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Tribology International
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Lubricity of bio-based lubricant derived from different chemically

modified fatty acid methyl ester
N.W.M. Zulkifli a,n, S.S.N. Azman a, M.A. Kalam a, H.H. Masjuki a, R. Yunus b, M. Gulzar a
a
Department of Mechanical Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia
b
Institute of Advanced Technology, University Putra Malaysia, 43400 Serdang, Selangor, Malaysia

art ic l e i nf o a b s t r a c t

Article history: In this research, polyol ester was used as the source of a biolubricant. The trimethylolpropane (TMP) and
Received 27 August 2014 pentaerythritol ester (PE) were produced from palm oil methyl ester; they are biodegradable and have
Received in revised form high lubricity properties. Two different conditions of lubrication were investigated. Under these test
18 February 2015
conditions, the wear and friction characteristics of different ester samples were measured and compared.
Accepted 16 March 2015
The esters derived from PE and TMP had comparable characteristics to the fully formulated lubricant
(FFL) in terms of the coefficient of friction (CoF). In terms of the mixed lubrication condition, the PE ester
Keywords: has the lowest CoF.
Synthetic lubricant & 2015 Elsevier Ltd. All rights reserved.
Biolubricant
Tribology

1. Introduction epoxidation of the vegetable oil [5,12] to eliminate vulnerable sites

for oxidation and to interrupt the formation of crystals at low
In an engine, engine oil plays an important role as a lubricant by temperatures.
lubricating moving parts such as the piston ring and cylinder liner. It It is thought that natural triglycerides may enhance lubricity as
also cleans, inhibits corrosion, improves sealing, and acts as a coolant they can provide an effective boundary layer due to the presence of a
by carrying heat away. Mineral, synthetic, and semi-synthetic engine polar structure, which disperses non-polar molecules or the base
oils are not directly involved in the ecological cycle with air and soil. lubricant and can act as an anti-wear additive and friction modifier
However, leakage, human error, and blown pipes may occur, and for commercial mineral-based lubricating oil [19,20]. Erhan and
disposal of engine oil may damage the ecosystem due to its toxicity. Sharma [21] found that the addition of 5% chemically-modified
Knowledge of and concern over the usage of petroleum-based prod- soybean oil (CMSO) products caused a 50% reduction in wear
ucts have created the opportunity to produce environmentally frien- using a hexadecane-based oil. The coefficient of friction obtained for
dly lubricants form biodegradable feedstock [1]. hexadecane (0.095) was reduced to 0.031 upon the addition of CSMO
Natural oils present an attractive substitute to conventional products under these experimental conditions. In another study,
lubricants, especially in environmentally sensitive areas like agri- Maleque and Masjuki [22] used viscosity test to show that 5% palm
culture, forestry, and mining since they have low toxicity, high oil methyl esters (POME) can improve the viscosity index (VI) of a
biodegradability [2–5], low friction and wear characteristics [6–8], mineral-based lubricant up to a load of 500 N. However, corrosive
and improve the surface finish [9]. However, natural triglycerides wear and the formation of pits on the damaged surface were the
have some drawbacks, including a low flash point, [10–12] and dominant modes of wear at higher temperatures. It is believed that
poor thermal stability [10,13]. In general, it has been widely corrosive wear occurs in situations where the POME additive reacts
understood that the hydrogen atoms on the β-carbon atom of with the metal surface at higher temperatures and the reaction
the alcohol fragment in ester molecule leads to poor oxidative and products are worn away from the surface, leading to greater wear
thermal stability [14]. The presence of hydrogen atoms will cause a and friction. In addition, Goodrum and Geller [23] found that castor
corrosion mechanism that produces acid and alkenes and hence methyl ester and Lesquerella oil methyl ester also enhanced lubricity
increases viscosity and acidity. These problems only can be solved to acceptable levels at concentrations below 1%. It is believed that the
partially by additives [5,12,15,16]. Consequently, vegetable oil high concentration of the unique fatty acid methyl ester methyl
has to be chemically modified by transesterification [17,18] or ricinolate could be responsible for the lubricity-enhancing properties
of castor oil methyl ester.
Several studies have found that oxidation stability and thermal
n
Corresponding author. Tel.: þ 60 3 79675204; fax: þ60 3 79675317. stability could be improved by replacing glycerol with an alcohol that
E-mail address: [email protected] (N.W.M. Zulkifli). does not contain β-hydrogen atoms, such as PE or TMP [24,25].

http://dx.doi.org/10.1016/j.triboint.2015.03.024
0301-679X/& 2015 Elsevier Ltd. All rights reserved.

Please cite this article as: Zulkifli NWM, et al. Lubricity of bio-based lubricant derived from different chemically modified fatty acid
methyl ester. Tribology International (2015), http://dx.doi.org/10.1016/j.triboint.2015.03.024i
2 N.W.M. Zulkifli et al. / Tribology International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Nomenclature POME palm oil methyl esters

SDL seizure delay load
COF coefficient of friction TAN total acid number
EHL elastrohydrodynamic TMP trimethylolpropane
EP extreme pressure VI viscosity index
FFL fully formulated lubricant WL weld load
ISL initial seizure load WSD wear scar diameter
PE pentaerythritol esters

However, our understanding of the mechanism and tribological proper- speed of 1200 rpm, and an operation time of 60 min. The wear
ties of TMP and PE ester is still vague. Therefore, this research was produced on the three stationary balls was measured using a
conducted in order to improve the understanding of the tribological calibrated microscope and reported as the wear scar diameter
properties of TMP and PE ester and to develop both TMP and PE ester (WSD) or calculated volume.
as a biolubricant. This research will investigate the effects of different For the extreme pressure conditions, the test standard was
sources of esters in different lubrication regimes. ASTM 2783. In the machine, a vertical driving spindle rotated a
chuck with a speed of 1770 rpm. The load was increased by 196 N
every 10 s until the ball was welded. Seizure was indicated by a
2. Experimental methods sharp rise in the coefficient of friction. A number of tribological
parameters were determined using the standard procedures pre-
2.1. Lubricant sample preparation scribed by the manufacturer [27]. For the purpose of illustration, a
wear–load curve ABCD is shown diagrammatically in Fig. 4. Each
In this investigation, TMP ester and PE ester were compared to test was carried out three times to determine the experimental
paraffin oil and fully formulated lubricant (FFL). Table 1 presents error. Error measurements specified in this experiment were based
some of their physical properties. The TMP ester and PE ester were on the maximum deviation between three measurements.
synthesized by the transesterification of methyl esters prepared
from palm oils (POME) with TMP and PE respectively, as shown in
2.2.1. Hertz line
Fig. 1 [25] and Fig. 2 [26]. A 200 g volume of POME and a known
The following equation is used to plot the hertz diameter
amount of TMP and PE was placed in a 500 ml three-neck reactor
against load which results in linear proportional line as shown
and constantly agitated using a magnetic stirrer. The weight of
in Fig. 4:
TMP and PE was determined based on the required molar ratio
and the calculated mean molecular weight of POME. The mixture dh ¼ 8:73 10 2 ðPÞ1=3 ð1Þ
was then heated to the reaction temperature and the catalyst was
The diameter of contact area, dh also called as hertz scar diameter, is
added. A vacuum was gradually applied to the system until the
the indentation produced by ball deformation and it is calculated by
desired pressure was reached. This pressure was maintained until
using equation above [28–31] where P is the applied load in Newton.
the reaction reached completion. Table 2 shows the fatty acid
The Hertz line increase linearly due to the linearity of the applied load,
content in the TMP ester.
causing the hertz diameter to increase linearly.

2.2. Four-ball wear test

2.2.2. Initial seizure load
The initial seizure load (ISL) is the load at which the wear–load
A four-ball machine was used to investigate the effect of esters
line deviates from the Hertz line [29] and it is denoted as point C
under boundary and extreme pressure conditions. The four-ball
in Fig. 4. It indicates the temporary breakdown of the lubrication
wear tester is the predominant wear tester used by the oil
film [30] and determined by sudden increase of WSD [28].
industry to study lubricant chemistry. The device consists of three
balls held stationary in a ball pot plus a fourth ball held in a
rotating spindle, as shown in Fig. 3. The balls used in this study 2.2.3. Weld load
were steel balls, AISI 52-100, 12.7 mm in diameter, with a hardness Weld load (WL) is the load at which the lubricant completely
of 64–66 Rc. The balls were thoroughly cleaned with toluene fails and at which so much heat is generated that the fusion of
before each experiment. The sample volume required for each test metal occurs between the rubbing surfaces. It is detected by the
was approximately 10 ml. apparent fusion of the rubbing surfaces of the steel balls [32],
To determine the anti-wear characteristics, the test conditions indicating the lubricant's EP level had been exceeded [30] and it is
were a 392 N load, operation at room temperature, a rotational identified by point D in Fig. 4.

2.2.4. Mean specific pressure

Table 1
Major physical properties of different lubricants. Mean specific pressure (Pm) is the pressure applied at the contact point
[29]. The unit is N/mm2 and it is expressed as equation below where P is
Specific gravity at 15.6 1C (g/ Viscosity (cSt) VI TAN the applied load in N and d is the diameter of contact area in mm.
ml) (mgKOH/g)
40 1˚C 100 1C 2
P m ¼ 52P=d 100 ð2Þ
Paraffin 0.8283 30.61 5.26 110 –
oil 2.3. Lubrication regime determination
FFL 0.8549 101.86 14.46 146 1.02
TMP 0.9021 40.03 9.50 194 0.44
PE 0.9300 68.40 12.70 183 0.20
During testing, the upper ball was lubricated through contact
with the lower three balls by a thin film of lubricant. On the basis

Please cite this article as: Zulkifli NWM, et al. Lubricity of bio-based lubricant derived from different chemically modified fatty acid
methyl ester. Tribology International (2015), http://dx.doi.org/10.1016/j.triboint.2015.03.024i
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TMP POME TMP ester Methanol

R=alkyl group C6-C20
Fig. 1. Synthesis of TMP ester.

Pentaerythritol POME PE ester Methanol

R’=alkyl group C6-C20
Fig. 2. Synthesis of pentaerythritol ester (PE).

Table 2 Table 3
Fatty acid content. Dimensionless film thickness parameter range for lubrication regimes.

Sources Fatty acid λ λZ3 34 λ 4 1 λr1

Tetraester (%) Triester (%) Diester (%) Monoester (%) Lubrication regime Full fluid film Mixed film Boundary lubrication

TMP – 82 9 1
PE 52 36 – –
uη 0:68 0:073
F
H min ¼ 3:63 0
0 0 ðαE'Þ0:49 1 e 0:68k ð4Þ
ER E0 R02
Rotating direction where H min is the dimensionless minimum film thickness, U the
dimensionless speed parameter ðuη0 =E0 R0 Þ, where u the mean
speed of contacts in u1 þ u2 =2, η0 is the coefficients of dynamic
viscosity, E' is the modulus of elasticity ðð1 v21 =E1 Þ þ ð1 v22 =E2 ÞÞ of
the interacting solids and R' is the reduced radii ð1=R1 þ 1=R2 Þ 1 , R
Fixed specimens is the radius of the ball, E is the modulus elasticity of the solids and
Oil cup v is the kinematic viscosity. G the dimensionless material para-
meter ðαE0 Þ, where α is the pressure viscosity coefficient. W the
dimensionless load parameter ðF=E0 R02 Þ ;where F the applied load
Fig. 3. Schematic of the four-ball test machine. and k the ellipticity ratio ðRy =Rx Þ, equaling 1 for point contact. The
minimum film thickness ðhmin Þ was calculated using the following
equation:
hmin ¼ H min R0 ð5Þ
In order to distinguish the different lubrication regimes, the
dimensionless film thickness parameter ‘λ’ is used according to its
appropriate range for each lubrication regime. The lambda factor is
a ratio calculated on the following below:
hmin
λ¼ ð6Þ
Rq
where λ is the dimensionless film thickness ratio whereas Rq is the
average surface roughness of the contacting surfaces. According to
EHL theory, the relationship between λ and the lubrication regime
is as in Table 3.
Fig. 4. Illustration of a wear load graph.

3. Results and discussion

of EHL theory, the instantaneous nominal film thickness was
calculated for circular point contact. The dimensionless local The results will be divided into two different sections. The first
minimum film thickness was calculated by using the following section describes the extreme pressure condition and the second
equations developed by Hamrock and Dowson [33]: section describes the mixed lubrication condition. The experiments
were repeated 3 times for each load to check its stability of the CoF
value. From the results, the value of mean and standard deviation for
H min ¼ 3:63U 0:68 G0:49 W 0:073 1 e 0:68k ð3Þ
all lubricant, it is noted that when the load is fixed, the lubricant

Please cite this article as: Zulkifli NWM, et al. Lubricity of bio-based lubricant derived from different chemically modified fatty acid
methyl ester. Tribology International (2015), http://dx.doi.org/10.1016/j.triboint.2015.03.024i
4 N.W.M. Zulkifli et al. / Tribology International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

0.8000

0.7000

0.6000

0.5000
CoF

196 N
0.4000
392 N
0.3000 588 N
785 N
0.2000
981 N
0.1000

0.0000
0 2 4 6 8 10
Time (s)

Fig. 5. Variation in CoF with load for paraffin oil (Error¼ 70.02). Fig. 7. Variation in CoF with load for TMP ester (Error¼ 7 0.02).

Fig. 6. Variation in CoF with load for FFL (Error¼ 7 0.02). Fig. 8. Variation in CoF with load for PE ester (Error¼ 7 0.02).

10.0
yielded consistent CoF value over multiple runs. The maximum error
is 8.58 10 3.
Log WSD (mm)

3.1. Extreme pressure condition 1.0

100 1000 10000
3.1.1. The effect of applied load on the coefficient of friction
Pm is calculated by using the definition provided in Eq. 2.
Table 4 shows the values of mean specific pressure, Pm applied 0.1
Paraffin Oil
during the EP test, where the pressure is dependent with the load FFL
and diameter of contact area of the balls. The results show that, TMP
both the diameter of contact area and mean specific pressure are PE
0.0
directly proportional to the load applied (Table 4). ISL, WL, COF Log Load (N)
and WSD at 1000N for all samples were summaries in Table 5. It
Fig. 9. Relationship between load and wear scar diameter (WSD).
can be seen that, Paraffin had the lowest ISL and WL values
compared to other samples and FFL shows the best performance
by having the lowest ISL, WL and WSD at 1000N. This might be
due to the presence of additives in the FFL compositions which
able to boost its performance. However, PE showed good results by peak of the asperities, thus increasing both the CoF and wear. This
having slightly higher ISL and WL value compared to Paraffin and regime is known as boundary lubrication [34]. In this regime, the
lowest COF at 1000N than FFL and TMP. However, PE had the contacting regions increase local pressures, which may lead to noise,
highest WSD among all the samples at 1000N even though it had fatigue damage, and high wear rates [35]. The rubbing surfaces are
the lowest COF, where this phenomenon will be explained later in thus smoothened and, at this latter stage, their wear rate is low and
Section 3.2.2. constant. At 981 N, the CoF continued increasing until the ball
Fig. 5 shows the correlation of CoF with different loads using welded. This occurred due to the high pressure and high temperature;
paraffin oil. At low loads (below 392 N), the CoF of paraffin oil is the lubricant evaporates and causes the balls to weld together.
nearly unchanged. It shows that the thin film is formed can still Fig. 6 shows the correlation of CoF with different loads using
sustain the load. However, as the load was increase, the thin film FFL. Even at 981 N, the lubricant still did not encounter the initial
started to break down and the CoF increased. As the load increased up seizure load. This shows that this lubricant has better extreme
to 785 N, the CoF increased sharply at the beginning and then pressure characteristics compared to paraffin oil. It is believed that
decreased. This is possibly due to the “running-in” effect, in which the extreme pressure additive package acted to maintain the low
the thickness of the oil film is too thin such that contact begins at the CoF value.

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Table 6
Calculated film thickness at 392 N load.

Sample Min film thickness (μm) Film thickness ratio Lubrication regime

Paraffin oil 0.0273 1.0 Boundary

FFL 0.0359 1.3 Mixed lubrication
TMP 0.0469 1.7 Mixed lubrication
PE 0.0539 1.9 Mixed lubrication

TMP ester. At low load, at 196 N and 392 N, the thin film formed by
PE still can sustain the load applied. However, it can be seen that
running-in effect started to occur. PE had the lowest CoF and the
best extreme pressure characteristics as compared to all other
samples as the weld point for this case is higher than 981 N.

3.1.2. The effect of applied load on the wear scar diameter

The WSD can be defined as two different regions in Fig. 9. The
first region is the anti-wear region, which is before the ISL. The
Fig. 10. Relationship between CoF and time (Conditions: Load¼ 400 N; WSD is similar to the elastically deformed area of contact under
Duration¼1 h; Temperature¼ 75 1C; Speed ¼ 1200 rpm).
static loading. The second region is the EP, which occurs after the
ISL. The WSDs here are much larger than in the previous region.
0.9
According to applied loads, we define initial seizure load as the
0.8 first load beyond the linear proportional line when the EP test
0.7 conducted was based on ASTM D2596. Fig. 9 shows that the WSD
0.6 increased gradually in the anti-wear region. However, it increased
WSD (mm)

0.5 abruptly after the ISL, up to a 2.5 s seizure delay load, followed by a
slow increase up to the WL. The slow increase in the WSD before
0.4
the ISL was reached may be attributed to the formation of a thin
0.3
film of lubricant and the adsorption of additive by the sliding
0.2 surfaces. The sudden increase in the WSD was due to the rise in
0.1 temperature and the consequent partial desorption of the
0 adsorbed thin layer of lubricant [36]. After a 2.5 s SDL, the WSD
Paraffin FFL TMP PE increased slowly due to the formation of a combined layer of the
Fig. 11. Comparison of the WSD of the lubricants (Conditions: Load¼ 400 N; additive and the reaction of the esters. This combined layer
Duration¼1 h; Temperature¼ 75 1C; Speed ¼ 1200 rpm). prevents metallic contact between the balls, even at higher loads.
In addition, Fig. 9 shows that the TMP and PE ester improved
Table 4 the load-carrying capacity and function of the lubricant up to high
Calculated diameter of contact area and mean specific pressure in EP test. loads. Furthermore, it can be observed that at low loads, there was
no significant difference between the TMP ester and FFL, in
Load, P Diameter of contact area, d Mean specific pressure, Pm (kN/
contrast to paraffin oil and PE. However, as the load increased to
(N) (mm) mm2)
over 490 N, the TMP ester and paraffin oil greatly increased the
196 0.5071 3963.33 WSD. Paraffin oil could not sustain a load of more than 785 N and
392 0.6389 4993.48 the ball was welded at 981 N. The TMP ester could maintain a load
588 0.7314 5716.11 up to 981 N. Therefore, the TMP ester improved the WSD. This is
785 0.8053 6294.07
because the TMP ester had a higher viscosity than paraffin oil.
981 0.8674 6779.50
Fig. 9 shows that PE ester had the lowest WSD at low load,
compared to all samples. As the load increased, WSD showed
Table 5 constant increment until 490 N. Beyond that, the WSD seem to
Extreme pressure conditions. increase drastically. As compared to FFL, the thin film formed can
sustain the load applied until 1100 N, where ISL and WL values
Sample ISL (N) WL (N) CoF at 1000 N WSD at 1000 N (mm) were the highest compared to others.
Paraffin 400 1000 – –
It is believed that the PE ester had a better CoF and WSD
FFL 1200 2000 0.08 0.54 compared to palm oil because of the presence of tetra-ester in the
TMP 400 1400 0.25 2.47 fatty acid content.
PE 600 1400 0.06 2.54

3.2. Mixed lubrication condition

Fig. 7 shows the correlation of CoF with different loads using TMP 3.2.1. Estimation of film thickness
ester. Fig. 7 shows a similar trend to paraffin oil. However, the value of Nominal local film thickness was calculated as per the relationship
CoF was lower compared to paraffin oil. The figure shows that the TMP provided in Eq. 4. Table 6 shows the calculated minimum film
ester had better extreme pressure characteristics compared to paraffin thickness and lubricant regime indication for each lubricant. In general,
oil. However, TMP ester still had a higher CoF compared to FFL. as the load increased, the film thickness decreased, hence the lubrica-
In Fig. 8, it can be seen that as the load increased, the CoF tion regime changed from mixed lubrication to boundary conditions. At
increased. In addition, the trend was also similar to paraffin oil and high contact loading, the stress intensity produced led to localized

Please cite this article as: Zulkifli NWM, et al. Lubricity of bio-based lubricant derived from different chemically modified fatty acid
methyl ester. Tribology International (2015), http://dx.doi.org/10.1016/j.triboint.2015.03.024i
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OL

Almost no wear,
protective ilm
protect the surface

Parafin

Oxidation ilm is generated

to protect the surface

PE ester

No protective ilm is
detected

Severe wear and grooves

TMP ester

Almost no protective ilm

is activated here

Severe abrasive wear

Fig. 12. Wear micrograph and EDX of steel ball at constant load (Conditions: Load¼ 400 N; Duration¼ 1 h; Temperature¼75 1C; Speed ¼1200 rpm).

plastic deformation followed by initiation and the steep propagation of same time the rheology and elastic and plastic surfaces deformation of
crack resulting in spall formation [37]. The nominal film thickness interacting surfaces becomes significant at high contact temperatures.
formation is majorly dependent upon the lubricant viscosity, but at the Such phenomenon results in instantaneous local film rise for even low

Please cite this article as: Zulkifli NWM, et al. Lubricity of bio-based lubricant derived from different chemically modified fatty acid
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viscosity lubricants as rubbing surfaces asperities are deformed to even compared to ordinary lubricant at around 0.07. In order to
provide remaining reservoir of lubricant before the rapture of film. This utilize TMP and PE esters as engine oils, many other properties
may not be the case if the contact mechanism between interacting including the oxidative, thermal, and hydrolytic stabilities need to
surfaces is changed. PE had the highest film thickness of around be examined. TMP and PE esters are environmentally superior to
0.054 μm, and paraffin had the lowest film thickness of around mineral oil-based lubricants, so research to investigate the proper-
0.028 μm. This could increase the life of steel ball with PE than that ties of esters to make them technologically competitive as auto-
of with paraffin oil. Even though, FFL has low film thickness compared mobile lubricants should be encouraged.
to TMP and PE esters, additive packages in the lubricant will help to
protect the surfaces. Based on the lambda ratio, nearly all of the
lubricants fall under mixed lubrication except for paraffin oil.
Acknowledgements

3.2.2. Effect of different lubricants on WSD and CoF

The authors would like to thank the University of Malaya, which
The CoF for the different samples at a constant load is shown in
made this study possible through the research Grant PV070/2011B
Fig. 10. A significant improvement in CoF was found for both esters
and high impact research Grant no. UM.C/HIR/MOHE/ENG/60.
compared to paraffin oil. The PE ester had a better CoF compared
to other sources.
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Please cite this article as: Zulkifli NWM, et al. Lubricity of bio-based lubricant derived from different chemically modified fatty acid
methyl ester. Tribology International (2015), http://dx.doi.org/10.1016/j.triboint.2015.03.024i
8 N.W.M. Zulkifli et al. / Tribology International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

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Please cite this article as: Zulkifli NWM, et al. Lubricity of bio-based lubricant derived from different chemically modified fatty acid
methyl ester. Tribology International (2015), http://dx.doi.org/10.1016/j.triboint.2015.03.024i