Tribology Letters, Vol. 16, No.

4, May 2004 (# 2004) 275

Boundary lubrication performance of free fatty acids in sunflower oil

N.J. Fox, B. Tyrer, and G.W. Stachowiak
Tribology Laboratory, School of Mechanical Engineering, Crawley, Western Australia

Received 14 February 2003; accepted 20 July 2003

Free fatty acids are released over time in vegetable oils, primarily through the hydrolysis of the triglyceride base. In mineral oils,
fatty acids are considered to be one of the classical boundary lubrication additives, but they may not have the same impact in
vegetable oils, due to the vast difference in chemistry between the base oils. The purpose of this study was to evaluate the influence
of free fatty acids on the boundary lubrication performance of sunflower oil, with particular focus on the impact of unsaturation
within the fatty acid and assessing the effect of elevated temperatures. The results obtained suggest stearic acid can effectively
reduce both the wear and friction of sunflower oil formulations under boundary lubrication conditions, although performance is
limited when bulk oil temperatures approach 150 8C.
KEY WORDS: sunflower oil, vegetable oil, fatty acid, boundary lubrication, additives, friction, wear

1. Introduction range of fatty acids used during testing allowed an

assessment of the influence of unsaturation on additive
Vegetable oils continue to be studied as a potential
performance. Selected additives were also examined at
source of environmentally favorable lubricants, but are
elevated temperatures.
limited by low thermal and oxidative stability. Free fatty
acids are one of the many products observed during the
oxidative degradation of vegetable oils [1]. In mineral
oils, fatty acids are considered as one of the classical
boundary lubrication improvers [2,3]. Lubricant beha-
2. Experimental details
viour, however, is dependent on many factors including
surface chemistry, additive combinations and the base 2.1. Preparation of sunflower oil formulations
oil [4]. Will free fatty acids have the same effect on the
A commercially available sunflower oil was selected
boundary lubrication properties when added to vege-
as the base oil for this study, to allow comparisons with
table oils, as compared to mineral oils?
a previous evaluation of the lubrication properties of
The boundary lubrication performance of free fatty
oxidized sunflower oil [1]. Selected properties of the
acids in vegetable oils has been the subject of a number
basestock are displayed in table 1. In the previous work
of previous studies. Cao et al. assessed the lubrication
free fatty acids were observed during the later stages of
properties of rapeseed oil formulations containing
sunflower oil degradation. Stearic acid, oleic acid, and
alcohols, fatty acids and sulfurized fatty acids [5,6].
linoleic acid were selected for testing in this study and
Minami et al. compared the performance of a range of
were chosen to represent fatty acids present in natural
organic compounds, including acids, amine, and thiols,
oils. All three acids contain a chain of 18 carbons, to
in high oleic sunflower oil under a variety of conditions
avoid any influence of chain length on lubricant
[7]. Vizintin and Arnsek tested fatty acids and sulphur-
performance. Stearic acid is fully saturated, containing
phosphorous antiwear additives in rapeseed oil, during
no double bonds. Oleic acid contains one double bond
an evaluation of rapeseed based hydraulic fluids [8]. The
(monounsaturated), located at the 9th carbon. Linoleic
general consensus of the studies was that fatty acids
acid contains two double bond (polyunsaturated)
were the most effective boundary lubrication improvers
located at the 9th and 12th carbons. The cis isomers of
in vegetable oils at low to medium loads.
both oleic acid and linoleic acid were used in this work.
The purpose of this study was to examine how free
Formulations were prepared for each fatty acid over
fatty acids influence the boundary lubrication perfor-
a range of concentrations from 0.5 to 5% by weight. The
mance of sunflower oil. Sunflower oil formulations
only concern during sample preparation was the lack of
containing stearic, oleic and linoleic acid were prepared
miscibility of stearic acid in sunflower oil. At ambient
and evaluated on a reciprocating ball on plate test. The
conditions the stearic acid dropped out of solution. To
combat this, the stearic acid formulations were gently
 To whom correspondence should be addressed. heated and mixed prior to the boundary lubrication
E-mail: gws@shiralee.mech.uwa.edu.au trials.

1023-8883/04/0500–0275/0 # 2004 Plenum Publishing Corporation

276 N.J. Fox et al./Boundary lubrication performance of free fatty acids in sunflower oil
Table 1.
Properties of the sunflower oil basestock.
Fatty acid composition Peroxide value 4 meq/kg
Palmitic, C16:0 5% Free fatty acids 0%
Stearic, C18:0 3.5%
Oleic, C18:1 30% Viscosity, 50 8C 20 cS
Linoleic, C18:2 61% Viscosity, 19 8C 56 cS
2.2. Measurement of boundary lubrication properties
A ball on plate reciprocating wear test rig was used to
evaluate the boundary lubrication properties of the
sunflower oil formulations. Operating conditions were
set up according to the ASTM standard G 133–95 [9].
The ball bearings used in the trial used were 6 mm in
diameter and made from SKF G20 grade carbon
chromium steel. The plate used as a counter sample
was made of mild steel, case hardened via treatment
with carburizing salts to an average hardness of
approximately 700 Vickers.
To ensure that the boundary lubrication regime
existed throughout the trials the entraining surface
velocity was set very low and the applied load kept
high. The stroke of the rig was set at 12 mm and the
revolution speed was set at 100 rpm, resulting in a
velocity of the ball relative to the plate of 0:04 m s 1 : The
6 mm ball was subjected to a total added load of 33.4 N
corresponding to an effective average pressure of
1.4 GPa.
A majority of the oil formulations were tested at a
constant bulk temperature of 50 8C, to avoid any effects
due to fluctuations in ambient conditions. A lubricant
bath was not used; instead enough lubricant to cover the
wear track was applied to the plate and allowed to
Figure 1. Ball wear volumes for reciprocating rig trials of sunflower oil formulations.
equilibrate to the test temperature before beginning the
trial. Later trials were conducted on sunflower oil
formulations containing stearic acid at bulk tempera-
tures of 100 and 150 8C. Temperature was monitored via
thermocouple located near the plate surface.
The rig was kept in motion for 15,000 revolutions,
equating to a sliding distance travelled of 360 m.
Images of the ball bearings were recorded via an
optical microscope following completion of the tests.
Wear scar dimensions were used to calculate an estimate
of ball wear volume. Coefficient of friction values were
periodically recorded throughout the trials. The record-
ing rate was varied throughout the trial to provide
periods of high and low sample rate.
3. Results and discussion
3.1. Effect of unsaturation
The level of unsaturation in the fatty acid additive
had a noticeable effect on the boundary lubrication
performance of the sunflower oil formulations.
3.1.1. Wear
The relationship between the level of unsaturation in
the fatty acid additive and the amount of wear on the
ball is displayed in figure 1. Linoleic acid when added to
sunflower oil did not have any significant effect on wear.
Addition of oleic acid consistently improved the wear
performance, ranging from a 20% reduction in wear at a
concentration of 0.5% by weight, up to a 30%
improvement at a concentration of 5%. Stearic acid,
however, was the most effective additive providing a
90% reduction in wear at a concentrations of 1% by
weight and higher.
 N.J. Fox et al./Boundary lubrication performance of free fatty acids in sunflower oil 277

These results suggest that increasing the level of

unsaturation has a negative influence on the perfor-
mance of fatty acids as boundary wear reducers and are
similar to measurements conducted by Vinzintin and
Arnsek [8]. In their study of the antiwear properties of
fatty acids, oleic (C18:1) and stearic (C18:0) acids
produced similar wear scars, whilst the polyunsaturated
linoleic (C18:2) and linolenic (C18:3) acids produced
significantly higher wear.
The observed trends of additive concentration and
wear are also similar to previous studies. At low
concentrations (0.15%), Vizintin and Arsnek observed
oleic acid had little influence on the wear performance of
rapeseed oil, but at 5% oleic acid wear was significantly
reduced. Cao and Yu observed a very similar trend to
the current study with the addition of palmitic acid in
rapeseed oil. An initially large reduction in wear,
levelled off after addition of around 1 to 1.5% by
weight acid.
The mechanism of boundary lubrication by the
sunflower oil itself may have some impact on the
effectiveness of the different fatty acid additives.
Sunflower oil consists primarily of a triglyceride
structure, with a fatty acid breakdown of approxi-
mately 6% palmitic, 4% stearic, 30% oleic, and 60% Figure 2. 3D representations of the fatty acid additives used in this
linoleic acid. In this triglyceride structure, three fatty study: (a) stearic acid, (b) oleic acid, and (c) linoleic acid.
acids are attached to a glycerol molecule. Under
boundary lubrication conditions, how do triglycerides the molecule to align itself as a straight chain. This
protect the surface? Free fatty acids are suggested to act suggests the stearic acid could be closely packed on the
as boundary additives, by the formation of protective surface, providing a strong protective layer. Both oleic
complexes of the acid with the metal surfaces [10,11]. If acid and linoleic acid, however, contain a double bond.
it is assumed that triglycerides protect the surface in a Addition of a double bond prevents rotation around
similar manner it suggests that the fatty acids are that point and forces a bend in the chain. The chain then
forced from the triglyceride structure to react with the continues on either the same (cis) or opposite side (trans)
surface to provide a boundary lubrication layer. of the double bond. The fatty acids selected in this study
Addition of free fatty acids similar to those already were in the cis form, to represent those that occur
present, would likely have little effect as the only naturally in vegetable oils. The unsaturated acids, in the
improvement would be eliminating the need to remove cis form, can no longer form straight chains and would
the fatty acids from the triglyceride. This could help become more difficult to pack close together, resulting in
explain why the addition of stearic acid, which is a weaker protective layer. In a previous study saturated
present in such a small extent in sunflower oil, had such fats were observed to have very high antiwear properties
a dramatic effect on wear in comparison to both oleic and greatly improved load carrying capacity when
and linoleic acids. compared to both vegetable and mineral oils [14].
The strength of intermolecular interactions may be
another reason for the observed differences in wear
3.1.2. Friction
performance of the fatty acid additives. Fatty acids react
An effective way to evaluate the friction performance
with the surface to form a protective layer. The strength
of the formulations is to examine the friction trace
of this protective film depends heavily on the strength of
throughout the trial. The concept of particular types of
the interactions between the molecules making up the
friction traces was introduced by Gates and Hsu and
film. Slimmer molecules allow closer packing, increasing
later discussed with respect to vegetable oil formulations
intermolecular interactions and providing a stronger
by Minami et al. [7,15]. Steady-state coefficient of
film [12]. Representations of the fatty acids used in this
friction traces can generally be classified as one of four
study are displayed in figure 2. The representations were
types:
prepared in ACD/Labs Chemsketch package, which
contains a 3D optimization algorithm, based on . Type A: constant coefficient of friction during steady
simplified CHARMM parameterization [13]. Stearic state.
acid contains no double bonds and it is possible for . Type B: friction gradually increases during the test.
278 N.J. Fox et al./Boundary lubrication performance of free fatty acids in sunflower oil
. Type C: friction gradually decreases during the test.
. Type D: friction fluctuates throughout the test.
Type A is considered the most preferable for a
lubricant and is usually associated with low wear. Types
B and C may be acceptable for lubricants, but type D is
unacceptable as it is usually associated with high wear.
The friction traces for formulations containing 1%
additive and 5% additive are presented in figure 3. In
this study the stearic acid formulations could be
considered as type A at concentrations of 1% and
above. Oleic acid formulations were considered as type
B at low concentrations and type C at higher
concentrations. Formulations with linoleic acid were
generally considered as type B, but in some trials there
was a great deal of fluctuation classifying them as type
D. The base oil alone was considered type B. These
friction trace results follow the same trend as the wear
tests. Stearic acid was observed to be the most effective
additive, providing a consistent steady-state reduction in
the coefficient of friction. Oleic acid was next, providing
a slight reduction in the coefficient of friction, with
linoleic acid the least effective additive, providing no
improvement.
The differences observed in the friction traces could
perhaps be related to the oxidation stability of the
saturated stearic acid compared to the unsaturated oleic
and linoleic acids. During boundary lubrication the high
load and slow speeds will increase the temperature in the
contact region, increasing any reaction rates. Unsatu-
rated fatty acids are less resistant to oxidation at high
temperatures [16]. It is likely that the protective films
formed by unsaturated fatty acids are unstable and
break down over time, becoming less effective. Stearic
Figure 3. Coefficient of friction traces of reciprocating rig trials of sunflower oil formulations at (a) 1% by weight additive and (b) 5% by weight.
acid is saturated and more resistant to oxidation, so the
protective film is more likely to be stable over time. A
protective film resistant to oxidation could also be a
reason for the improved wear performance of the stearic
acid over the other acids.
The constant steady state coefficient of friction
observed for stearic acid formulations could also be
related to the strength of the intermolecular interactions
and the ability to form a strong protective layer.
3.2. Effect of temperature
Stearic acid was observed to be the most effective
fatty acid additive in sunflower oil, reducing both the
coefficient of friction and wear. The next step was to
examine how changes in bulk temperature would affect
the boundary lubrication performance of the stearic acid
formulations. Trials were conducted with the formula-
tions at 50, 100, and 150 8C and the results are presented
in figures 4 and 5.
Wear and friction increased during base oil trials as
the temperature was raised. At 150 8C the base oil failed
to protect the surface resulting in catastrophic wear. No
wear volume was calculated for the base oil at 150 8C,
but an image of the wear scar is displayed in figure 6.
Addition of stearic acid to the base oil improved the
boundary lubrication properties at all temperatures
tested. Very similar results were observed for the trials
at both 50 and 100 8C, with the stearic acid reducing
friction and wear. At 150 8C the amount of wear on the
ball significantly increased, but the coefficient of friction
remained low and, as seen in figure 6, there is no sign of
catastrophic failure on the ball surface. Also at 150 8C the
 N.J. Fox et al./Boundary lubrication performance of free fatty acids in sunflower oil 279

Figure 4. Effect of temperature on ball wear during trials of stearic acid/sunflower oil formulations at 50, 100, and 150 8C.

addition of fatty acid continues to steadily improve wear
properties right up to 5%, instead of the improvement
levelling of at around 1% as seen at lower temperatures.
The lowest recorded wear at 150 8C, corresponded with
the only stable coefficient of friction trace.
Jahanmir examined the impact of temperature and
chain length on the boundary lubrication performance
of fatty acid additives in mineral oils [17]. Two
temperature transitions were observed to occur during
the trials. The first, and lower temperature, transition
was an increased variability in the coefficient of friction
readings, attributed to an irregular stick/slip mechan-
ism. The second transition was a dramatic rise in
coefficient of friction, attributed to film desorption or
failure. For stearic acid in hexadecane the first and
second transitions were observed at oil temperatures of
approximately 130 and 140 8C, when conducted under
boundary lubrication conditions.
In relation to this current study it would appear, from
the much higher coefficient of friction and significant
damage to the ball surface, that the sunflower base oil at
150 8C is above the second transition temperature. The
stearic acid doped samples, however, with a variable, but
still low coefficient of friction trace and increased wear,
would appear to be around the first transition tempera-
ture at 150 8C. The stick/slip mechanism of a disoriented
film at the first transition, suggested by Jahanmir [17],

Figure 5. Coefficient of friction traces of stearic acid/sunflower oil formulations during trials at (a) 50 8C and (b) 150 8C.
280 N.J. Fox et al./Boundary lubrication performance of free fatty acids in sunflower oil
Figure 6. Ball wear scar images for sunflower oil dosed with 5% w/w stearic acid. Trial at (a) 50 8C, (b) 100 8C, (c) 150 8C, and (d) the base oil at
150 8C.
would account for both the observed instability of the
coefficient of friction and increased wear.
The difference in the ability of the protective films of
the base oil and the stearic acid doped samples to resist
temperature could be due to the level of intermolecular
interactions. In the study by Jahanmir, shortening the
chain length of the fatty acid additive reduced the level
of intermolecular interactions and the temperature
stability of the protective film decreased [17]. In a
similar manner the observed increased temperature
resilience of the stearic acid doped protective films in
the current study could be due to the greater level of
intermolecular interactions possible between straight-
chained stearic acid molecules compared to the non-
linear fatty acids in the sunflower base oil.
The oxidation stability of the fatty acids present in
the system may also have an impact on the wear at
higher temperatures. If the fatty acids are unable to
resist oxidation at the higher temperatures any protec-
tive layer would quickly degrade, resulting in a rapid
increase in wear. The layer could be continually
replenished, but would just as quickly degrade again.
In a previous study sunflower oil was found to oxidize at
temperatures around 150 8C, so it is possible that the
observed catastrophic failure was due to oxidative
degradation of the film [16]. As stearic acid is saturated
it would be able to resist higher temperatures before
oxidizing and possibly provide a more stable film.
4. Conclusions
The following conclusions can be made following this
study of the boundary lubrication performance of free
fatty acids in sunflower oil:
. Addition of free fatty acids can improve the boundary
lubrication performance of sunflower oil, under
sliding conditions.
. Increasing the level of unsaturation in the fatty acid
has a negative influence on the performance as a
boundary lubrication improver.
. Stearic acid was the most effective boundary lubrica-
tion additive in sunflower oil, reducing wear and
providing a steady reduction the coefficient of
friction.
. Boundary lubrication properties of sunflower oil
formulations are significantly poorer at temperatures
approaching 150 8C.
 N.J. Fox et al./Boundary lubrication performance of free fatty acids in sunflower oil
References
[1] N.J. Fox and G.W. Stachowiak, Lubr. Eng. 59(2) (2003) 15.
[2] J.A. Williams, Engineering Tribology (Oxford University Press,
New York, 1994).
[3] G.W. Stachowiak and A.W. Batchelor, Engineering Tribology
(Elsevier, Amsterdam, 1993).
[4] T.C. Ovaert, H.S. Cheng and M.C. Shen, SAE Trans. 100(4)
(1991) 1131.
[5] Y. Cao, L. Yu and W. Liu, Wear 244 (2000) 126.
[6] Y. Cao and L. Yu, Mocaxue Xuebao/Trib. 20(4) (2000) 288.
[7] I. Minami, H.S. Hong and N.C. Mathur, J. Synth. Lubr. 16(1)
(1999) 3.
[8] J. Vizintin, A. Arnsek and T. Ploj, J. Synth. Lubr. 17(3) (2000)
201.
281
[9] ASTM Astm designation: G 133–95. Standard Test Method for
Linearly Reciprocating Ball on Flat Sliding Wear. (1998).
[10] Z.S. Hu, S.M. Hsu and P.S. Wang, Tribol. Trans. 35(1) (1992)
189.
[11] M.J.D. Low and H. Inoue, Can. J. Chem. 43 (1965) 2047.
[12] A.G. Papay, Lubr. Eng. 39(7) (1983) 419.
[13] B.R. Brooks, R.E. Bruccoleri, B.D. Olafson, D.J. States,
S. Swaminathan and M. Karplus, J. Comput. Chem. 4 (1983)
187.
[14] S. Odi-Owei, Lubr. Eng. 45(11) (1988) 685.
[15] R.S. Gates and S.M. Hsu, Tribol. Trans. 34 (1991) 417.
[16] N.J. Fox, A.K. Simpson and G.W. Stachowiak, Lubr. Eng. 57(10)
(2001) 14.
[17] S. Jahanmir, Wear 102 (1985) 331.