Energy for Sustainable Development 52 (2019) 33–39

Contents lists available at ScienceDirect

Energy for Sustainable Development

Effect of oxidation of Jatropha curcas-derived biodiesel on its

lubricating properties
Zuowen Liu a,b, Fashe Li a,b,⁎, Jiaxu Shen d, hua Wang a,b,c
a
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
b
State Key Laboratory of Complex Nonferrous Metal Resources Cleaning Utilization in Yunnan Province, Kunming 650093, China
c
Dali University, China
d
Yunnan Electric Power Research Institute, China

a r t i c l e i n f o a b s t r a c t

Article history: The oxidation of a Jatropha curcas-derived biodiesel was accelerated through the Rancimat method. High-fre-
Received 23 February 2019 quency reciprocating friction, wear testing and gas chromatography coupled with mass spectrometry (GC–MS)
Revised 7 June 2019 were utilized to analyze the influence of composition changes during the oxidation of Jatropha biodiesel on its
Accepted 18 June 2019
lubricating properties. This research indicated that: The polar functional ester group of Jatropha biodiesel could
Available online xxxx
be adsorbed on a metal surface to form a physical adsorption membrane, while its carbon‑carbon double bond
Keywords:
would enhance the electrostatic force among the adsorbed membrane molecules, to improve the lubricating
Biodiesel properties of Jatropha biodiesel; the oxidation had a significant effect on the lubricating properties of biodiesel.
Oxidation The peroxides generated by the short-time oxidation would stimulate the decomposition of the fatty acid
Lubrication chain, destroying the stability of the lubricative adsorption membrane. The highly polar products and epoxy com-
Composition changes pounds formed at the later stage of oxidation contributed to the formation of a stable boundary film on the metal
surface and enhanced the lubricity of biodiesel.
© 2019 Published by Elsevier Inc. on behalf of International Energy Initiative.

Introduction
At present, the pollution of petrochemical diesel to the environment
is becoming increasingly severe. In order to alleviate environmental
pressure and achieve sustainable development, the research on
alternative fuel of petrochemical diesel has received extensive atten-
tion. Biodiesel is not only a biodegradable, renewable, clean and envi-
ronmentally friendly liquid fuel, but it is completely miscible with
conventional diesel. Diesel-biodiesel blends and pure biodiesel could
be directly used in the compression ignition engines, currently without
any improvement. Subsequently, biodiesel is the most potential alterna-
tive fuel of petrochemical diesel. Studies have demonstrated that bio-
diesel has better lubricating performance than petrochemical diesel.
Kumar, Varun, and Chauhan (2014) studied the wear and friction char-
acteristics of Jatropha biodiesel-diesel blends (20%, 40%, and 100%
JOME) with a four-ball tester at 1800 rpm. The results demonstrated
that as the biodiesel content increased, the load and temperature de-
creased, while the fuel presented improved lubricity. The lubricating
properties of the fuel play an important role in the friction reduction be-
tween the components. Holmberg et al. (Holmberg et al., 2014) found
⁎ Corresponding author at: Faculty of Metallurgical and Energy Engineering, Kunming
University of Science and Technology, Kunming 650093, China.
E-mail address: asanli@foxmail.com (F. Li).
that for heavy machinery, 33% of the fuel energy loss was caused by fric-
tion, for which, the engine accounted for 7.3%, the transmission
accounted for 5.1%, the rolling resistance accounted for 13.2% and the
brakes accounted for 7.2%. Mineral oil as lubricant could improve the
wear resistance and reduce the energy loss, but mineral oil is toxic
and not biodegradable, polluting the environment (Adhvaryu, Liu, &
Erhan, 2005; Mosarof et al., 2015; Shahabuddin et al., 2013). The pollu-
tion does not only harm plants and animals, but also human lives (Rani,
Joy, & Nair, 2015). Therefore, it is necessary to eliminate the mineral oil
contamination problem through the lubricating properties exploration
of biodegradable biodiesel.
Biodiesel lubrication performances are usually evaluated through
high frequency reciprocating friction and wear testing (HFRR) (De
Farias & Alves, 2014; Lapuerta et al., 2016; Luo et al., 2013). Sulek et
al. (Sulek, Kulczycki, & Malysa, 2010) utilized HFRR to study the tribo-
logical properties of rapeseed biodiesel. It was observed that the friction
coefficients of B5 (diesel mixed with 5% of rapeseed biodiesel) and B100
were 20% and 30% lower compared to diesel. Although the Jatropha Bio-
diesel has good lubricating properties, it also has significant drawbacks,
such as poor oxidation stability. Biodiesel has a high content of unsatu-
rated fatty acid methyl esters, which makes it very susceptible to oxida-
tion (Yang et al., 2017).
Biodiesel components have a major impact on their lubricating
properties. An increase in carbon chain length and a reduction in

https://doi.org/10.1016/j.esd.2019.06.003
0973-0826/© 2019 Published by Elsevier Inc. on behalf of International Energy Initiative.
34 Z. Liu et al. / Energy for Sustainable Development 52 (2019) 33–39

Table 1
Testing equipment and manufacturers.

Equipment name Type Manufacturer

Vacuum drying oven DZF-6020 Shanghai Yiheng Technology Co., Ltd.

Rotary evaporator RE-52AA Shanghai Yarong Biochemical Instrument Factory
Ultrasonic cleaning machine SK5200HP Shanghai Kedao Ultrasonic Instrument Co., Ltd.
Electronic balance XPE105 METTLER TOLEDO
Digital display electric heating water bath HWS12 Shanghai Jingke Instrument Co., Ltd.
Biodiesel oxidation stability energy meter 873Biodiesel Rancimat Switzerland Vantone
Gas chromatography coupled with mass spectrometry Agilent 5973N United States Agilent Technology Co., Ltd.
High-frequency reciprocating friction and wear tester WFD-C1 Shanghai Mylar Laboratory Equipment Co., Ltd.
Fourier infrared spectroscopy FTS-40 United States Biorad

number of double bonds tended to enhance the lubricity of FAME Rockwell hardness values were in HRC, which were 58–66 and the sur-
(Lapuerta et al., 2016). Knothe and Steidley indicated that comparing face roughness was Ra ≪0.05 μm (Table 1).
with compounds obtained from petrodiesel, the fatty compounds ex-
hibited better lubrication behavior, which was attributed to the polar- Test equipment
ity-imparting oxygen atoms in their structure. Oxygen-containing
polar functional groups can improve the lubricating properties of bio-
diesel (Knothe & Steidley, 2005). Chong et al. indicated that balance of
saturated and unsaturated fatty acids in biodiesel can optimize bound-
Test methods
ary lubrication of biodiesel (Chong & Ng, 2016). E. Sukjit Partial thought
that hydrogenation of unsaturated fatty acid methyl esters(H-FAME)
Biodiesel preparation
produces strong and stable lubricating film, and the reduction of unsat-
The biodiesel was prepared through transesterification. 100 ml of
urated molecules in H-FAME decreases sensitivity to humidity (Sukjita,
vegetable oil was mixed with 220 ml of methanol. The reaction temper-
Tongroon, et al., 2019).
ature was controlled at 75 °C and 3 g of KOH was used as the catalyst.
In this article, the lubricating properties of the main components of
The reaction time was 2 h. Following the reaction completion, the bio-
biodiesel through GC–MS, high-frequency reciprocating friction and
diesel was poured into a separatory funnel and distilled water was
wear testing were analyzed. Simultaneously, the Rancimat method
added to remove glycerin and impurities. The preparation is presented
was adopted to accelerate the biodiesel oxidation. The effect analysis
in Fig. 1. Consequently, the methyl ester was dried with a rotary evapo-
of component changes during the oxidation of biodiesel on its lubrica-
rator and filtered with filter papers. Finally, the final product was col-
tion characteristics provided the data to support and for the research
lected for experimentation. The basic physicochemical parameters are
and application of biodiesel, as well as the theoretical basis.
presented in Table 2.
Materials and methods
Oxidation method
Raw materials and reagents The oxidation of the J. curcas biodiesel (20 ml) was carried out fol-
lowing the Rancimat method. Therefore, air (10 l/h) was introduced at
The raw materials and reagents were Jatropha oil from Yunnan 110 °C to accelerate the oxidation of Jatropha biodiesel. During oxida-
Baoshan, custom-made ultrapure water, methanol (analytically pure), tion, oil samples were taken every 4 h for testing.
petroleum ether (analytically pure), KOH (analytically pure), methyl
stearate (C18:0), methyl oleate (C18: 1). Methyl linoleate (C18:2) and Compositional analysis of biodiesel
methyl palmitate (C16:0) were produced in the laboratory. The test Oxidized biodiesel samples were diluted 5-fold with methanol and
samples were processed and annealed AISIE-52100 steel rods of Vickers analyzed through gas chromatography coupled with mass spectrometry
hardness of “HV30” 190–210. Following, grinding and polishing were (GC–MS). The GC conditions used were as follows: HP-5MS silica capil-
conducted for the samples to reach a surface roughness of Ra ≪0.02 lary column (30 mm × 0.25 mm × 0.25 μm); column temperature 80–
μm. The counterbody was a ball of 6 mm in diameter. The material 260 °C; program temperature: 5 °C/min; column flow rate:
was AISI E-52100 steel, ANSI B3.12 (metal ball) grade 28, The achieved 1.0 ml/min; inlet temperature: 250 °C; column front pressure:

Fig. 1. Biodiesel preparation. 1- Condenser pipe 2- Magnetic stirrer 3- Flask 4- Temperature sensor 5- Water bath.
 Z. Liu et al. / Energy for Sustainable Development 52 (2019) 33–39 35

Table 2 was expressed by the corrected wear track diameter. The wear track di-
Physicochemical properties of Jatropha biodiesel used in the current work. ameter mentioned in this article was the corrected spot wear diameter.
Property Jatropha biodiesel Method

Density (20 °C)/kg/m3 862 ASTM D341

Calculation of test data
Kinematic viscosity (40 °C)/mm2/s 4.35 ASTM D445 The measured spot wear diameter was required to be corrected ac-
Flash point/°C 185 ASTM D93–02 cording to the water vapor pressure of 1.4 kPa. The corrected spot wear
Cold filter plugging point/°C 3 ASTM D97 diameter was expressed by WS1.4. The calculation method was as
Sulfur content/% 0.002 ASTM D4269–2010
follows:
Water content/% 0.119 ASTM D1744
Copper corrosion (50 °C, 3 h)/level 1a ASTM D130 (1) Unadjusted average spot wear diameter is expressed in MWSD
EN14112–2003
and is calculated as follows:
Oxidation stability 3.01 ASTM D341

XþY
MWSD ¼ ð1Þ
2
100 kPa; sample volume: 0.40 μl; split ratio: 10:1, and carrier gas: high-
purity helium. where, X is the vertical wear track diameter in the direction of vibration
The MS conditions were as follows: ionization method (EI); electron and its unit is μm; Y is the horizontal wear track diameter in the direc-
energy 70 eV; transmission line temperature 250 °C; ion source temper- tion of vibration and its unit is μm.
ature 230 °C; quadrupole rod temperature 150 °C; mass scan range 35–
500; and software used: Wiley7n.1 standard library computer retrieval (2) Absolute vapor pressures (AVP1 and AVP2) at the beginning and
qualitative. end of testing. The mean absolute vapor pressure (AVP) during
the experiment was calculated as follows:

Working principle of high frequency reciprocating friction and wear testing

The working principles of high frequency reciprocating friction and RH1 −10v1
AVP1 ¼ ð2Þ
wear testing are presented in Fig. 2. 2 ml of the test oil sample was 750
placed in an oil bath at a given temperature. The steel ball was fixed ver-
tically loading the horizontally installed steel sheet. The ball recipro- RH2 −10v2
AVP2 ¼ ð3Þ
cated at a frequency of 50 Hz and a stroke of 1000 μm. The test load 750
was 200 g, while the test temperature was 60 °C. The contact interface AVP1 þ AVP2
between the test ball and the test piece was completely immersed in AVP ¼ ð4Þ
2
the oil. According to the test environment variables (temperature and
humidity), the wear track diameter of the steel ball was corrected to where, RH1 is the relative humidity of the incubator at the beginning of
the value under the standard condition. The lubricity of the test sample testing. RH2 is the relative humidity of the incubator at the end of

Fig. 2. Schematic diagram of high frequency reciprocating friction and wear testing.
36 Z. Liu et al. / Energy for Sustainable Development 52 (2019) 33–39

Table 3
Jatropha biodiesel lubrication test results.

Sample Jatropha biodiesel WS1.4 (μm) 170.21 Stroke (μm) 1000

Wear track diameter X/Y (μm) 174.83 160.39 Setting temperature (°C) 60 Hertz (Hz) 50
Average wear track diameter (μm) 167.61 Test time (min) 75 Average friction coefficient 0.1
Start/end temperature (°C) 22.1 22.6 Record interval (s) 1 Average absolute vapor pressure (kPa) 0.05
Start/end humidity 51.9 47.6 Test load (g) 200 Average film formation (%) 90.38

testing. The unit is %. V is the volume of the sample. V1 is the volume of
the sample at the start of the test. V2 is the volume of the sample at the
end of the test. The calculation equations for V1 and V2 were as follows:
1705:984
V1 ¼ 8:017352−
231:864 þ t1
1705:984
V2 ¼ 8:017352−
231:864 þ t 2
where t is the temperature of the incubator, t1 is the temperature of the
incubator at the beginning of testing and t2 is the temperature of the in-
cubator at the end of testing.
(3) WS1.4 is calculated as follows:
WS1:4 ¼ MWSD þ HCFð1:4−AVPÞ
Note: For unknown oil samples, the HCF value was 60.
Results and discussion
Lubrication performance of Jatropha biodiesel
The Jatropha biodiesel lubricating performance test results are pre-
sented in Table 3. Table 3 demonstrated that the Jatropha biodiesel
wear track diameter and average friction coefficient were 170.21 μm
and 0.1. Also, the wear track diameter was significantly lower than the
European standard EN590 value (460 μm). This signified that the
Jatropha biodiesel had better lubricating properties. Moreover, the
film formation capability measurements were included in Table 3. A
higher oil film reading indicated that the metal surface was in a sepa-
rated state, forming a good chemical protective film. The oil film forma-
tion content of Jatropha biodiesel was 90.38%, further illustrating the
corresponding good anti-wear and anti-friction properties.
oleate, methyl linoleate and stearic acid. The relative content of methyl
ester reached 95.28% and the relative content of methyl oleate, contain-
ing methyl carbon double bond and methyl linoleate, reached 82.29%,
which indicated that the Jatropha biodiesel had a high degree of
unsaturation, poor oxidation stability and was susceptible to environ-
ð5Þ
mental influences.
The wear track diameters of methyl palmitate (C16:0), methyl ole-
ð6Þ ate (C18:1), methyl linoleate (C18:2), and methyl stearate (C18:0) are
presented in Fig. 3. As it could be observed from Fig. 3, compared with
0# diesel, the biodiesel and single fatty acid methyl ester produced a
lower wear track diameter, while the wear track diameter of biodiesel
was lower compared to most single fatty acid methyl esters. This was
due to the fact that the fatty acid esters contained polar functional
ester groups, while the polar molecules were more easily adsorbed on
the metal surfaces, forming physical adsorption membranes. The ad-
sorption principle is presented in Fig. 4. Therefore, the fatty acid methyl
esters were superior to 0# diesel oils in lubricity. In addition, a synergis-
ð7Þ tic effect existed among various fatty acid esters, resulting in good lubri-
cating properties of the mixed fatty acid esters and biodiesel (Goodrum
& Geller, 2005). Simultaneously, it could be seen from Fig. 4 that the
wear track diameters of unsaturated methyl esters C18:1 and C18:2
containing carbon‑carbon double bonds, were significantly lower than
the C18:0, which indicated that carbon‑carbon double bonds of biodie-
sel had a certain influence on the lubricating performance. The main fac-
tor for the lubrication performance influence was the strength of the
adsorption membrane. The stronger the intermolecular binding in the
adsorption membrane was, the stronger the stability and denseness of
the adsorption membrane itself were. The interaction among molecules
in the adsorption membrane was mainly electrostatic. The higher the
number of double bonds was, the higher the electrostatic force was
(Xiaomin & East China University of Science and Technology, 2012).
The introduction of double bonds positively contributed to the fatty
acid esters forming a dense adsorption film on the metal surfaces, in-
creasing the strength of the lubricating film, which was also consistent

Lubricating properties of main components of biodiesel

The composition of Jatropha curcas biodiesel was analyzed through

GC–MS. The composition of the biodiesel is presented in Table 4. The
main components of Jatropha biodiesel were methyl palmitate, methyl

Table 4
Components of Jatropha biodiesel.

Compounds Molecular Molecular Relative

formula mass content/%

4-Methyl-hydroxy-2-pentanone C6H12O2 116.425 2.38

Phenol C19H24O 268.446 0.11
Methyl palmitate C17H34O2 270.456 12.99
9-Hexadecenoic acid, methyl ester, C17H32O2 268.633 0.89
(Z)-
Methyl oleate C19H36O2 296.499 40.08
trans-9-Octadecenoic acid, methyl C19H36O2 296.332 0.91
ester
Methyl linoleate C19H34O2 294.483 36.99
Methyl stearate C19H38O2 298.514 5.22 Fig. 3. Spot wear diameter of major components of biodiesel.
 Z. Liu et al. / Energy for Sustainable Development 52 (2019) 33–39 37

Fig. 4. Principle of adsorption of biodiesel on friction pair surface.

with previous research results (Fox, Tyrer, & Stachowiak, 2004; Geller &
Goodrum, 2004).

Effect of oxidation on lubrication performance of biodiesel

As it could be observed from Table 4, the Jatropha biodiesel had a Fig. 5. FTIR of Jatropha curcas-derived biodiesel prior to and following oxidation.
high degree of unsaturation, poor oxidation stability and was suscepti-
ble to environmental influences. The oxidation of biodiesel had a certain
influence on its lubricating properties. Consequently, it was necessary to
analyze the influence of the changes in composition of the Jatropha
curcas biodiesel during oxidation on its lubricating properties.

Changes in composition of biodiesel during oxidation

The composition changes of Jatropha biodiesel during oxidation are
presented in Table 5. From Table 5, it could be observed that during ox-
idation, the biodiesel saturation gradually increased, whereas the rela-
tive content of methyl linoleate containing two carbon‑carbon double
bonds gradually decreased. The relative content of Jatropha biodiesel
methyl linoleate was 42.21% at oxidation of 0 h. Subsequently to accel-
erated oxidation for 28 h, the relative content was 0, while the methyl
linoleate was completely oxidized. It could be observed from Fig. 5
that the 3006 cm−1 absorption peak was attributed to the stretching vi-
brational absorption of carbon hydrogen bonds in C=C-H groups, while
no peaks were observed in this region following oxidation. The results
indicated that the double bonds within the biodiesel were oxidized.
Simultaneously, aldehydes, ketones and macromolecular oxygen-
ates were formed during oxidation. This was because polyunsaturated
fatty acid methyl esters were more susceptible to oxidation than the Fig. 6. Variations of wear track diameters during biodiesel oxidation.
monounsaturated fatty acid methyl esters. The relative oxidation rate
of methyl linolenic acid (C18:3), methyl linoleate (C18:2) and methyl additional diallyl sites (Karavalakis, Stournas, & Karonis, 2010), while
oleate (C18:1) was 98:41:1 (Frankel, 1980). Compared to monounsatu- the diallyl protons were sensitive to the attack of oxygen radicals, lead-
rated fatty acids, the carbon chain of methyl linoleate contained ing to the oxidation of the molecules and the formation of Peroxy

Table 5
Composition changes during oxidation of Jatropha curcas biodiesel.

Compound Relative content (%)

0h 4h 8h 12 h 16 h 20 h 24 h 28 h

Hexanal (C6H12O) 0 0 0 0 0 0 0.1 1.25

4-methyl-hydroxy-2-pentanone (C6H12O2) 2.38 1.69 2.35 3.03 3.36 2.36 1.22 6.27
Octanoic acid, methyl ester (C9H18O2) 0 0 0 0 0.12 0.10 0.19 1.06
Octadecanoic acid, 9,10-dihydroxy-, methyl ester (C19H38O4) 0 0 0 0 0.24 0.29 0.34 3.69
Nonanedioic acid, dimethyl ester (C11H20O4) 0 0 0 0 0 0.1 0.12 12.64
Methyl palmitate (C17H34O2) 12.99 13.06 13.15 13.28 14.76 15.56 16.47 18.52
9-Hexadecenoic acid, methyl ester, (Z)- (C17H32O2) 0.89 0.59 0 0 0 0 0.76 0
9-Octadecenoic acid, methyl ester (C19H36O2) 40.58 48.67 48.89 48.96 52.78 54.56 55.35 36.34
trans-9-Octadecenoic acid, methyl ester (C19H36O2) 0 1.18 0.85 0 0 0.56 1.42 0
9,12-Octadecadienoic acid (Z,Z)-, methyl (C19H34O2) 42.21 34.02 34.25 34.23 27.48 24.08 19.43 0
Hexanoic acid, methyl ester (C7H14O2) 0 0 0 0 0 0 0 4.42
Nonanal (C9H18O) 0 0 0 0 0.2 0.18 0.25 0.45
Octadecanoic acid, 4-oxo-, methyl ester (C19H36O3) 0 0 0 0 0.65 0.89 1.02 1.73
Oxiraneoctanoic acid, 3-octyl-, methyl ester (C19H36O3) 0 0 0 0 0.26 1.25 2.69 7.75
Oxiraneoctanoic acid, 3-octyl (C18H34O3) 0 0 0 0 0 0 0 4.93
38 Z. Liu et al. / Energy for Sustainable Development 52 (2019) 33–39
Fig. 7. Octadecanoic acid, 9,10-dihydroxy-, methyl ester.
compounds. The peroxy compounds were further oxidatively converted
to aldehydes, ketones and other compounds.
Effect of composition changes on lubricating properties of biodiesel during
oxidation
Fig. 6 presents the wear track diameter variations during various ox-
idations of Jatropha curcas biodiesel. As it could be observed, the wear
track diameter of the unoxidized Jatropha biodiesel was 170.21 μm. As
the oxidation time increased, the wear track diameter of Jatropha bio-
diesel increased first and consequently decreased. Also, the wear track
diameter reached the maximum value of 355.83 μm subsequently to
16 h of oxidation, indicating that the long-term oxidation would im-
prove the lubricating properties of biodiesel. In contrast, the short-
term oxidation would have a negative impact on the friction and wear
characteristics of the oil. In the early stage of oxidation (0–16 h), the
peroxide formed by biodiesel may destroy the stability of the lubricating
adsorption film, thereby significantly reducing the lubricating proper-
ties of the ester. In fact, in the early stage of oxidation, the presence of
higher amounts of peroxide in biodiesel stimulates the decomposition
of fatty acid chains and produces monocarbonic acids such as formic
acid, acetic acid, propionic acid and caproic acid, which seriously affects
their ability to provide lubrication (Kreivaitis et al., 2011). In addition,
peroxide directly interacts with the lubricated surface, increasing
wear. The peroxide interacted directly with the lubricating surface, in-
creasing the wear. The reaction between hydroperoxide and metal sur-
face was as follows (Habeeb, Rogers, & May, 1987; Habeeb & Stover,
1987):
ROO∙ þ Fe→RO∙ þ FeO
2ROOH þ Fe→2RO∙ þ 2OH− þ Fe2þ
ROOH þ Fe2þ →RO∙ þ OH − þ Fe3þ
Fig. 8. Variation of friction coefficient during biodiesel oxidation.
The reaction product might be FeO, ferrous salts or iron salts. As the
amount of hydroperoxide increased, the triglyceride structure changed
and the free fatty acid content increased. The hydroperoxide formed
during the oxidation was detrimental, because it not only promoted
its own wear, but it also reduced the lubricating effect of biodiesel.
Simultaneously, through increased oxidation (exceeding 20 h), the
wear track diameter of Jatropha biodiesel was reduced. This situation
could be attributed to the highly polar products (acids, alcohols, and
monoesters) formed during the later stages of oxidation, such as
octanoic acid. The methyl esters contributed to the formation of a stable
boundary film on the metal surface (Wu et al., 2013) and in the later ox-
idation stage, to the formation of compounds with OH groups, such as
9,10 stearyl dihydroxymethyl ester, as presented in Table 4. The corre-
sponding fatty acid methyl ester chemical structure is presented in
Fig. 7. This fatty acid methyl ester contributed to the formation of hydro-
gen bonds and had a stronger plasticizing effect, which was consistent
with the findings of Goodrum and Geller (Goodrum & Geller, 2005).
Fig. 8 presents the friction coefficient changes during the Jatropha
biodiesel oxidation. It could be observed from the fluctuation curve
that the average coefficient of friction of the unoxidized Jatropha biodie-
sel was 0.107. Compared to the unoxidized biodiesel, the friction coeffi-
cients of biodiesel oxidation for 8 h and 16 h were improved,
accompanied by rapid fluctuation, indicating that the samples had
poor antifriction lubrication performance; when the oxidation time
exceeded 20 h, the friction coefficient of biodiesel was reduced and it
gradually stabilized, while the friction coefficient of 28 h of oxidation
was reduced to 0.08. This was due to the formation of epoxidized com-
pounds, such as 3-octyl-oxiranyloctanoic acid methyl ester, as pre-
ð8Þ sented in Table 4, at the later stage of oxidation. The corresponding
chemical structure is presented in Fig. 9. The epoxidation of oils gener-
ð9Þ ally improved the oxidative stability and acid number, increasing the
adsorption capacity on the metal surface, while lowering the viscosity
index, as well as resulting in improved lubricity (Castro et al., 2006;
ð10Þ Doll, Sharma, & Erhan, 2008; Erhan et al., 2008; Salih, Salimon, &
Yousif, 2011; Somidi, Sharma, & Dalai, 2014; Lopes et al., 2010; Gorla
et al., 2013; Silva et al., 2015).
Conclusions
(1) The main components of Jatropha biodiesel were methyl palmi-
tate, methyl oleate and methyl linoleate, while the relative con-
tent of methyl oleate and methyl linoleate with carbon‑carbon
double bonds reached 82.29%.
(2) Compared to single fatty acid methyl esters, the mixed fatty acid
esters and biodiesel had better lubricating properties. The polar
functional group ester group of Jatropha biodiesel was adsorbed
on the metal surface, forming a physical adsorption film. Also,
its carbon‑carbon double bond enhanced the electrostatic force
among the molecules of the adsorption membrane and pro-
moted the lubricating performance of Jatropha biodiesel.
(3) The components of Jatropha biodiesel sustained significant
changes during oxidation. The methyl linoleate contained multi-
ple bisallyl sites that were sensitive to oxidation and became eas-
ily oxidized. During oxidation, the aldehydes, the ketones and
the molecular weights were crucial. Higher oxygenates and solu-
ble polymers were formed.
 Z. Liu et al. / Energy for Sustainable Development 52 (2019) 33–39
Fig. 9. Oxiraneoctanoic acid, 3-octyl-, methyl ester.
(4) The oxidation of biodiesel had a significant effect on the lubricat-
ing properties. The peroxide generated by short-time oxidation
would stimulate the decomposition of fatty acid chains and
destroyed the stability of the lubricating adsorption film; long-
term oxidation would produce highly polar products and epoxy
compounds. A stable boundary film would be desirable on the
metal surface to improve the lubricating properties of biodiesel.
Comparing to fresh biodiesel, long-term storage of biodiesel can im-
prove the lubricity of biodiesel, and short-term oxidation can have a
negative impact on oil friction and wear characteristics. Some perfor-
mance improver additives such as Zinc dialkyldithiophosphates
(ZDDPs) are added in biodiesel to decompose the hydroperoxides.
Acknowledgements
The authors would like to acknowledge the support provided by Na-
tional Natural Science Foundation of China (51766007), NSFC-Yunnan
Joint Fund Project (U1602272), and Research Fund from State Key Lab-
oratory of Complex Nonferrous Metal Resources Clean Utilization
(CNMRCUTS1704).
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