use these calculators in a variety of ways. For instance, if you know the viscosity of a
lubricant at two different temperatures, you can use the calculator to give you an estimation
of the VI. Better yet, you can enter a single known viscosity (and temperature) and VI
(commonly found on a lubricant’s product data sheet) to calculate the viscosity of the same
lubricant at any other temperature (say, a machine’s operating temperature).
Lubricants with VIs as low as minus 60 are available today. Other lubricants can have VIs
ranging over 400. However, the vast majority of lubricants on the market will have VIs in the
range of 90 to 160.
Let’s take a look at two different oils that share one common property - they’re both ISO VG
150. However, one of these oils (Oil A) has a VI of 95 (mineral oil), while the other (Oil B)
has a VI of 150 (synthetic). Now let’s examine the viscosity of these oils from minus 20
degrees C (minus 4 degrees F) to 100 degrees C (212 degrees F). This is shown in the
table below.

of lubrication professionals consider an oil’s viscosity

89% index when selecting a lubricant, according to a recent
survey at machinerylubrication.com
Comparing the 95 VI oil to the 150 VI oil, there is a 236-percent difference in viscosity at
minus 20 degrees C and a minus 25-percent difference at 100 degrees C. Of course, there
is no difference at 40 degrees C.
As mentioned previously, the machine dictates the viscosity requirements based on its
design and operating conditions. These conditions influence temperature, which in turn
influences viscosity, which influences the protection provided.
Many machines use a common lubricant across numerous frictional zones and have varying
loads, speeds and temperatures. Outdoor mobile equipment typically works under these
challenging conditions. For such machines, there is no easy way to identify optimum
viscosity by a theoretical calculation.
Instead, the ideal viscosity is estimated using actual field measurements by applying a trial-
and-error approach (simply testing with different viscosity oils and measuring temperature
and wear protection).
 

Comparison of Two Different Oils with the Same Viscosity Grade

 
For machines of constant load, constant speed and constant ambient temperatures, the
ideal viscosity very often results in the lowest stabilized oil temperature. Oils of lower or
higher viscosities (than the optimum viscosity) will typically increase the oil’s stabilized
temperature due to either churning losses (too much viscosity) or mechanical friction (too
little viscosity).
If conditions are not constant (variable loads, variable speeds, variable ambient
temperatures, etc.), then there is a need for not only the optimum viscosity but also a high
viscosity index to stabilize the optimum viscosity. The more variable the conditions, the
greater the need for high VI oils.
Also, keep in mind that for a great many machines there has been no past experimental or
theoretical effort to identify the optimum viscosity. Viscosity selection is more of a wild
guess. This too calls for a high VI lubricant.
 

 
You must also consider that the ISO Viscosity Grade system (ISO 3448) is based on 50-
percent increments between grades. As such, if you go from ISO VG 100 to VG 150, it is a
50-percent jump. When the viscosity options are all 50 percent apart, it is difficult to achieve
precision lubricant selection. These large viscosity steps are further magnified at lower
temperatures. This is yet another reason to select high VI lubricants.
 

High or Low Viscosity Index?

A lubricant may merit having a high VI for one or more of the following reasons:

 The optimum viscosity is not known

  Varying loads and speeds exist
 Varying ambient temperatures exist
 To boost energy efficiency
 To boost oil service life (lower average temperature)
 To boost machine service life (fewer repairs and downtime)

Cheaper, lower VI lubricants may make sense if:

 Speeds and loads are constant

 Temperature is constant (constant ambient temperature or a heat exchanger is in
use)
 The optimum viscosity at the operating temperature is known and is consistently
achieved

An oil’s VI can also tell you useful information about a lubricant’s formulation, including the
type and quality of base oils. For instance, highly refined and pure mineral oils will have
correspondingly higher VIs. Certain additives, such as viscosity-index improvers and pour-
point depressants, influence VI as well. Remember, oils loaded with VI improvers,
especially of certain types, are prone to permanent loss of VI and viscosity over time. There
are ASTM tests for measuring the VI stability of lubricants exposed to high shear.
Viscosity index values are on almost all product data sheets for commercially available
lubricants. This simple number is there for a reason and should be strongly considered
when writing a specification for lubricants in nearly all machine applications.

5 Ways Aerated Oil Wrecks Machines

Jim Fitch, Noria Corporation
We’re told machines should not be allowed to swallow air. But what if they do?
What harm could be caused by this bubbly stuff anyway? Do we really have to make the
machine burp? Will a few pats on the back do the trick?
For many of you, air contamination is no laughing matter. Why? Because air contamination
is a serious condition.
There are five deadly problems associated with aerated oil. By aerated oil, I’m referring to
entrained air, foam or both, which is the usual case. The five problems include the following:

 Oxidative Oil Degradation

 Thermal Degradation
 Impaired Heat Transfer
 Retarded Oil Supply
 Cavitation

Depending on the machine design, application and aeration severity, it is possible that all
five of these conditions could be happening at the same time. Let’s discuss each of these
killers in more detail:

Oxidative Oil Degradation

Aeration exposes oil to oxygen. The bubbles produce a high surface area interface between
the air and the oil. The interface serves as reaction sites for oil oxidation to initiate,
particularly when the oil is hot and moist.

Thermal Degradation
Aerated oil generates heat by the following mechanisms:

 adiabatic compression of air bubbles (localized heat generation)

 aeration-induced oil flow resistance in piping and components (energy is converted
to heat)
 loss of bulk modulus (air makes oil compressible which generates heat)

The heating problem is compounded by impaired cooling, as described below. The building
heat leads not only to oil oxidation but also to thermal degradation (such as from
microdieseling) forming varnish, sludge and carbon insolubles. Additives such as zinc
dialkyldithiophosphate (ZDDP) will also deplete prematurely due to the heat.

Impaired Heat Transfer

Aeration degrades the heat transfer properties due to the following reasons:

 Aerated oil is not a good thermal conductor.

  Restricted oil flow from aeration impedes convection (movement of the heat from
movement of the fluid).

While foam retards the oil’s ability to release heat in the reservoir, entrained air also
interferes with heat transfer (and movement) in coolers and through machine casing, piping
and other thermally conductive surfaces. When oil runs hot, viscosity runs thin which
degrades film strength in frictional zones leading to wear. Of course, impaired heat transfer
properties compounds the problems described in numbers 1 and 2 above.

Retarded Oil Supply

Many factors contribute to oil supply problems associated with air. Some of these factors
include:
 Oil Compressibility. Aerated oil is hard to pump. It’s like trying to pump against a
sponge. The actual delivered oil volume (oil flow rate) may be only a fraction of what
the pump normally supplies without the aeration condition.
 Dampening. Foam causes the dampening of important headspace oil movement in
machines that depend on oil lifting (throwing) mechanisms, including splash
lubrication, paddle gears, flingers and slingers. The foam retards the oil travel (toss)
through the air, resulting in it failing to reach critical zones of the machine, including
bearings and gears.
 Reduced Oil Density. Many machines depend on oil flowing efficiently by
gravitational forces. A bubbly oil has very low density and gravitational pull. For
instance, a ring oiler my lift some foamy oil to the upper port of the journal bearing,
however its low density (and increased apparent viscosity) impair its ability to
penetrate downward into the bearing’s channels and grooves for lubrication. The
same is true in gravity oil drains and headers from bearings and gears in circulating
oil systems.
  Air-Lock. Foamy, low-density oil can cause air-lock resulting in a complete
cessation of oil flow (restricted oil drains, loss of pump prime, redirected oil flow,
etc.). An aerated oil has an apparent viscosity sharply greater than that of the oil
alone which compounds the problem.
 Reduced Oil Level. Foam robs liquid-phase oil from the reservoir or sump which
means the working oil level falls. This often brings the oil level below what is needed
to adequately prime pumps (head), supply oil to lifting devices (ring, collars, paddles,
flingers, slingers, etc.) and supply oil to bath/splash-lubricated gears and bearings.
Low oil level is a circular problem causing more aeration, more heat and less air-
release residence time.

Cavitation
When vapor bubbles become rapidly pressurized, such as in a pump or journal bearing,
destructive microjets of oil can collide with machine surfaces at extremely high velocities.
Some have estimated that the velocities may approach the speed of sound. The result is a
progressive localized erosion of these surfaces. Note that vapor bubbles cause
most erosive damage from cavitation, not air bubbles. Vapor bubbles form from the oil itself
(light oil fractions) as well as from water contamination (water vapor).
Now that we know the harm caused by aeration and foam, let’s direct our attention to what
can be done to prevent its occurrence. I’ve broken the strategies to control aeration into four
plans labeled A through D, meaning you move sequentially through the plans until you find
a strategy that works.
Ideally, aeration should be held in check by deploying a Plan A strategy which conforms to
proactive maintenance. However, because of frequent deficiencies in machine design and
the difficulty of performing proactive fixes on the run (to control root causes), other
strategies may be left as the only remaining options.
Below is a brief description of the four plans or strategies and how they can be implemented
to control aeration:
Plan A - Stop air from becoming entrained. When you control entrained air, by default, you
also control foam. Below are the top four ways air becomes entrained in lubricating oils
and hydraulic fluids:
 Plunging oil returns (free falls that cause churning and aeration) versus return lines
with diffusers that ooze the oil back to tank
 Suction leaks or pump seal leaks that entrain air
 Over agitation of tanks (low oil level or poor tank design) causing turbulence,
vortexes and/or lapping (folding in air on tank surfaces)
 Vented drains where air and oil mix coming down drain lines before returning to tank
Plan B - Keep air buoyant to aid its rapid detrainment from your oil. If air does become
entrained, the following are strategies for rapid release to the atmosphere without forming
foam:
  Ensure healthy condition of defoamants additives
 Keep air bubbles large and buoyant by keeping oil interfacial tension high. The
smaller the air bubble, the longer it takes to reach the surface and detrain. Factors
that reduce interfacial tension:
 emulsified water
 oxides
 polar additives or contaminants
When entrained air passes through oil filters, pumps, bearings, etc. air bubbles are crushed
to such an extent that they don’t release quickly. In extreme cases, the air/oil mixture has
the consistency of whipping cream.
Plan C - Give air detrainment sufficient residence time. Given enough time, even finely
crushed air bubbles can migrate out of the oil. Strategies for accomplishing this include:
 Large-volume reservoirs
 Reservoirs with flow-directed baffling to avoid short circuiting
 Use of settling and air detrainment tanks
Plan D - Deploy air detrainment practices and technologies to accelerate separation time.
Options include:
 Apply slight reservoir vacuum.
 Use an off-line vacuum chamber for both air release and dehydration purposes.
 Install vortex deaeration technologies.
 Install wire-cloth air coalescers/separators in the reservoir.

Role of Oil Analysis

While routine oil analysis is not effective at detecting or measuring the actual presence of
air in oil, it can pick up common properties associated with root causes (C) and symptoms
(S) of air-related problems, such as those in following:
 Depleted silicone defoamants additive - C
 Prematurely oxidized/thermally degraded oil (RPVOT, viscosity, FTIR, RULER, etc.)
- C and S
 Elemental analysis of contaminants - C S Interfacial tension analysis - C S
Ultracentrifuge/total insolubles analysis - C and S S ASTM air release and foam
tendency/stability tests - C
In summary, managing aeration and the air-handling ability of lubricants is no insignificant
matter. Air is a real contaminant that requires thoughtful monitoring and control. Perhaps
your contamination control program began with dirt, then progressed to moisture, but now
it’s time to give your machine a gentle burp.
The Importance of Oil Oxidation Stability
Noria Corporation

What is meant by the term “oxidation stability”

and why is it important?
Oxidation stability is a chemical reaction that occurs with a combination of the lubricating oil
and oxygen. The rate of oxidation is accelerated by high temperatures, water, acids and
catalysts such as copper. The rate of oxidation increases with time. The service life of a
lubricant is also reduced with increases in temperature. Oxidation will lead to an increase in
the oil's viscosity and deposits of varnish and sludge.
The rate of oxidation is dependent on the quality and type of base oil as well as the additive
package used. Some synthetics, such as polyalphaolefins (PAO), have inherently better
oxidation stability than do mineral oils. This improved oxidation stability accounts for the
slightly higher operating temperatures that these synthetic oils can accommodate.
Generally, oxidation will reduce the service life of a lubricant by half, for every 10 degrees C
(18 degrees F) increase in fluid temperature above 60degrees C (140 degrees F). This
concept is based on the Arrhenius rate rule, which is named for the 19th-century Swedish
chemist Svante Arrhenius.
There is a little controversy concerning the oxidation stability of natural mineral base oils as
determined by the refining method. There is one school of thought that suggests that
hydrotreated base stocks have superior oxidation resistance and thermal stability than does
solvent-refined base oil.
This is based on the misconception that since hydrotreating removes all of the potentially
undesirable compounds, the base oil tends to automatically reduce deposit-forming
tendencies and thereby will better resist oxidation. However, removing all of the compounds
considered undesirable can in fact be detrimental.
Solvent refining results in the production of base oils, which retain some sulfur compounds
that are natural antioxidants. These base oils retain a natural ability to prevent oxidation,
while hydrotreated base oils must be further fortified with antioxidants in order to maintain
thermal and oxidation stability. Once the antioxidants are weakened or depleted, oxidation
of some hydrotreated oils can occur very rapidly.
Severely hydrotreated base oils also have poor solubility characteristics. Without proper
formulation, additives may not remain suspended, and some additive drop out could occur.
Several methods may be used to determine or evaluate the oxidation stability of an oil,
which is usually regarded as the number of hours until a given increase in viscosity is noted
or until there is a given increase in the acid number (AN).

Water In Oil Contamination

Noria Corporation

Much has been said about particle contamination and its effect on component longevity. It is
well known that an improvement in particle contamination by one ISO Cleanliness Code can
result in a 10 to 30 percent increase in the life of contamination-sensitive components such
as hydraulic valves, pumps, and journal and rolling element bearings.
Industry spends millions of dollars each year on improved filtration technology in an attempt
to reduce particle contamination, with some of the more advanced companies reducing
failure rates by up to 90 percent simply by controlling fluid cleanliness. However, in some
industries and environments, water is a far more insidious contaminant than solid particles,
and is often overlooked as the primary cause of component failure.

Water In Oil States of Coexistence

Water can exist in oil in three states or phases. The first state, known as dissolved water, is
characterized by individual water molecules dispersed throughout the oil. Dissolved water in
a lubricating oil is comparable to moisture in the air on a humid day - we know the water is
there, but because it is dispersed molecule-by-molecule, it is too small to see.
For this reason, an oil can contain a significant concentration of dissolved water with no
visible indication of its presence. Most industrial oils such as hydraulic fluids, turbine oils,
etc., can hold as much as 200 to 600 ppm of water (0.02 to 0.06 percent) in the dissolved
state depending on the temperature and age of the oil, with aged oils capable of holding
three to four times more water in the dissolved state than new oil.
Once the amount of water has exceeded the maximum level for it to remain dissolved, the
oil is saturated. At this point, the water is suspended in the oil in microscopic droplets known
as an emulsion. This is similar to the formation of fog on a cool, spring day. In this case, the
amount of moisture in the air exceeds the saturation point, resulting in a suspension of
small droplets of moisture or fog. In a lubricating oil, this “fog” is often referred to as haze
with the oil said to be cloudy or hazy.
The addition of more water to an emulsified oil/water
mixture will lead to a separation of the two phases
producing a layer of free water as well as free and/or
emulsified oil. This is like rain falling when the amount
of moisture in the air becomes excessive. For mineral
oils and PAO synthetics whose specific gravity is less
than 1.0, this free water layer is found on the bottom of
tanks and sumps.

The Effects of Water

Contamination
In a lubricating system, the two most harmful phases
are free and emulsified water. In journal bearings for example, the incompressibility of water
relative to oil can result in a loss of the hydrodynamic oil film that in turn leads to excessive
wear. As little as one percent water in oil can reduce the life expectancy of a journal bearing
by as much as 90 percent.
For rolling element bearings, the situation is even worse. Not only will water destroy the oil
film strength, but both free and emulsified water under the extreme temperatures and
pressures generated in the load zone of a rolling element bearing can result in
instantaneous flash-vaporization causing erosive wear to occur.
Under certain conditions, water molecules can be ripped up into their constituent oxygen
and hydrogen atoms as a result of the high pressures generated in the load zone of a rolling
element bearing. Due to their relatively small size, the hydrogen ions produced by this
process can absorb onto the surface of the bearing raceway resulting in a phenomenon
known as hydrogen embrittlement.
Hydrogen embrittlement is caused by a change in subsurface bearing metallurgy. This
change causes the bearing material to become weak or brittle and prone to cracking
beneath the surface of the raceway. When these subsurface cracks spread to the surface,
the result can lead to pitting and spalls.
Because the effects of free and emulsified water are more harmful compared to dissolved
water, a general rule of thumb is to ensure that moisture levels remain well below the
saturation point. For most in-service oils this means
100 to 300 ppm or less depending on the oil type and
temperature.
However, even at these levels, a significant amount of
damage can still occur. Generally speaking, there is no
such thing as too little water and every reasonable
effort should be made to keep water contamination as
low as possible.

The Effects of Water on

a Lubricant Water-Related Bearing Damage
Not only does water have a direct harmful affect on
machine components, but it also plays a direct role in the aging rate of lubricating oils. The
presence of water in a lubricating oil can cause the progress of oxidation to increase
tenfold, resulting in premature aging of the oil, particularly in the presence of catalytic
metals such as copper, lead and tin.
In addition, certain types of synthetic oils such as phosphate esters and dibasic esters are
known to react with water, resulting in the destruction of the base stock and the formation of
acids.
It is not just the base oil that can be affected by moisture contamination. Certain additives
such as sulfurous AW and EP type additives and phenolic antioxidants are readily
hydrolyzed by water, resulting in both additive mortality and the formation of acidic by-
products.
These acidic by-products can then cause corrosive wear, particularly in components
containing soft metals such as Babbitt used with journal bearings and bronze and brass
components. Other additives such as demulsifying agents, dispersants, detergents and rust
inhibitors can be washed away by excessive moisture. This results in sludge and sediment
buildup, filter plugging and poor oil/water demulsibility.

Measuring Water
In order to control moisture levels, one must be able to detect its presence. There are five
basic test methods used to determine the moisture content of a lubricating oil. These
methods range from a simple apparatus to a more complex chemical test or slightly more
expensive percent saturation probe test ideal for on-site screening purposes. It may also
include more advanced technology typically used in laboratories for precise determination of
the water level in ppm.
The most basic is the Crackle Test. In this test, a hot plate is held at 320°F (130°C) and a
small drop of oil placed in the center. Any moisture present in the oil is reflected in the
number of bubbles observed as the water vaporizes. Depending on the lubricant, relatively
few small bubbles indicate approximately 500 to 1,000 ppm (0.05 to 0.1 percent) water.
Significantly more bubbles of a larger size may indicate around 1,000 to 2,000 ppm water,
while an audible crackling sound indicates moisture levels in excess of 2,000 ppm. The
Crackle Test is sensitive only to free and emulsified water.
Another simple on-site test is the use of a pressure cell where the sample is prepared with a
chemical reagent (calcium hydride) and placed in a container and shaken vigorously. A
change of pressure within the cell is monitored to determine if free water is present.
The cost of this type of product is relatively low, although the running costs must be
considered with regard to the reagents, as well as the health and safety issues of these
reagents. Suppliers include Kittiwake, Koehler and Dexsil.
A third type of on-site screening test for water is the use of a relative humidity sensor. The
sensor uses a thin film capacitance grid that can determine the amount of moisture
permeating through the film. Whether used in air or oil, the technology is the same and the
output of data is normally in a percent RH value.
As discussed earlier, the percent RH is an indication of whether the oil has yet reached the
saturation point, although as in the atmosphere, the lower the temperature, the lower the
saturation point in terms of water concentration. While it is mathematically possible to derive
a ppm value from the percent RH against the saturation curve for the oil at a known
temperature, the thinking behind this type of sensor is to provide a proactive early warning
of imminent problems as well as providing a screening capability prior to sending a sample
to a commercial laboratory.
The water saturation article gives a clear description of the performance and applicability of
this tool. The advantage of this method is its relatively low running costs and that it can be
permanently mounted on critical plant equipment to provide real-time monitoring. Suppliers
include Pall Corporation and Rockwell Automation - Entek.
Aside from the on-site screening methods, another commonly used method to screen for
water is Fourier Transform Infrared Spectroscopy (FTIR). This test is sensitive to free,
emulsified and dissolved water, however it is limited in precision to a lower detection limit of
about 1,000 ppm.

This is adequate for some applications, but insufficient for typical industrial applications.
Commercial laboratories that use this method often report that less than 0.1 percent volume
of water is present in the sample. Suppliers include Bio-Rad, MIDAC, Nicolet and
Thermolube.
The most precise method for determining the amount of free, emulsified and dissolved
water in a lubricating oil is the Karl Fischer moisture test. When used correctly, the Karl
Fischer test is capable of quantifying water levels as low as 10 ppm or 0.001 percent and
should be the method of choice when more exact water concentrations need to be known.
Care should be exercised when using the Karl Fischer moisture test to avoid interference
effects caused by sulfurous EP and AW additives. Suppliers include Mettler and Metrohm.
Whichever method is used to determine water levels, one thing is certain: Water is a major
cause of lubricant failure, component failure and poor machine reliability. Like all
contaminants, it is important not only to recognize its presence, but also to take steps to
control or eliminate the source of water ingression. If possible, water levels in all equipment
should be kept below the saturation limit, with every effort made to keep moisture levels as
low as possible.
Whether you choose to install desiccant style breathers, improve seals, or to use a
centrifugal filter or a large vacuum dehydration unit, reducing the level of water in all types
of equipment can dramatically extend the life of the lubricant and the machine.
Read more on water-in-oil contamination:
How to Measure Water In Oil
Options for Removing Water in Oil
Removing Water Contamination from Oil
Best Ways to Test for Water in Oil

Oxidation - The Lubricant's Nemesis

Dave Wooton, Wooton Consulting
Oxidation is the most predominant reaction of a lubricant in service. It is responsible for
numerous lubricant problems - including viscosity increase, varnish, sludge and sediment
formation, additive depletion, base oil breakdown, filter plugging, loss in foam control, acid
number (AN) increase, rust formation and corrosion. Therefore, understanding and
controlling oxidation is a priority of the lubricant chemist.
Many new oil formulation tests (such as ASTM D4310 - the sludge and oxidation test,
turbine oxidation stability test (TOST) D943 and D4485 - the engine oil performance
categories) and used oil analysis tests (such as fourier transform infrared (FTIR) oxidation
ASTM D2412, linear sweep voltammetry (LSV) RULER™ - ASTM 6971, QSAsm and acid
number D664) are used to study this lubricant's nemesis.

Common Oxidation Indicators

Every lubricant is designed with an oxidation controlling method. The formulation of each
lubricant, therefore, contains antioxidants. These antioxidants are designed to be sacrificial,
meaning they react or oxidize before the remainder of the lubricant (the base oil) to provide
protection.
This protection is the only mechanism saving the lubricant from premature failure. To
develop a lubricant, the chemist should know what types and how much of these
antioxidants to incorporate into the formulation. Anyone monitoring the used fluid's life
expedience should also track these additives.
This article discusses oxidation with respect to the tools used for monitoring this problem.

Table 1. Oxidation Test Conditions

The Steps of Oxidation
The oxidation of a hydrocarbon fluid involves three basic steps: initiation, propagation and
termination.
With these steps in mind, oxidation can be managed through the control of one or more of
its steps or phases. This is achieved by limiting the source of oxygen (the initiation),
shortening the number of reaction cycles (the propagation) or adding alternate stopping
methods (increasing termination). To some extent, all of these methods are employed in the
lubricant formulation. The initiation starts the process, and preventing oxygen is the first line
of defense.
Understanding what is causing the propagation steps can also enable the decrease of
oxidation. The termination step stops the cycle. Antioxidants are used to break into this
propagation and form radicals that are stable, thus halting the cycle. One of the most
effective testing methods for understanding the health of the fluid is to be aware of the
health of these antioxidants.

Figure 1. Oxidation Analyses from Sequence Testing

Temperature
Heat is often employed to accelerate the oxidation process because temperature has two
effects on any reaction. The first effect involves activation energy. If the system does not
contain enough energy to push the reaction over the threshold, nothing will happen. The
second effect is related to the speed of the reaction. A reaction (oxidation) will
approximately double in rate for every 10°C (18°F) increase in temperature. Which means
that the oil life will be reduced by one-half for every 10°C (18°F) increase in temperature.
Tests are often developed to study the fluid's oxidation that has resulted with an increase in
temperature or an addition of a catalyst. For convenience, these modifications of "real life"
are used to conduct a test in a shorter time frame.
The application of these methods is often useful; however, the resulting data should always
be carefully studied because it may not agree with the fluid's behavior in real-life
applications. Additional reaction pathways can become the major pathway and mislead the
researcher.

Analysis
Although most lubricants are formulated with antioxidants to control oxidation, the inevitable
breakdown cannot be prevented. For this reason, many tests have been developed to
evaluate the oxidation state of the lubricant. Some of these tests study the potential lifetime
of the lubricant while others look at the results of oxidation.

Oxidation Reserve
When an oil formulation is designed, a series of tests is required for this formulation to
meet. Regardless of the formulation's ultimate application, the test series always includes
several oxidation tests. The oxidation test requirement (time, temperature, catalyst,
atmosphere and interpretation methods) is designed around the lubricant's application.
In most cases, the remaining oxidation reserve is measured by testing the lubricant's
behavior under an oxidation experiment. For example, rotary pressure vessel oxidation test
- RPVOT (D2272), universal oxidation test (D6514), turbine oil stability test - TOST (D943),
universal oxidation test (D5846) and pressure differential scanning calorimetry - PDSC
(D6186) are used to study the oxidation potential of a turbine oil.
The tests differ in the reaction temperature or concentration of oxygen. A lubricant is often
measured by several of these tests to assess the temperature effects of the lubricant.1
Because a lubricant is operating in multiple temperature zones, testing at different
temperatures provides a better assessment of the lubricant's overall quality.
 Figure 2. FTIR Spectra of an Engine Sequence Test

Test Methods
Except for the PDSC and RPVOT, the resulting oxidized lubricant from the above test is
also evaluated by another oxidation consumption or property test method. The oxidized
lubricants are analyzed by tests including base number, AN, FTIR oxidation or viscosity
change. This evaluation further indicates the lubricant's oxidation state.
In the automotive sector, crankcase lubricants are subjected to engine tests (D4485)
designed to cause severe oxidation, forcing the lubricant to easily oxidize in a short time.
The resultant used oil is measured for BN, AN, FTIR-oxidation and viscosity to determine
speed and amount of oxidation. These engine tests are analogous to the actual use that the
lubricant could be subjected to in the field, but at a shorted interval.
Figure 1 shows an example from one of these test studies. The effects of the acids reacting
to lower the base reserve, BN, are clear, while the oxidation cannot immediately be
observed in the FTIR or viscosity regions.

Oxidation Profile
These results are common when trending the lubricant's oxidation profile. As oxidation
occurs to the lubricant, it depletes the antioxidants and produces carboxylic acids. The base
reserve will neutralize these oxidation-produced acids to carboxylate salts; thus, resulting in
a depletion of the base reserve. As previously discussed, many of the esterification and
condensation reactions that produce viscosity increases are acid catalyzed.
The base reserve will help prevent this chain growth and viscosity problem. Therefore, in
addition to the corrosion problems of the acid components, it is important to prevent BN
from getting too low or AN too high. The oxidation reaction produces esters and carboxylate
salts (from the base reserve neutralization); however, carboxylate salts are not being
measured by the oxidation analyses2 even though it is an oxidation product.
Figure 2 shows how oxidation is progressing in this complex experiment. The lowest plot
(line) in the figure was generated on an oil sample early in the test. Successively higher
lines are generated from additional oil samples taken during the test.
In Figure 2, the acids can be observed at 1,715 cm-1, while nitrate oxidation is at 1,631 cm-
1 and carboxylate salts at 1,555 cm-1. All the components in the 1,800 to 1,500 cm-1 range
are oxidation-related components.

Figure 3. LSV (D6971) of New and Used Turbine Oil

Protection
The majority of analytical tests that measure oxidation protection measure the amount of
oxidation that has occurred to the lubricant. The Linear Scanning Voltammetry (LSV)
(D6971) and FTIR are two tests capable of measuring the concentration of the antioxidant
additive(s) present in the oil to control oxidation.
The LSV is an application of linear sweep voltammetry (LSV), which utilizes a sweep
voltage to measure both amine and phenolic antioxidants (Figure 3). When calibrated
against the new oil, the remaining antioxidant concentration can be determined to estimate
the lubricant's remaining oxidative life.
Similar information can be obtained from FTIR. As shown in Figure 4, the phenolic and
amine antioxidants are visible in the FTIR spectrum. Like LSV, the peak area of the FTIR
spectrum can be used to quantitate the antioxidant's concentration.
The remaining lifetime of the lubricant obtained from both FTIR and LSV can be expressed
only as a percentage of the new oil life. It can be related to the number of hours of oil life
remaining only if the historic life of the oil is known in hours and the application's conditions
have remained stable. For systems like turbine oils that have controlled operations, there
can be established contaminations limits for the percentage useful life.

Figure 4. FTIR Spectrum Showing Antioxidants

Oxidation Progress
A common method for studying oxidation is to trend its progression. Oxidation results can
be followed by measuring the increase in the acid number of the fluid (or the loss in base
number in engine oils caused by the formation of acids), viscosity (caused by the formation
of condensation products), FTIR carbonyl oxidation (the ketones, aldehydes, esters and
acids formed form the oxidation reactions) and insoluble products.
Although certain tests like the Pentane/Toluene Insolubles D893 measure both hard and
soft insolubles, applying tests like Pentane Insolubles by Membrane Filtration D4055,
QSAsm3 or the filter paper Blotter Spot Test can also follow the amount of oxidation
products. In the case of oxidation, measuring the formation of condensation products that
are insoluble in the fluid is tracking or monitoring the oxidation.
Performing these different methods and following the results can provide an understanding
of the root cause and mechanism of oxidation. For example, if oxidation occurs at low
temperature, significant FTIR oxidation and a small amount of insoluble products will be
apparent.
On the other hand, high temperatures can cause condensation reactions and increase
insoluble products. Many thermal-cracking processes (like microdieseling or combustion)
will promote oxidation, but will also produce nitrates that can be observed through FTIR
nitration as a flag of the process.
Other less widely utilized tests have been used to measure oxidation. The most promising
of these methods employs the measurement of the electrical polarity or permittivity of the
fluid.5, 6 Both the real and imaginary parts of the impedance measurement contains
information about the fluid.
The real parts of the impedance, the conductivity, and the imaginary part, the permittivity or
dielectric coefficient, are both affected by the change in polarity of the fluid. Oxidation is a
major source of this change in lubricant polarity. Therefore, new sensor technologies are
emerging that utilize these resistance-related measurements to assess the oil quality, in
many cases as a real- time measurement.
Although oxidation has been studied for more than 140 years, it remains to be fully
understood. Fluid chemistry, reaction temperature and reaction conditions are varied in
testing experiments in an attempt to predict the in-service behavior of the lubricant.
Tests have been designed to measure oxidation reserve (the amount of protection
remaining) and oxidation progress (the amount of oxidation that has occurred). Both testing
methods have their advantages, and the effectiveness of these tests depends on the
operation of the in-service fluid. The better that a test can measure what is occurring, the
more information is available concerning the life of the fluid.
Understanding how the fluid is handling the oxidation problem can enhance the attempt in
correcting this root cause of fluid failures. The lubricant chemist should be aware of the
measuring tools available and what they may indicate. Therefore, one can address and
potentially reduce this source of fluid failure.
References
1. V. Gatto, W. Moehle, T. Cobb and E. Schneller. "Oxidation Fundamentals and Its
Application to Turbine Oil Testing." ASTM Symposium on Oxidation and Testing of Turbine
Oils. December 5, 2005, Norfolk, Virginia.
2. Annual Book of ASTM Standards. "E2412." American Society for Testing and Materials.
West Conshohocken, Penn., 2000.
3. QSAsm is a registered service mark of Analysts Inc. (www.Analystsinc.com).
4. G. Trujillo. "The Blotter Spot Method." Practicing Oil Analysis magazine, July-August,
2003.
5. C. Koehler, D. Wooton, D. Sosnowski and R. Hirthe. "Fluid Condition Monitoring Using
Broad Spectrum Impedance Spectroscopy." U.S. Patent Application 20050110503.
6. C. Collister. "Electrical Measurement of Oil Quality." U.S. Patent 6,459,995.

The Importance of Lubricant Film

Strength
Bennett Fitch, Noria Corporation
Film strength is one of the most critical lubricant properties for protecting a machine’s
internal components from wear and degradation. It is heavily influenced by the lubricant’s
base stock and additives. This article will discuss the importance of a lubricant’s film
strength and what impacts its effectiveness.

Film Thickness
When you think of lubrication, what comes to mind? It might be the base oil creating a film
thickness to separate two metal surfaces. After all, the primary intent is to avoid metal-on-
metal surface contact. For the base oil to provide separation in this situation, there must be
a balance of three contributing factors: the relative velocities, the base oil viscosity and the
amount of load.
These three factors are also influenced by other elements such as temperature and
contamination. When the film thickness is the result of a balance between these factors, it is
called hydrodynamic lubrication.
In applications with rolling contact (and thus negligible relative sliding motion), film thickness
between the metal surfaces can still occur, even with greater localized pressure points. In
fact, these pressure points play an important role.
The base oil’s pressure-viscosity relationship allows the oil’s viscosity to increase
temporarily due to the higher pressures. This is called elastohydrodynamic lubrication. A full
film separation remains, albeit a very thin one.
In practice, it is best to keep machine surfaces separated, with the film thickness providing
the best opportunity for reduced friction and wear. But what happens if these film thickness
conditions are not met, such as when there is insufficient relative velocity, inadequate
viscosity or too much load?
Most machine designs and operating parameters will require instances when insufficient
velocity exists, such as starts and stops or changes in directional motion. There may also
be concerns when the temperature increases too much, causing the viscosity to decrease,
or excessive contamination contributes to abrasive contact in the film gap.
When the hydrodynamic or elastohydrodynamic lubrication prerequisites are not met,
the base oil will require support during what is called boundary contact conditions. This
support involves wear and friction-control additives.
The base oil and additives are carefully blended together to produce the specific lubricant
product (either oil or grease), which is formulated to mitigate the anticipated boundary
conditions. The lubricant then possesses film strength and boundary lubrication properties.

Boundary lubrication

Film Strength
Film strength can be described as the lubricant’s ability to lessen the effects of friction and
control wear by means other than the film thickness. As mentioned, the viscosity is the
primary contributor to film thickness during hydrodynamic and elastohydrodynamic
lubrication.
When the base oil viscosity is insufficient to overcome metal-to-metal surface contact, the
base oil and additive chemistry work together to create a surface protection mechanism.
During these boundary conditions, boundary lubrication is also influenced by the chemical
and physical properties of the mechanical surfaces and any contributing environmental
factors.
Even when loads and temperatures are higher and relative surface velocities are lower, the
film strength is improved.

Unlubricated Surface Interactions

If you were to observe contacting mechanical surfaces on a molecular level, you would see
that they can be relatively rough, even if they are machined to be very smooth and appear
that way to the unaided eye. This could be compared to how the earth looks like a perfect
sphere from the perspective of an astronaut in space but is brimming with mountains and
valleys of all heights and depths when viewed by someone standing on the earth’s surface.
This is relevant because when two unlubricated metal surfaces come in contact, the actual
contact area will be substantially less than the apparent contact area. The surfaces will only
come in contact where these “microscopic mountains” called asperities are the tallest and
reach to the other surface, preventing lower asperities from making contact.
These asperity surfaces can then elastically deform based on the corresponding shear
strength of the metals. Thus, the real contact area will increase proportionally with an
increase in load because the initial contact points will elastically deform first and more
contact points will connect.

Friction
Friction, the resistance to sliding motion of interacting surfaces, is subject to several
influencing parameters or processes. Most people consider the roughness of the surface as
the primary contributing parameter for friction.
However, when considering that the real contact area may be less than 1 percent that of the
apparent contact area, the actual roughness becomes much less relevant. The significant
process contributing to friction is a result of the adhesive bonds occurring at the atomic level
of asperity contact.

Wear Generation
In conditions where there is inadequate lubricant film thickness between the metal surfaces,
the asperity contact points can lead to cold welding, which is the prerequisite for adhesive
wear. The adhesion at these asperity points undergoes a work-hardening process, which
strengthens the material.
Thus, the shear point happens at layers below the asperity contact point where the metal
has not been strengthened. As the metal shears, the asperity tip is then either transferred to
the other surface or broken off as an abrasive particle.
Adhesion is often seen as the initial form of mechanical wear, but as abrasive particles
present themselves (either from wear or from an external source), abrasive wear can
become more destructive. This form of abrasion is called three-body abrasion, whereas
two-body abrasion is caused by cutting or gouging of sharp surface contact points.
During rolling contact, surface fatigue can occur. Fatigue mechanisms stem from cracks
propagated at the surfaces or up from layers under the surface that contain inclusions or
other impurities. The high stresses from rolling conditions at these surfaces will lead to
fatigue wear.

Mitigating Surface Interactions

Friction and wear-control additives are formulated in small quantities within the base oil and
have polar properties that foster metal surface attraction. These attractions are then further
encouraged to chemically react with the surface as a result of the interacting conditions,
which are inversely associated to the conditions leading to sufficient film thickness: higher
pressure and higher temperature.
When machine surfaces interact with higher pressures and temperatures, the additives
mitigate the typical effects of metal-to-metal contact (wear) by creating initial molecular
layers on the machine surface that are more ductile. These friction-control layers directly
reduce the shear strength during contact and become sacrificial.
The initial layers can mitigate friction by allowing the lubricant’s weaker molecular bonds to
release with less force compared to that of the strong bonds that result from the metal-to-
metal asperity boundary conditions. The formation of low-shear-strength films is also
influenced by the base stock type and the metallurgy of the mechanical surfaces.
There are three types of lubricant additives that help reduce this friction and control wear
formation: friction modifiers, anti-wear additives and extreme-pressure additives.

Friction Modifiers (Lubricity or Oiliness

Agents)
Polar compounds, such as a fatty acid added to the base oil, decrease friction at low sliding
speeds by forming a soap film. They typically are used in components that are sensitive to
fuel economy to reduce friction and stick-slip at low speeds, such as in an engine or
transmission.
They act like anti-wear additives but are more effective with lighter loads and do not require
high temperatures. The resulting low-shear-strength soap breaks down at higher
temperatures. However, when the surface metal is more reactive to the fatty acid, creating a
metal soap, the breakdown temperature is higher.

Anti-wear Additives
These polar compounds are typically sulfur- or phosphorus-based, such as a zinc
dialkyldithiophosphate (ZDDP) type of additive. They are designed to chemically react with
the metal surface only at boundary conditions.
However, anti-wear additives are more effective at higher temperatures, where they
become more activated and create a barrier film. ZDDP-type additives have been widely
used for wear protection and are also beneficial as antioxidants in the oil.

Extreme-pressure Additives (Anti-scuff

Additives)
Friction modifiers and even anti-wear additives become less useful and break down when
surface temperatures get too high. Extreme-pressure additives, which are also sulfur- and
phosphorus-based, are the best choice when high surface temperatures are expected.
These additives form a low-shear-strength, soap-like film with metal surface reactions and
can withstand fairly high temperatures. While the reaction is beneficial for the film to be
developed, it is important to take caution when the reaction has the potential to result in
chemical corrosion of more reactive metals.

Physics and Chemistry

The physical molecular interactions of asperities at the actual contact pressure points are
the main concern when unlubricated or poorly lubricated machine surfaces come into sliding
contact. At this molecular scale of the machine surfaces, boundary conditions are subject to
numerous principles of physics and chemistry.
The role of oxidation, corrosion, chemisorption and other chemical reactions at the machine
surfaces must be carefully balanced when additive compounds are selected for film strength
protection.
These friction and wear-control additive films on the metal surfaces reduce the shear
strength at the contact points. The low-shear-strength films are sacrificial during physical
interactions and protect the surface from the effects of adhesive, abrasive and fatigue wear.
These submicron films have a gradation of liquid to solid properties as they get closer to the
metal surface. While the base oil is preferred to protect the machine surfaces with
hydrodynamic and elastohydrodynamic lubrication, boundary conditions will exist.
Therefore, to protect against boundary conditions, a properly formulated lubricant with
friction and wear-control additives should be used to provide a film strength that is
proportional to the exhibiting mechanical interactions within reasonable limitations.

References
Fitch, E.C. (1992). “Proactive Maintenance for Mechanical Systems.”
Fitch, J.C., Scott, R., & Leugner, L. (2012). “The Practical Handbook of Machinery
Lubrication - Fourth Edition.”
Fein, R.S. (1991). “Lubrication Engineering.” Journal of the Society of Tribologists and
Lubrication Engineers.
Fein, R.S. (1997). “Boundary Lubrication Relations.” Tribology Data Handbook.
Rabinowicz, E. (2014). “Friction.” Access Science.
Mortier, R.M., Fox, M.F., & Orszulik, S.T. (2010). “Chemistry and Technology of Lubricants -
3rd Edition.”
Rigney, D.A. (1980). “Fundamentals of Friction and Wear of Materials.” ASM