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Grease
additives:
Important contributors
not to be overlooked
28 Basics of MWFs: Register for Metalworking Fluid Management Certifi cate Course,
This article focuses on the variety Table 1 | Additives Performing in the Bulk of the Grease
of additive types available to grease
Antioxidants Extend the life of the lubricant by inhibiting oxida-
formulators and how to use them
tion, thus minimizing base oil thickening, sludging and
properly.
deposits.
To seek a broad range of opinions,
TLT interviewed the following eight Scavengers Chosen to react with undesirable contaminants such
as acids or sulfur to render them less harmful.
industry experts:
Evaluation of
greatly prolong the onset of molecular
ZnDTP with various
ZnDTP with various
Moment of the bearing
30,00
Alcohol chain length degradation of the lubricant.”
Conditions:
Dan Vargo, senior research chemist
25,00
Treat Level: 3%‐wt.
Bearing: 7312B 536050 Hi09 with
Bearing: 7312B.536050.Hi09 with
for Functional Products Inc., in Mace-
Friction M
brass cage
Axial load Fa: 80 KN donia, Ohio, discusses the use of water
20,00 duration: 500h
Temperature: room temperature spray-off and shear stability improvers
speed: 7,5rpm
in greases. He says, “Usually, these ad-
15,00
0,00 50,00 100,00 150,00 200,00 250,00 300,00 350,00 400,00 450,00 500,00 ditives are polymers that form an in-
running time (h)
terpenetrating physical (sometime
chemical) network with soap thicken-
Figure 1 | Variations within an additive group such as ZDDP can influence performance, as ers that improves the stay-in-place
shown in this FAG-FE8 test. (Courtesy of Rhein Chemie Rheinau GmbH) ‘tackiness’ of a grease. The polymers
greatly improve water resistance and
and the type of alcohol (primary, sec- Specialist), technical fellow and indus- water spray-off/washout performance
ondary) utilized in its manufacture. trial technology manager for The Lu- (see Figure 2).”
Sulfurized isobutylene (SIB) and poly- brizol Corp. in Wickliffe, Ohio, indi-
sulfides are good sources of active sul- cates that there are about 12 different 3D nETWoRk
fur that are particularly effective at of- chemistries used as rust inhibitors. He All the respondents indicate that the
fering protection under boundary says, “Sulfonates work well in normal three-dimensional nature of grease has
lubrication conditions.” water.” an effect on the ability of additives to
In differentiating the performance Dr. Fish also discusses specific fulfill their functions. Bessette says,
of ZDDP chains, the frictional behavior types of antioxidants and metal deacti- “Effective tribochemistry involves
of roller bearings is measured by the vators used. He says, “Aminic and chemical reactivity and mobility. Since
FAG-FE8 test. Janeda says, “This spe- phenolic antioxidants are used either the rheology of the grease is assumed
cial performance test was developed by as single components or in combina- to be a factor, grease formulators usu-
an OEM. The results shown demon- tions. Triazole and mercaptothiadia- ally circumvent the problem by in-
strate that variations within the same zole additives are used in metal deacti- creasing the concentration of additives
additive group can have a significant vators to reduce yellow metal used in greases.”
impact on performance (see Figure 1).” corrosion.” Vargo indicates that the three-di-
Kaperick indicates that there are STLE-member Paul Bessette, presi- mensional grease network can physi-
also ashless antiwear and EP options dent of TriboScience & Engineering cally trap additive molecules and can
available. He adds, “For corrosion pro- Inc., in Dartmouth, Mass., comments be especially effective in preventing
tection, imidazoline componentry is
often used as an effective inhibitor
with low-molecular weight succinates.
Amine phosphates also can be very
useful in preventing corrosion in the Add polymer
presence of saltwater, while low total
base number (TBN) calcium sulfo- Heating Mix Cool down
nates are often successful in protecting
metal surfaces under salt fog condi-
tions.”
Soap thickener Network
Other ashless corrosion inhibitors
network dissociation Interpenetrating
include amine sulfonates, alkenylsuc- networks
cinimides and oleoyl sarcosine. A past
Soap thickener
study compares the performance of
Polymer
ash-producing versus ashless corro-
sion inhibitors.2
STLE-member Dr. Gareth Fish Figure 2 | Polymers can form an interpenetrating network with soap thickeners that improves
(Certified Lubrication Specialist and tackiness, water resistance and water spray-off or washout performance. (Courtesy of Func-
NLGI Certified Lubricating Grease tional Products, Inc.)
Just for laughs: 2.4 statute miles of intravenous surgical tubing at Yale University Hospital = 1 IV League. 31
ener used is compatible with the addi-
tives selected to boost grease
performance. Coe says, “The additive ‘Antioxidants do not prevent oxidation under the combined
types and dosages must be optimized
to work with the given thickener sys-
ravages of heat and oxygen, but they greatly prolong the
tem, not vice versa.” onset of molecular degradation of the lubricant.’
Kaperick points out that formula-
tors can change the thickener to im- –Paul Bessette, TriboScience & Engineering Inc.
prove specific grease properties such
as oxidation. He says, “Use of metallic
soap thickeners can act as a catalyst for
oxidation, so the use of alternative without excessive churning is another oil adjustment and cool-down stage.”
thickeners can prolong the oxidative way to reduce the effect.”
stability of a grease formulation and Bessette states that processing of the gREASE PRoPERTiES
increase the effectiveness of its anti- grease is very important in minimizing Kaperick states that the first objective
oxidant system.” thickener problems. “Mill, homogenize for the formulator is to use additives
Besides increasing the additive or filter the final product in order to re- that will not harm the grease. He says,
treat rate, Kaperick indicates that duce or eliminate thickener agglomer- “The physician’s aphorism primum, non
changing the polarity of the thickener ates,” Bessette says. “An excellent nocere—first, do no harm—is an apt
may help. He says, “Reducing the po- method to determine the deagglomera- guideline for the use of additives in
larity of the thickener system, while tion of the thickener in the oil is FT-IR grease formulations with respect to the
often impractical, would lessen the analysis. Lithium 12-hydroxystearate structural stability of the thickener sys-
negative impact on additive perfor- has a prominent absorption band at tem. Aggressive additives can soften a
mance.” 1579 cm.-1 The intensity of that band grease and destroy its ability to act as a
Zhang goes further by indicating increases as a function of the dispersion lubricant in the intended application.”
that nonpolar thickeners can be used. of the thickener. When the intensity of A number of different additive types
He says, “It is known that nonpolar the 1579 cm-1 remains constant, no ad- can cause grease problems, according
thickener systems such as certain ditional milling is required.” to Dr. Fish. He says, “Some additives
types of polyolefins will have little or Dr. Fish indicates that the degree of can have an effect on the physical
almost no interaction with additive alkalinity built into the thickener has properties of greases. Dropping point
systems.” an effect on additive performance. enhancers improve the thermal stabili-
Hunter states that additive effec- “Highly basic thickener components ty of greases and increase their drop-
tiveness is due in part to whether the can react with additives and neutralize ping points, but others have been
application is in motion or static. “An- their effectiveness. This can be an is- shown to cause a significant reduction
tiwear and EP additives do their func- sue with gelled overbased calcium sul- in dropping points in both complex-
tion when the part is in motion, allow- fonate greases. It is also important and urea-thickened greases.”
ing transport and wetting. Corrosion when making soap-thickened greases Odor also can be an issue in using
inhibitors, on the other hand, have a that the amount of free alkalinity is extreme pressure additives. Dr. Fish
significant role when the grease is stat- within tightly controlled bands,” Dr. continues, “Most high-sulfur, content
ic,” Hunter says. “All of the grease cor- Fish says. “In lithium greases, too additives emit sulfurous species. With
rosion tests include some time in the much free lithium hydroxide can in- all of these effects, treating the grease
static condition, and the treat rate of terfere with additive components and with the right level of additive or se-
the rust inhibitor necessary to provide impact their ability to function. How- lecting additives to carefully match
the desired performance may be 10 ever, a reasonable excess of lithium hy- thickeners is part of the skilled formu-
times the level required where contin- droxide has been shown to increase lator’s armory.”
ued wetting of the additive occurs.” grease life in accelerated component Another potential concern is the
Zhang also points out that chang- tests.” use of a specific additive to improve a
ing the physical properties of the Beyond compatibility, Vargo con- particular property can lead to prob-
thickener system can improve additive tends that the procedure used to pro- lems in a second area. Coe explains,
effectiveness. He says, “Use of a softer duce the grease is important. He says, “When too much or the wrong type of
or semifluid grease can reduce the “To get optimum performance from ad- polymer is utilized to improve oil
blocking or hindering effect on addi- ditives and to lessen the chance that ad- bleed, mechanical stability or water re-
tive migration from bulk to metal sur- ditives will react with the thickener, it is sistance, the result is that low-temper-
faces. Suitable mechanical design that best to add them at the end of the soap- ature performance, particularly pump-
will promote enough grease agitation making process, usually during the final ability, is reduced.”
34 Tribo-dictionary: Thixotropy – The tendency of grease or other material to soften or flow when subjected to shearing action.
17%,” Vargo says. “By adding 1% of an
ethylene/propylene copolymer into a
mineral oil-based grease, the weight
loss percentage decreased from 73% to
15%. The water resistance improve-
ment is due to the formation of inter-
penetration networks by the polymer
and the soap thickener. The polymer
networks can be formed by several
ways such as the physical crosslinking
via crystalline phase, hydrogen bond-
ing or chain entanglement.”
Kaperick believes that two key
grease problems addressed by additives
are fretting wear and corrosion. He
says, “Fretting wear has been shown to
respond positively to phosphorus-
based antiwear components, especially Figure 5 | Fretting wear reduction as a function of the concentration of an amine sulfurized
in more lightly-loaded applications or phosphite in a fully formulated aluminum grease is shown. (Courtesy of Afton Chemical Corp.)
those that might be accurately modeled
by the Fafnir Fretting tester.”
To illustrate this point, Figure 5 re- are a number of different polymer types EVALuATion TESTS
veals data generated by the Fafnir that retard this effect.” “Although some methods used to evalu-
Fretting tester (ASTM D4170) that Zhang indicates that there is an ad- ate greases are similar to those used in
shows a reduction in wear as the per- ditive that will affect the dropping testing fluid lubricants (e.g., EMCOR
centage of an amine-sulfurized phos- point of a grease. He says, “A certain corrosion, 4-ball wear/weld, Timken),
phite is increased. The relationship ap- boron ester can complex with the many are unique to the study of greases
pears to be linear in nature for the thickener soap structure to further in- and are employed to assess such proper-
aluminum complex grease tested. crease the dropping point of or the ties as consistency, oil separation, pump-
Corrosion problems are difficult to consistency of a grease.” ability and high- or low-temperature
correct with additives because they are Janeda points out the problem that performance,” Kaperick says. “Evalua-
very dependent on the application. can occur if a highly active sulfur car- tion of the importance of tests is a matter
Kaperick says, “Often the final solu- rier is used to provide EP performance. of opinion which can vary widely, espe-
tion is not a single additive, but a syn- She says, “These additives can cause cially between those with a bent toward
ergistic combination of componentry copper corrosion, wear and can also fundamental research and those who
that is more effective than a single in- negatively influence stability. Long- need to meet specifications set by cus-
hibitor.” term copper corrosion, even at higher tomers or equipment builders.”
This point is illustrated by showing temperatures, often cannot be con- He continues, “For evaluation of
results from a corrosion study on a trolled by additional dosage of a yel- friction and wear under a variety of
fully formulated lithium grease. The low metal deactivator.” conditions (temperature, load, speed,
study used the standard industry test
known as the EMCOR corrosion
method (ASTM D6138). The results
shown in Table 3 indicate that a com-
bination of a succinimide with a suc-
cinate ester and an imidazoline pro-
vide better performance than either an
amine phosphate or the succinimide
or a combination of the two.
Polymers also can be used to control
the release of oil from the grease, which
is known as bleed control. Coe says, “If
a grease bleeds too much oil, it can dry Table 3 | A synergistic combination of additives such as the corrosion inhibitors shown in this
out, leaving mostly thickener behind, study often provide more effective performance than a single additive. (Courtesy of Afton
which can cause many problems. There Chemical Corp.)
2139 High Tech Road • State College • PA • 16803 814-353-8000 • 800-676-6232 • Fax 814-353-8007
cannon@cannoninstrument.com • www.cannoninstrument.com
38 Science quiz: Name the scientist who first discovered that the earth revolves round the sun?
(Copernicus)