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Gabi Nehme
To cite this article: Gabi Nehme (2013) The Importance of Variable Speeds under Extreme
Pressure Loading in Molybdenum Disulfide Greases Using Four-Ball Wear Tests, Tribology
Transactions, 56:6, 977-985, DOI: 10.1080/10402004.2013.816812
There is recent concern regarding grease behavior in ex- (petroleum oil, synthetic or vegetable oils), thickener (soaps, or-
treme pressure applications. The research described here is ganic or inorganic nonsoap thickeners), and additives to enhance
aimed at providing good friction and wear performance while the performance and protect the grease and lubricant surfaces.
optimizing rotational speeds under extreme loading conditions. The additives in greases have been in use over the years to
A design of experiment (DOE) was used to analyze molybde- achieve antiwear and load bearing capacity, to varying degrees of
success. Chief among them are MoS2 and graphite (Gansheimer
num disulfide (MoS2 ) greases and their importance in reduc-
and Holinski (1); Misty and Bradbury (2); Tamashuasky (3)) for
ing wear under extreme loading and various speeds conditions
extreme pressure applications.
(schedule 1 and schedule 2 speeds). The lamellar structure of
In previous studies, different rotational speeds and extreme
MoS2 provides very good weld protection by forming a layer pressure loading were studied by Nehme and Dib (4) and Nehme
that can be easily sheared under the applications of extreme (5), (6) using fully formulated oils and plain zinc dialkyldithio-
pressures. An extreme load of 785 N was used in conjunction phosphate oils. It has been found that varying sliding speeds
with different schedules of various rotational speeds to exam- and contact loads will affect the tribofilm formation and addi-
ine lithium-based grease with and without MoS2 for an equal tive interactions. A substantial effort was devoted to understand-
number of revolutions. A four-ball wear tester was utilized to ing these interactions by using a design of experiment (DOE)
run a large number of experiments randomly selected by the software model. The model was used to optimize several factors
DOE software. The grease was heated to 75◦ C and the wear and responses for specific ranges of loads and rotational speeds.
scar diameters were collected at the end of each test. Previous studies showed that bearing damage by electrical wear
has negative effects on deterioration of lubricating greases
The results indicated that wear was largely dependent on
(Komatsuzaki, et al. (7)). More recent studies reported that the
the speed condition under extreme pressure loading, and thus a
amount of MoS2 in a grease at low test loads and different vari-
lower MoS2 concentration is needed to improve the wear resis-
able loading conditions resulted in increased wear scars, indicat-
tance of lithium-based greases. The response surface diagram ing that MoS2 may actually behave abrasively and at extreme
showed that the developed molybdenum disulfide greases ex- pressure conditions it helps increase the load wear index and the
hibited both extreme pressure as well as good wear properties weld load (Aswath, et al. (8); Patel, et al. (9); Fusaro (10); Nehme
under various rotational speeds when compared to steady-state (11)). The load wear index determines the load-bearing proper-
speed. It is believed that MoS2 greases under schedule 1 speeds ties of lubricating greases according to the ASTM designation
perform better and provide an antiwear film that can resist ex- D2596-97; one steel ball was rotated against three stationary steel
treme pressure loadings. balls. The weld test, on the other hand, ascertains the lowest ap-
plied load at which the sliding surfaces seize and weld together.
KEY WORDS Analysis of the performance of molybdenum compounds in mo-
tor vehicles and their reactions with water and sulfur were exten-
Lithium-Based Grease; Wear; Extreme Load; Cyclic Frequen-
sively studied and were found to be of great importance in the
cies; Aircraft-Grade Bearing
enhancement of antiwear resistance films (Norton and Cannon
(12); Scott, et al. (13); Braithwaite and Greene (14)).
INTRODUCTION
According to Gow (15), some 90% of all lubricant additives
Lithium-based greases make up over 50% of the greases used destroy the thickener structure of greases because they are of-
in the industry today. Grease are mixtures of fluid lubricant ten based on surface-active materials and this leads to what is
commonly called the mayonnaise effect (softening and discolor-
Manuscript received February 5, 2013
Manuscript accepted June 14, 2013 ing). He also mentions that of the remaining 10%, some 90%
Review led by Robert Errichello do not work. He ascribes this to the fact that the thickener
977
978 G. NEHME
material is almost always very polar (metallic soaps) and that the r Schedule 1: 2,400 rpm, 1.875 min; 1,800 rpm, 2.5 min;
(also polar) extreme pressure (EP) additives will adhere to the 1,200 rpm, 3.75 min; 600 rpm, 7.5 min; 2,400 rpm, 1.875 min;
soap structure rather than to the metal surface (Gow (16)). This 1,800 rpm, 2.5 min; 1,200 rpm, 3.75 min; 600 rpm, 7.5 min.
is in contradiction to the results found by McClintock (17), who Each rotational speed was conducted at equal number of rev-
tested lubricant life of a number of greases and found an increase olutions for a total run of 36,000 revolutions.
in life. Aswath, et al. (18) and Antony, et al. (19) show in an r Schedule 2: 2,400 rpm, 3.75 min; 1,800 rpm, 5 min; 1,200 rpm,
evaluation of high-performance grease that fluorinated additives 7.5 min; 600 rpm, 15 min. Each rotational speed was conducted
and graphite have positive effects on EP pressure and antiwear at equal number of revolutions for a total run of 36,000 revo-
resistance in complex grease formulations. Although leakage of lutions.
grease when additives decrease viscosity can cause problems in
products or manufacturing equipment under extreme pressure This research examined different loads testing using chrome-
operations, few cases investigating the mechanisms and damage plated steel balls (bearing quality) that simulate the conditions
involved have been reported, with the exception of some reports of high-pressure contacts in real applications. The balls are air-
on the behavior, distribution, or deterioration of grease in rolling craft grade E52100. During landings, the aircraft bearings are sub-
bearings (Cann, et al. (20); Lugt (21)). Therefore EP additives jected to shock loads with very rapid acceleration. Most bearings
could contribute greatly to the antiwear performance in roller should be protected from excessive wear and heat by a grease or
bearing applications. lubricant. This research shows that at accelerating frequency and
As a rule of thumb, approximately 30% of the free volume speed, the use of MoS2 greases will enhance the superior resis-
of the bearing should be initially filled with grease (Lugt (21)). tance to scuffing and scoring under an extreme load of 785 N as
It is clear that this is much more than required to provide the indicated by the wear scar data presented in Table 1. Aerospace
bearing with a (fully flooded) lubricant film. In the beginning, ball bearings are not always easily accessible for routine mainte-
excessive grease churning, or grease flow, takes place, which is nance but must perform flawlessly at a variety of speeds. There-
responsible for the high-temperature peak caused by the churn- fore, repeated frequencies and different speeds were used in
ing component of the friction torque (Lugt (21)). Kaneta, et al. these experiments to check the importance of MoS2 greases in
(22), using a scoop to ensure fully flooded conditions, have shown preventing wear under EP conditions. Nehme (11) worked ex-
that the film thickness is indeed higher than the fully flooded film tensively on previous tests using different DOE combinations
thickness. to check the performance of the grease lubricants with respect
The goal of this study was to examine the influences of two to variable and steady-state speeds. Different rotational speeds
different schedule speed conditions on the wear properties of were studied previously on several oil combinations and proved
lithium-based grease under extreme load and compare them to effective in preventing wear depending on the process and appli-
a steady speed of 1,200 rpm. Essentially, two different schedules cations (Nehme (11); Elsenbaumer, et al. (23)).
were selected after extensive studies with number of rotations
for each. In Schedule 1, the number of rotations at each rota- EXPERIMENTAL PROCEDURE
tional speed is halved so that going through the schedule twice Greases were prepared by weight percentage in batches of
gives a tribological exposure that is seemingly equivalent to go- 200 g using a Kitchen Aid blender (4.5 quart capacity with power
ing through schedule 2 once. rating of 250 W). Lithium-based greases and technical fine-grade
Pressure Loading in Molybdenum Disulfide Greases 979
TABLE 2—PROGRAM SETUP ADJUSTMENTS USING PLINT MACHINE SOFTWARE (TE92) FOR VARIOUS TESTING PROCEDURES
Step Data Specimen
Step Next Loop Time Mode Motor Load Temperature Clutch Counter Speed Drive
Comment No. Step Count (s) (s) Enable (N) (◦ C) Enable Reset (rpm) Enable Test Control Unit
Apply load 1 2 0 CStp+ Disabled 785 20 Disengaged Reset/on 0 Enabled Current time
Wait for 75◦ C 2 3 0 CStp+ Disabled OR 75 Disengaged 0 Enabled Elapsed time Per test
Reset PID 3 4 0 2 Disabled OR OR Engaged 0 Enabled Current step
Run test 4 5 0 900 10 Enable OR OR Engaged 2,400 Enabled Total time Per step
Decrease rpm 5 6 0 CStp+ Enable OR OR Engaged 1,800 Enabled Elapsed time Per step
Reset PID 6 7 0 2 Enable OR OR Engaged 1,800 Enabled Residual time Per step
Run test 7 8 0 450 10 Enable OR OR Engaged 1,800 Enabled Test status
Decrease rpm 8 9 0 CStp+ Enable OR OR Engaged 1,200 Enabled Test file
Reset PID 9 10 0 2 Enable OR OR Engaged 1,200 Enabled Data file
Run test 10 11 0 300 10 Enable OR OR Engaged 1,200 Enabled Data points In step
Decrease rpm 11 12 0 CStp+ Enable OR OR Engaged 600 Enabled Total data
Reset PID 12 13 0 2 Enable OR OR Engaged 600 Enabled
Run test 13 14 0 225 10 Enable OR OR Engaged 600 Enabled Start
Stop motor 14 15 0 10 Disabled OR 0 Disengaged 0 Enabled Stop
MoS2 were mixed together. Lithium-based greases have a higher used in the analyses should be converted into corresponding de-
melting point than calcium-based greases and are very common. sirability functions. The desirability is high when the target values
The sequence of adding MoS2 to the grease and mixing is im- are approached simultaneously. Each target value is linked to its
portant for the final preparation. The mixture was mechanically own desirability function. Therefore, the evaluation of the factors
mixed in the blender for 1 h. Two compositions of this grease with and responses base on the percentage probability vs. effects and
3% MoS2 and without MoS2 were developed. analysis of variance were investigated. The optimized conditions
Tests were carried out at the University of Texas at Arling- were calculated using the desirability value.
ton using a Plint four-ball wear tester (model TE92) according to
the testing procedure D2266 that is implemented by ASTM stan-
RESULTS AND DISCUSSION
dard. Four chromium steel balls of bearing quality and aircraft
grade E52100 were used (Fig. 1). Three steel balls with a 1/2-in. Frictional Events and SEM Analysis of Greases with
diameter were clamped together and covered with grease, and the MoS2 Additives
fourth was clamped in a ball chuck and the load was applied. The Figure 2 shows the frictional events that occur during typical
temperature of the grease was maintained at 75◦ C. A program MoS2 grease tests at extreme loads and the scanning electron im-
was written for each specific condition to adjust for the speed and ages for the repeated various speed schedule tests. It presents the
load according to the specific schedule. The setup of the program consistency of two repeated tests at different schedules by pre-
is provided by the Plint machine software where the operator can senting the friction coefficients as a function of the number of
adjust the components and variables base on the test conditions revolutions. The stable antiwear film formed in schedule 1 at an
shown in Table 2. The wear scar diameters were measured for extreme load of 785 N is responsible for the low friction coeffi-
the four balls and the average diameters were used in the DOE cient. The dominance of the beneficial effects of the tribofilm for
analysis using the response surface diagram software. protection of the surface is very significant in schedule 1 and is
Tests for the different factors considered in the analysis and reflected in the SEM images in Figs. 3c and 3d. The increase in
the measured wear scar averages are presented in Table 1. The friction and some inconsistencies in the repeated tests can be eas-
coefficient of friction and surface temperature of the cylinder as ily identified when using schedule 2, possibly due to the repeated
a function of the number of revolutions or time were measured breakdown of the protective antiwear film, which corresponds
directly using the Plint machine Compend software setup where to the abrasive action of the debris present in the wear track
the data are converted into an Excel file. Some of the data were (Figs. 3a and 3b). The breakdown region of the tribofilm shows
graphed and compared at a later stage and some were used to a rapid increase in the friction coefficient and abrasive wear
compare friction fluctuations for different grease combinations (Fig. 3). The fluctuations of friction coefficients under different
(see Table 1). Posttest analysis such as wear scar diameters of speeds and loading regimes are summarized in Table 1 and clearly
the rotating and fixed balls were measured and examined using indicate the importance of schedule 1 speeds under extreme con-
a JEOL JSM 845 scanning electron microscope (SEM) at the ditions because minor fluctuations were observed. The abrasive
end of each test providing that the test balls are cleaned with wear and protective antiwear film depend greatly on the various
hexane–acetone mixture to remove the debris and grease from speed conditions under an extreme load of 785 N, whereas un-
the surface. The average wear diameter was calculated and input der a load of 392.5 N, the different variable speeds did not vary
into the DOE matrix for analysis. The DOE methodology spans significantly the wearing conditions, as indicated in the average
a wide range of analytical approaches developed for different sit- wear scar data in Table 1. The wear scar diameter did not vary
uations or final targets (Barrentine (24)). A DOE is used when and was approximately the same, especially when using 3% MoS2
multi-objective optimization is sought; all responses and factors additives. On the other hand, the variation was very clear under
980 G. NEHME
Fig. 1—Schematic of the four-ball wear test apparatus showing the continuously rotating ball and the three fixed balls covered with grease in the Plint
model TE92 four-ball wear tester (color figure available online).
an extreme load of 785 N with and without MoS2 additives (Ta- ings. It shows that schedules 1 and 2 performed better when com-
ble 1). Therefore, the analysis was focused on various schedule pared to steady-state speed with more improvement indicated in
speeds under an extreme load of 785 N. schedule 1 because the scanning electron images show wider wear
The overall variation in the repeated tests was less than 12%, track diameters and more abrasive particles in the steady-state
which is insignificant considering the number of deterministic and speed tests. A careful examination of the wear surfaces shown in
nondeterministic variables in a tribological test. The wear scar Fig. 5 indicates that an unstable tribofilm is formed with more
diameters on the balls were measured and the average was used asperity protrusions on the surfaces. These large deformations
to optimize the data using DOE analysis. in the contact region of the steady-state and schedule 2 speed
Figure 4 presents the variation in the friction coefficient for tests cause small cracks on the surface, where wear particles are
two repeated tests at steady-state speed of 1,200 rpm and load formed and an adhesive transfer layer is formed on all balls. In
of 785 N. The repeated frictional events were not as consistent abrasive wear the track is rougher and small metal scraps or de-
as the schedule 1 tests; the friction coefficients and SEM images bris can be seen. Abrasive wear will occur when the protective
(Fig. 5) indicated the importance of schedule speeds when used tribofilm breaks down and the two surfaces are under direct con-
with MoS2 greases in specialty applications such as aircraft bear- tact. As a result, a certain volume of surface material is removed
and abrasive scratches are formed on the weaker surface; in this
case, the tribofilms on the steel surfaces are wearing out. This
corresponds to extreme conditions. Friction events in variable-
speed schedule 1 tests were observed to be smoother and the
plateau region lasted longer when compared to the same events
at 1,200 rpm and schedule 2. It was also clear that schedule 1 ro-
tational speeds played an important role in reducing friction and
wear when compared to all other testing conditions. The stable
antiwear film formed during schedule 1 frequencies is responsible
for the steady-state friction behavior where it is reflected in the
SEM images of the MoS2 grease. The wear scar diameter is very
small compared to schedule 2 frequencies and steady-state fre-
quency under the same loading conditions. The secondary elec-
tron image of the tribofilm is very smooth. In regions where a
stable tribofilm is present the surface roughness is very low; the
images indicate a featureless wear track with minimum abrasive
wear and the presence of a wear-resistant film protecting the sur-
faces. It is more likely that the activation energy resulted from
Fig. 2—Frictional events of lithium-based grease with 3% MoS2 at 785 N
load and schedule 1 and 2 speeds for 36,000 revolutions (color mechanical rubbing and the increase in temperature observed un-
figure available online). der extreme contact were responsible for the self-healing of the
Pressure Loading in Molybdenum Disulfide Greases 981
Fig. 3—Scanning electron microscopy (SEM) images of lithium-based grease with 3% MoS2 at 785 N load and schedule 1 and 2 speeds for 36,000
revolutions (color figure available online).
tribofilm, which can be concluded from Fig. 3 and the secondary dicated a very high degree of repeatability of the tests. Therefore,
electron image in Fig. 5. Extreme contacts and thermal activa- the DOE analysis would be very significant when running analysis
tion energy where tribofilms could results from surface interac- on the MoS2 grease samples.
tions were studied extensively in oils under boundary lubrication
(Gansheimer and Holinski (1); Nehme and Dib (4); Nehme (5);
Aswath, et al. (8)) and similarities could be deduced under these SEM Analysis of Greases without MoS2 Additives
conditions, because variable speeds and extreme load also suggest The effects of 3% MoS2 greases on reducing wear under dif-
the formation of wear-protective films in particular cases (Nehme ferent speeds and different loads are clearly indicated in Table 1.
and Dib (4); Nehme (5)). The data shown for each condition in- There were large increases in wear scar diameter when greases
without MoS2 additives were used. The breakdown of the protec-
tive film in the majority of these tests was due to abrasive wear,
resulting in a rapid increase in friction coefficient and eventual
increase in the wear scars. In most cases the wear scar indicated
that abrasive wear is the mechanism of material removal as ev-
idenced by the deep scratch marks on the surface shown in the
SEM images in Fig. 6. There were also some indications of adhe-
sive wear caused by plastic deformation introduced in the contact
region. At this stage, large deformations caused small cracks on
the surface, where wear particles are shown and adhesive transfer
layers are formed on the balls as reflected in the lower and higher
magnifications images for schedule 1 and 2 speeds.
MoS2 is an extreme pressure additive that is used extensively
in grease. Strong covalent bonding holds the Mo and S together
(Fusaro (10)). Van der Waals bonding and multiple layers can
be sheared easily along the S-S bond, providing physical lubrica-
tion. The particles of MoS2 are sheared and thus prevent the con-
tacting layers from seizing together (Fusaro (10); Nehme (11)).
The severity of the wear and material transfer at extreme load
Fig. 4—Frictional events of lithium-based grease with 3% MoS2 at 785 N
load and 1,200 rpm for 36,000 revolutions (color figure available without MoS2 suggest that no lubrication film protected the
online). metal surfaces and more metal-to-metal contact resulted where
982 G. NEHME
Fig. 5—Scanning electron microscopy (SEM) images of lithium-based grease with 3% MoS2 at 785 N load and 1,200 rpm for 36,000 revolutions: (a) re-
presents test 1 of lithium-based grease mix; (b) represents test 2 of lithium-based grease mix under the same conditions (color figure available
online).
extensive adhesive and abrasive phenomenon were dominant uled speed regimes. The data indicated an improvement in wear
during the test, leading to both higher friction and wear. It ap- in schedule 1 compared to the schedule 2 test regime. The desir-
pears that tribofilms were unstable under extreme loads and were ability, which is based on what is targeted in the model when the
unable to provide protection and were replaced by wear debris responses are evaluated before optimization, supports these find-
and excessive abrasive wear. This indicates that the wear debris ings. The desirability established by the model presents a clear
formed because of pulling of asperities diminished the presence improvement when schedule 1 is used under an extreme load of
of the tribofilm in the absence of MoS2 in that specific lubrication 785 N as reflected in Fig. 7. A concentration of MoS2 less than 3%
regime. or between 2.35 and 3% under schedule 1 variable speeds was suf-
ficient to establish a good desirability of over 88% and the wear
Design of Experiment and Optimization Analysis scar diameter was less than 0.9 mm (Figs. 7a and 7b). The 3D de-
and Discussion sirability study (Fig. 7b) suggests that 2.35% MoS2 is suitable and
Design of experiment is the simultaneous study of several performs the same functions as the 3% MoS2 ; a saddle point in
variables. Table 1 shows the wear scar diameters data for the the 3D desirability study (Fig. 7b) of schedule 1 variable speed
grease blends used in the experiments with and without MoS2 can be seen with a value of 0.881. The presence of MoS2 was
under two different loads (392.5 N, 785 N) and different sched- crucial for all grease tests and its optimum concentration can be
Fig. 6—Scanning electron microscopy (SEM) images of lithium-based grease without MoS2 at different scheduled speeds and 785 N load: (a), (c) schedule
1 speeds at lower and higher magnifications (50 and 2000 ×); (b), (d) schedule 2 speeds at lower and higher magnifications (color figure available
online).
Pressure Loading in Molybdenum Disulfide Greases 983
Fig. 7—(a) Optimization for schedule 1 and 2 variable speeds regarding desirability with respect to MoS2 percentage concentration and variations in load;
(b) 3D desirability study for schedule 1 and 2 variable speeds with respect to MoS2 percentage concentration and variations in load (color figure
available online).
reduced by more than 20% in machinery running at high variable establish a minimum desirability of 42% under an extreme load
speeds and extreme pressure without compromising the forma- condition, as indicated in Figs. 7a and 7b.
tion of a wear-resistant film. Reducing the MoS2 concentration The reduction of MoS2 to 2.35% in lithium-based grease did
is not sufficient when using schedule 2 because the desirability not significantly affect the wear protection in schedule 1. Perhaps
will be reduced significantly. Thus, setting longer time at specific most notable is the great similarity between the 2.35% and the
frequency as in schedule 2 will involve a higher concentration of 3% concentrations when using schedule 1, as evidenced by the
Molybdenum Disulfide grease, and 3% MoS2 will be necessary to disappearance of the large frictional events after a short time
984 G. NEHME
Fig. 9—Response surface diagram and scanning electron micrographs of the wear scar variations for 2.3% MoS2 greases under schedules 1 and 2 at an
extreme load of 785 N (color figure available online).
Pressure Loading in Molybdenum Disulfide Greases 985