Renewable and Sustainable Energy Reviews 93 (2018) 145–157

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Tribological behavior of biolubricant base stocks and additives T

⁎ ⁎
Chung-Hung Chan , Sook Wah Tang, Noor Khairin Mohd, Wen Huei Lim , Shoot Kian Yeong,
Zainab Idris
Advanced Oleochemical Technology Division, Malaysian Palm Oil Board, 43000 Kajang, Selangor, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: Biolubricants are gaining popularity and acceptance globally due to their sustainable and environmentally
Vegetable oil friendly properties; being derived from feedstocks from vegetable oils. Indeed, the potential for biolubricants to
Biolubricant eventually replace conventional lubricants is currently viewed in the literature as a real possibility. This study
Additives will provide valuable information pertaining to the formulation of biolubricants, by assessing and evidencing the
Tribology
tribological performances of various types of biolubricant base stocks and their related additives. This study
Friction coefficient
begins with a presentation of the basic tribological parameters in lubrication. Following that, the criteria for the
Wear
molecular structure of biolubricant base stocks for high tribological performance are discussed, based both on
the tabulation of the friction coefficient and on the measurement of wear scar from experimental studies. The
biolubricant base stocks under review in this study include vegetable oils (VO), epoxidized VO, ring-opened
products from epoxidized VO, estolides, and polyol esters. This review also discusses recent advances in eco-
friendly tribological additives such as plant-derived compounds and polymers, particulate and layered materials,
and ionic liquids. The performance and various applications of these additives are also reviewed.

1. Introduction
Biolubricants, or bio-based lubricants, are generally perceived as
environmentally friendly, biodegradable and non-toxic lubricants
which are derived from renewable resources such as plant oils and
animal fats. Most biolubricant products currently on the market are
made up either entirely or partially from bio-based oils, providing these
oils fulfill the requirements of international standards in terms of re-
newability, biodegradability, toxicity and technical performance.
According to European standards [1,2], a certified biolubricant must
have a bio-based carbon content of at least 25% and biodegradability of
at least 60%. The biolubricant must also be non-toxic to the environ-
ment and fit for the purpose of an application. The market demand for
biolubricants is driven by various factors, which include: consumer
environmental awareness, government directives and the global de-
mand for lubricants. A long-running and increasingly urgent issue is the
environmental cost of hazardous and non-degradable lubricants en-
tering the ecosystem through total loss applications, spillages and so on
[3]. It is, in fact, well-attested that about half of the total production of
lubricants in the world accumulates in the environment every year
[3,4]. Continuing efforts have been made to fight this crisis through
various government directives and environmental legislation. For in-
stance, the European Union (EU) Renewable Energy Directives 2009/
28/EC were mandated to promote the use of energy from renewable
sources in various sectors including fuels and lubricants [5]. At a con-
sumer level, environmental awareness is being raised by the awarding
of environmental labels such as Blue Angel, Nordic Swan and European
Eco-label for lubricant products [3], with the aim of highlighting the
consequences of consumer purchasing and hiring decisions for the
planet. In addition to the above initiatives, the market growth of bio-
lubricants is further substantiated by the increase in global lubricant
demand due to the specific development of end-user industries in
China, India, South Africa, Brazil and Iran [6,7]. In the current scenario,
the global market for lubricants is growing at approximately 2% an-
nually; amounting to approximately 144.45 billion USD in 2015 [7].
Indeed, the global biolubricant market has always been rising steadily
at 10% annually, in spite of it constituting only about 1% of the total
market in lubricants [8,9]. From this perspective, the shift towards bio-
based lubricants represents a global trend in the global lubricant
market; as part of the global effort to mitigate the environmental im-
pact of hazardous and non-degradable conventional lubricants.
The successful formulation of any lubricant product is built upon a
multi-objective optimization of the types and concentrations of base
stocks and additives, to meet specific application specifications and
requirements [10]. On average, a typical lubricating oil consists of 93%
base stock and 7% additives, though the additive content may vary

⁎
Corresponding authors.
E-mail addresses: rykenz87@yahoo.com, chan@mpob.gov.my (C.-H. Chan), limwen@mpob.gov.my (W.H. Lim).

https://doi.org/10.1016/j.rser.2018.05.024
Received 17 March 2017; Received in revised form 27 March 2018; Accepted 13 May 2018
Available online 23 May 2018
1364-0321/ © 2018 Elsevier Ltd. All rights reserved.
C.-H. Chan et al.
from 1%, as in simple compressor oils, or up to 30%, as in gear oil and
metal-working fluids [11,12]. In any lubricant formulation, base stock
is viewed as the essential part of the lubricating oil, as base stock
possesses the vital lubricant physical properties such as viscosity,
thermal stability, lubricity and so forth. Among all base stocks, vege-
table oil (VO) is the simplest choice for a biolubricant [13–19]. It has in
fact always been the alternative to mineral oil due to its superior lu-
bricity, viscosity index, and wear resistance; not to mention its biode-
gradability and the sustainability of its feedstock [13,20–22]. Un-
fortunately, VO is known to have poor thermal and oxidative stability
[23–25], but by means of chemical modifications, VO may be converted
into better-performing products such as epoxidized VO [26–28], ring-
opened products from epoxidized VO [23,29–31], estolides [32–35],
and polyol esters [36–42]. These base stocks have been seen as pro-
mising for use in biolubricant formulations. Further improvement to
VO-based lubricant performance is possible through additivation. Ad-
ditives are able to enhance the physical properties of the lubricant by
providing additional features, including anti-corrosion, metal scaven-
ging, and anti-wear to the base stock [12]. The most important group of
additives are tribological additives, as far as lubrication is concerned,
since the ability to reduce wear and damage to machines is ultimately
the goal. Indeed, the aim of any new formulation is to achieve better
performance, higher energy efficiency, and a longer life cycle for the
machinery, as well as longer intervals for the replacement of the lu-
bricating oil [43]. It should be mentioned here, of course, that not all
conventionally-used additives are compatible with biolubricant base
stock [12], but tribological additives for biolubricants have so far been
advanced in the field with favorable regard to their lubricity, wear
protection and load-carrying capacity. The additives from this group
which are currently enjoying most research focus are those containing
sulfur and phosphorus [44–47], environmental-friendly polymers
[15,48–50], plant-derived compounds [35,51], particulates [52–56],
two-dimensional (2D) layered materials [57–60], and ionic liquids
[61–64].
In practice, the varying performance of different lubrications in
terms of friction and wear is usually assessed based on the coefficient of
friction (COF) and wear scar diameter (WSD), or volume (WSV), re-
spectively [13,35,65,66]. COF denotes the ratio of friction force be-
tween two bodies and the normal force pressing the bodies together
[67], whereas WSD and WSV are respectively the diameter and volume
of wear after sliding activity. These measurements are often used in
sub-scale machine or laboratory tests to investigate the tribological
behavior of lubricant products in the workings of real machinery. When
evaluating and comparing the tribological behavior of different lu-
brications, it is important to specify the type of lubricant, the tribo-
system, and the lubrication conditions to minimize the discrepancy
between the laboratory test and the field performance [65,67]. In the
context of biolubricants, most of the literature simply discusses over-
views, developments, synthesis and applications of biolubricants in a
very general context [24,28,68–76], or in specific applications [77–87],
while other studies focus only on the development and performance of a
specific type of additive [88–95]. In fact, a thorough search of the re-
levant research yielded no reviews which provided any adequate detail
about aspects of tribological behaviors. This review, therefore, seeks to
address this gap in the literature by providing comprehensive evidence
and valuable discussion pertaining to the tribological performances of
recent biolubricant base stocks, and related additives. This study fo-
cuses on their influencing parameters, molecular structure criteria, sy-
nergisms, and mechanisms; concerning lubricity, wear protection, and
load-carrying capacity. In addition, a detailed tabulation of friction and
wear responses of various biolubricants is presented for comparison
purposes. The aim is for interested parties to be able to utilize the tri-
bological information presented in this review as a guide to selecting
and formulating biolubricants for their own applications.
146
Renewable and Sustainable Energy Reviews 93 (2018) 145–157
2. Basic tribological parameters
The most important consideration for selecting a suitable lubricant
is that it fulfills the lubrication requirements of the particular applica-
tion, especially in its tribological aspects. Tribological performance in
lubrication concerns lubricity, friction and wear. Generally speaking,
lubricity is associated with the formation of the lubrication layer, or
tribofilm, on sliding surfaces. High lubricity reduces the direct contacts
of the surface asperities and thereby lowers friction and energy loss
[11,96]. High lubricity is not always accompanied by better wear
protection, since the mechanism of forming a protective layer on the
sliding surfaces occurs through the adsorption of the surface active
materials of the lubricant, which can be certain types of base stock or
additives [97]. Whenever there is surface asperity contact during the
sliding activity, there is the possibility that three types of mechanical
wear are produced: abrasion, adhesion, and fatigue [46,97]. Abrasive
wear (e.g. grooves) is produced via the removal of a certain volume of
surface material by hard asperities on the sliding surface [98]; adhesive
wear (e.g. attachment of wear debris) is the result of plastic deforma-
tion and strong bonding of the interface materials [98]; fatigue wear
(e.g. crack, fracture) is due to the weakening of surface materials after
repeatedly contact with high local stress for a large number of times
[98]. The obvious solution to the wear problem is to employ thicker
tribofilm, though this is not always efficient and desirable in some
applications, such as metalworking. Prior to any discussion of tribolo-
gical performance, it is essential to understand what are known as the
three basic tribological parameters: the mechanical properties of a tri-
bosystem; the lubrication regime and its conditions; and also the phy-
sical properties and tribochemistry of the lubricant as illustrated in
Fig. 1. The details of each parameter are elucidated as follows.
2.1. Mechanical properties of a tribosystem
The mechanical characteristics of a tribosystem can essentially be
described as the material hardness, the surface roughness, the contact
geometry, and the sliding mechanism of the interacting part and its
counterpart, as presented in Fig. 1(A). Limiting the discussion to the
laboratory tribometer, most sliding materials have a 30–64 Rockwell C
Hardness (HRC) and a 0.01–1.0 µm surface roughness, depending on
the following: the type of material (e.g. steel, magnesium, copper), the
hardening process (e.g. nitriding, carburizing), and the coating (e.g.
carbon-based coating, ultra-high molecular weight polyethylene)
[15–17,26,37,66,99]. Basically, a higher hardness value provides a
lower wear rate, while a lower roughness value provides better lubricity
[100]. Comparing tribological results across different types of trib-
ometers is not possible due to varying sliding geometries (e.g. four-ball,
pin-on-disk, ball-on-disk) and the particular sliding mechanism (e.g.
unidirectional or reciprocating, sliding to rolling ratio) [65,67]. For a
valid comparison, the measurements should be conducted using a si-
milar type of machine and method (e.g. ASTM D5183, ASTM D4172,
and ASTM D6079). Even if all of these conditions are closely matched,
researchers are required to reproduce the measurements in their in-
struments to ensure accuracy.
2.2. Lubrication regimes and conditions
The operating conditions of any tribosystem play a significant role
in characterizing tribofilm and, subsequently, tribological behavior.
According to the famous Stribeck curve [67,101] there are three lu-
brication regimes, namely: boundary; mixed and elastohydrodynamic
(EHL); and hydrodynamic lubrication regimes, as illustrated in
Fig. 1(B). Boundary lubrication usually occurs at high contact load or
low sliding speed lubrication, whereby thin or unstable tribofilm is
formed, causing the contacting surfaces to rub against each other and
generate high friction and wear [102]. As the film thickness in this
regime is less than the surface roughness [102], the presence of surface
C.-H. Chan et al.
Fig. 1. Three basic parameters affecting friction and wear behaviors of a lubricated tribosystem.
active materials is vital in order to protect the contacting surfaces from
sliding damage. Further increase in the sliding speed or decrease in the
contact load shifts the lubrication to a mixed/EHL regime, and then to a
hydrodynamic lubrication regime. Along with this transition, the as-
sociated friction and wear rate decrease since the contacting surfaces
are now separated by a thicker tribofilm due to hydrodynamic lift
[102]. The film thickness is about 1–3 times that of the surface
roughness under mixed/EHL regime, and 3 times greater than the
surface roughness when under a hydrodynamic lubrication regime
[102]. In the latter regime, the sliding contacts are now fully lubricated
and the associated friction is dominated by the viscous drag and re-
sistance of the lubricant. In this manner, there is no significant me-
chanical wear on the moving parts except fatigue [98]. According to
rough tabulations [97], a typical boundary lubrication has a coefficient
of friction (COF) value greater than 0.1, whereas mixed/EHL lubrica-
tion produces a COF in the range of 0.01–0.10, and hydrodynamic lu-
brication gives COF less than 0.01. Note that the sliding speed and
contact load to achieve a certain lubrication regime vary according to
both the tribosystem and the physical properties of the lubricant;
especially the physical property of viscosity. Other influential operating
parameters such as lubrication temperature and assessment time also
need to be specified. In most tribological assessments, the lubrication
operates within a boundary or mixed/EHL regimes, at an operating
temperature which closely matches the required equilibrium tempera-
ture of an application. The friction and wear measurements are taken
after reaching the steady state, which is about an hour of operation, as
adopted in most standard practices.
2.3. Physical and tribochemical properties of lubricant
The physical properties and the tribochemical properties of any
lubricant are the most crucial parameters for tribological performance,
as depicted in Fig. 1(C). In view of the physical properties of base stock,
viscosity and its relationship with temperature and pressure is the
primary property responsible for the thickness of tribofilm, and
147
Renewable and Sustainable Energy Reviews 93 (2018) 145–157
ultimately of tribological performance. For as more viscous lubricant
creates thicker tribofilm but gives lower efficiency due to higher flow
resistance [3], the selection of lubricant viscosity for an application is a
trade-off between lubrication and energy performance. In cases where
elevated temperature and high contact load are involved, a high visc-
osity index and high pressure-viscosity coefficient are preferred in lu-
bricants to ensure stable tribofilm [3]. Other properties that affect the
strength and the stability of tribofilm include: pour point, volatility,
thermal degradation temperature, and oxidative stability [3,98]. On the
other hand, where the tribochemical properties of a lubricant are
concerned; lubricity, wear protection, and load carrying capacity are
exhibited by so-called surface active materials. These surface active
materials mainly act as a friction modifier (FM), an anti-wear additive
(AW), and an extreme pressure additive (EP). More generally, FM
promotes softer and easily sheared protection layers which reduce
sliding friction [20,103], whereas AW and EP actually form a sacrificial
protective layer on the sliding surface to minimize wear [45,46,103].
The typical COF of an FM layer (0.01–0.05) is generally lower than that
of EP and AW layers (0.06–0.15), but higher if compared to tribofilm in
a hydrodynamic regime (< 0.001) [103]. The differences between AW
and EP are that the latter has a higher reactivity and its protective layer
is tougher and thicker, allowing for a higher load tolerance [103]. The
above additives are mostly employed to minimize wear and enhance
lubricity for boundary lubrication and mixed/EHL lubrication regimes.
3. Molecular structure criteria of biolubricant base stocks
The physical and tribochemical properties of biolubricant base
stocks depend very much on the molecular structure of their constituent
compounds. In most biolubricant base stocks, there are polar and non-
polar regions in the molecules [12]. The polar region is responsible for
adsorption or adhesion on a sliding surface, whereas the non-polar re-
gion is responsible for the strength and oiliness of the lubricating fluid
[3]. Some examples of the molecular structure of the base stocks can be
found in Fig. 2. The simplest biolubricant base stock of all is vegetable
C.-H. Chan et al. Renewable and Sustainable Energy Reviews 93 (2018) 145–157

Fig. 2. Molecular structures of biolubricant base stocks and their basic property-structure relationships. Molecular structure: (1) triglyceride, (2) oleic acid, (3)
ricinoleic acid, (4) epoxidized oleic acid, (5) epoxidized ricinoleic acid, (6) oleic estolide, (7) 9-hydroxy-10-acyloxyoctadecanoic acid, (8) octyl 9-hydroxy-10-
acyloxyoctadecanoate, (9) octyl 9-(lauroyloxy)-10-(acyloxy)octadecanoate, (10) 10,12-dihydroxy-9-acyloxystearic acid, (11) octyl 10,12-dihydroxy-9-acylox-
ystearate, (12) trimethylolpropane (TMP) ester, (13) pentaerythritol (PE) ester, (14) neopentyl glycol (NPG) ester.

oil (VO). VO is triglyceride consisting of three straight chained fatty
acids attached to a glycerol backbone by ester linkage. Typically, the
fatty acid chains in VO triglyceride have a 14–24 carbon atoms chain
length, with varying degrees of unsaturation [24], although coconut oil
has mostly 12 carbon atoms in its fatty acid chain [104] and castor oil
has an additional hydroxyl group (-OH) in the fatty acid chain (i.e. ri-
cinoleic acid) [33]. Due to the intrinsic instability of the β-hydrogen
atom in the glycerol backbone coupled with the unsaturation site at the
fatty acid chains in VO, it is accepted that chemical modifications on
such sites are possible with the aim of generating better oxidative and
thermal stabilities for products such as, epoxidized VO, ring-opened
products from epoxidized VO, estolides, and polyol esters [69]. Epox-
idized VO is actually produced by forming a highly reactive oxirane
ring at the unsaturation site of the fatty acid chain [105]. Subsequently,
the oxirane ring reacts with suitable organic acid or aliphatic alcohols
to produce poly-functional molecules [105,106]. Estolide, on the other
hand, is produced through homopolymerization of fatty acids at its
unsaturation sites by ester linkage. It is characterized by the degree of
polymerization or estolide number [32,107]. Lastly, polyol esters can
be produced from VO methyl ester or fatty acid through transester-
ification or esterification with polyols, including neopentyl glycol
(NPG), trimethylolpropane (TMP) and pentaerythritol (PE) [108–111].

148
C.-H. Chan et al.
The performances of the aforementioned base stocks can essentially be
based on four criteria: degree of unsaturation, carbon chain length,
functional group(s) and branching effect [112,113]. A schematic dia-
gram showing the effects of the molecular structure criteria on the
physical and tribological properties of biolubricant base stocks is pre-
sented in Fig. 2. The details of each criterion will be elucidated as
follows.
3.1. Degree of unsaturation
Degree of unsaturation refers to the number of unsaturation sites in
the carbon chains of a molecule. This criterion is often used to assess the
non-polar regions of VO molecules, since the oil contains different
compositions of saturated and unsaturated fatty acid chains. A thorough
study performed by Reeves et al. [16] found that the higher the degree
of unsaturation of VO, the higher were the COF and WSV produced.
This is because the unsaturation site disrupts and prevents the carbon
chains of VO from forming a densely packed bundle, weakening the
stability of the tribofilm [16,17,114]. It is also evidenced that highly
unsaturated VO tends to have a higher composition of free fatty acids,
which may induce chemical wear on the sliding material due to its
reactive carboxyl group (RCOOH) [17,49]. Nevertheless, at extreme
pressure lubrication, the reactive carboxyl group of the free fatty acid
may have an excellent anti-wear effect [18], as it allows better coupling
of the fatty acid with the sliding material to produce low friction car-
boxylate soap protective film [115]. As a whole, the effect of un-
saturation of VO on tribological performance is significant only in
metallic-to-metallic contact, since the metallic oxide layer allows che-
misorption of VO or free fatty acid [98]. Otherwise, it does not result in
any substantial difference, as is reported in the lubrication of ultra-
high-molecular-weight polyethylene (UHMWPE) sliding contacts using
sesame and Nigella sativa oils [66]. In spite of the fact that a low degree
of unsaturation is preferred in tribological performance, and also for
better thermal and oxidative stabilities, it is desirable to keep certain
degree of unsaturation, so that the unsaturation sites disrupt the
stacking of molecules and crystallization to prevent any hardening of
the base stock and subsequently to improve the cold flow property (e.g.
a low pour point) [116]. It is therefore agreed that a monounsaturated
carbon chain like the oleic acid chain is the best tradeoff in most base
stocks, including VO [16,19,29] and other synthetic esters
[109,117,118].
3.2. Carbon chain length and molecular weight
Carbon chain length in the non-polar region of biolubricant base
stock molecules usually amounts to 8–22 carbon atoms chain length.
Longer chain length molecules tend to create thicker tribofilm due to
their increase in molecular weight and viscosity. Longer chain length
also reduces the contact of asperities while increasing the protected
surface area. With the increase in molecular weight and viscosity, long
chain length base stocks tend to shift the lubrication regime (as in
Fig. 1(B)) to the right to give lower COF, WSD and WSV [66,119].
While increasing the chain length of biolubricant molecules is desirable
for better tribological performance, it nonetheless affects some of the
physical properties of the biolubricant. Usually, a long chain length in
biolubricant molecules improves tribological performance and viscosity
index, but at the cost of both pour point and oxidative stability [34,39].
These effects are not obvious for VOs, since their average chain length
spans only a narrow range, typically in between 16 and 18 carbon
atoms [17,104], but the effects are profound and significant in esto-
lides, polyol esters and the ring-opened products from epoxidized fatty
acids. For example, estolide capped with shorter chain fatty acids (C2 to
C10) gives a better pour point (−12 to −30 °C) [34,107] when it is
capped with a long chain fatty acid or when it undergoes a large degree
of polymerization and its anti-wear property is enhanced due to viscous
tribofilm [35]. Another example can be seen in the case of TMP ester
149
Renewable and Sustainable Energy Reviews 93 (2018) 145–157
[39], where incorporating a longer chain of alkyl (C5 to C18) into the
ester actually enhances both its pour point (−75 °C to −42 °C) and
viscosity index (80–208). A different length of alkyl chain can tailor the
ester to a specific application [39]: Valeric acid-TMP ester (C5) is sui-
table, as cutting fluids at low-temperature application due to low
viscosity; Caprylic acid–TMP ester (C8) is used for high viscosity and
stability applications like dielectric coolants and rail wheel lubricants;
in addition to TMP-oleate (C18), which is mostly employed for hy-
draulic fluid. It is important to know that the above relationship be-
tween the carbon chain length and the pour point is not applicable for
biolubricant molecules that have significant steric hindrance, such as
base stocks from ring-opening of epoxidized VO. In this case, the re-
lationship is in reverse: the increase in the chain length creates a larger
steric barrier to inhibit the molecule from crystallization [29,120], thus
improving its cold flow property [105].
3.3. Functional groups
The polarity in the polar region of a biolubricant molecule affects its
intermolecular interaction and its interaction with sliding surfaces. This
polarity influences both the tribological behavior and the physical
properties of the biolubricant molecule. The most common functional
group in biolubricants is the ester group (RCOOR). The ester group has
only a mild polarity, but it is able to provide sufficient adhesive
strength to form tribofilm with a sliding surface. It exhibits better anti-
friction capability [13,17,37,99] and promotes lower operating tem-
perature in gear compared to mineral oils [121–123]. However, the
ester group does not have any superior anti-wear effect on the boundary
lubrication regime, due to its mild polarity and adhesiveness [13,14].
Another functional group which is commonly found in biolubricant
molecules is the hydroxyl group (OH). The hydroxyl group creates a
thick and viscous fluid as a result of hydrogen intermolecular bonding.
A biolubricant with a hydroxyl group such as castor oil is suitable for
applications which operate in a mixed/EHL and hydrodynamic lu-
brication, such as hydraulic fluid [15,48]. Other than strong inter-
molecular bonding, the presence of a hydroxyl group favors micro-
crystal particle solubilization [124], but it compromises the cold flow
property and oxidation stability, unless the molecule possesses steric
hindrance [29,106]. Among all groups, the strongest polar group
available in biolubricant base stocks is the carboxyl group (RCOOH)
such as fatty acids and their derivatives [106,120]. The molecule with
the carboxyl group has a strong adhesion to metallic surfaces in addi-
tion to possessing good anti-wear properties in boundary lubrication
[16,20,125,126]. If the oxide layer of a sliding surface is worn off and
there is no chemisorption site for adhesion, a chemical attack on the
material may occur in which the reactive carboxyl group causes soft-
ening and melting of the metallic soap [98]. The above effects of
functional groups can be multiplied and intensified with the increase of
the number of functional group in the molecule. Taking the ester group
as an example, ring-opened products from epoxidized oil that have
more ester functional groups provide greater resistance to shear force
and better wear protection [119].
3.4. Branching and steric hindrance
Introducing branching around the polar region of a biolubricant
molecule helps to shield the molecule from physical and chemical in-
teractions due to steric hindrance. As mentioned previously, biolu-
bricant molecules with steric hindrance such as ring-opened products
from epoxidized oil [105,106] and polyol esters [108] are able to in-
hibit the stacking of molecules and crystallization. At low temperature
conditions, the molecules instead form a microcrystalline structure.
This structure allows the molecules to tumble and glide over one an-
other to give fluidity [25]. In addition to that, other known advantages
of having a branching structure in the molecule include better thermal,
oxidative and hydrolytic stabilities [53,116]. In spite of the favorable
C.-H. Chan et al. Renewable and Sustainable Energy Reviews 93 (2018) 145–157

Table 1
Tribological performances of biolubricant base stocks.
a a
Ref. Tribosystem Lubrication Base stock, viscosity (40 °C) COF WSD / WCV
conditions

[16] Pin-on-disk test: pin (oxygen-free electronic 10 N, 36 mm/s, 25 °C soybean oil, 25.9 cP 0.406 0.384 mm3
copper C101, 6.35 mm diameter, 50 mm length, corn oil, 26.8 cP 0.446 0.297 mm3
hemispherical tip); disk (aluminum alloy 2024, sesame oil, 28.6 cP 0.318 0.215 mm3
70 mm diameter, 6.35 mm thickness, 0.3 µm canola oil, 29.9 cP 0.087 0.201 mm3
roughness) peanut oil, 31.9 cP 0.098 0.168 mm3
genetically-modified safflower oil, 31.9 cP 0.494 0.195 mm3
avocado oil, 31.9 cP 0.020 0.104 mm3
olive oil, 32.7 cP 0.078 0.175 mm3
[17] Four-ball test: ball (AISI E-52100 chrome alloy 2574 MPa, 1200 rpm, coconut oil, 24.8 cSt 0.101 0.601 mm
steel, 12.7 mm diameter, extra polish EP grade 75 °C sunflower oil, 27.8 cSt 0.060 0.616 mm
25, 64–66 HRC hardness) rice bran oil, 40.6 cSt 0.073 0.585 mm
mineral oil, 105 cSt 0.117 0.549 mm
[66] Pin-on-disk test: pin (stainless steel, 0.06 µm 20 N, 30 mm/s, 25 °C sesame oil, 58.0 cP b 0.028 0.024 mm3
roughness); disk (ultra-high-molecular weight Nigella sativa oil, 64.5 cP b 0.032 0.028 mm3
polyethylene UHMWP, 0.31 µm roughness) dry or no lubricant 0.290 0.051 mm3
[18] Four-ball test: ball (Chrome alloy steel, 12.7 mm load, 1200 rpm, 75 °C olive oil, 37.042 cSt 0.052 0.621 mm
diameter, 0.1 µm roughness, 62 HRC hardness) load = 400 N commercial SAE15W40 oil, 103 cSt 0.080 0.717 mm
load = 500 N olive oil, 37.042 cSt 0.061 0.850 mm
commercial SAE15W40 oil, 103 cSt 0.084 1.172 mm
load = 600 N olive oil, 37.042 cSt 0.073 1.254 mm
commercial SAE15W40 oil, 103 cSt 0.090 1.640 mm
load = 800 N olive oil, 37.042 cSt 0.077 1.501 mm
commercial SAE15W40 oil, 103 cSt 0.097 2.095 mm
[19] Ball-on-disk (High frequency reciprocating rig load, speed (8 mm Jatropha Curcas L. oil, 36.61 cSt 0.126 < 0.001 mm3
(HFRR)): ball (AISI E52100 steel, 10 mm stroke), 20 °C hydrotreated rapeseed oil (paraffinic hydrocarbon containing free 0.164 < 0.001 mm3
diameter), disk (X210Cr12 steel) load = 10 N fatty acid and triglycerides), 4.68 cSt
speed = 10 Hz. rapeseed methyl ester (biodiesel), 2.83 cSt 0.139 0.001 mm3
load = 10 N Jatropha Curcas L. oil, 36.61 cSt 0.109 0.001 mm3
speed = 20 Hz hydrotreated rapeseed oil, 4.68 cSt 0.134 < 0.001 mm3
rapeseed methyl ester (biodiesel), 2.83 cSt 0.115 0.002 mm3
load = 20 N Jatropha Curcas L. oil, 36.61 cSt 0.129 0.003 mm3
speed = 10 Hz hydrotreated rapeseed oil, 4.68 cSt 0.153 < 0.001 mm3
rapeseed methyl ester (biodiesel), 2.83 cSt 0.132 0.002 mm3
load = 20 N Jatropha Curcas L. oil, 36.61 cSt 0.106 0.010 mm3
speed = 20 Hz hydrotreated rapeseed oil, 4.68 cSt 0.134 < 0.001 mm3
rapeseed methyl ester (biodiesel), 2.83 cSt 0.125 0.008 mm3
[26] Ball-on-disk test (HFRR): ball (AISI 52100 steel, 2 N, 20 Hz (1 mm moringa oil, 44.9 cSt 0.084 0.15 mm
570–750 HV hardness, 6 mm diameter); disk stroke), 60 °C passion fruit oil, 31.8 cSt 0.060 0.076 mm
(AISI 52100 steel, 190–210 HV hardness, 10 mm epoxidized moringa oil, 80.4 cSt 0.080 0.146 mm
diameter, #1200 polished surface) epoxidized passion fruit oil, 185.7 cSt 0.068 0.131 mm
commercial hydraulic oil A, 80–100 cSt 0.123 0.181 mm
commercial hydraulic oil B, > 150 cSt 0.103 0.164 mm
[29] Four-ball test: ball (AISI E-52100 chrome alloy 392 N, 1200 rpm, epoxidized oleic acid, 0.804 g/cm3 c 0.58 0.89 mm
steel, 12.7 mm diameter, extra polish EP grade 75 °C monoester
25, 64–66 HRC hardness) 9-hydroxy-10-octyloxyoctadecanoic acid, 0.813 g/cm3 c 0.47 0.83 mm
9-hydroxy-10-nonanoxyoctadecanoic acid, 0.819 g/cm3 c 0.42 0.75 mm
9-hydroxy-10-lauroxyoctadecanoic acid, 0.822 g/cm3 c 0.38 0.68 mm
9-hydroxy-10-myristoxyoctadecanoic acid, 0.826 g/cm3 c 0.27 0.56 mm
9-hydroxy-10-palmitoxyoctadecanoic acid, 0.830 g/cm3 c 0.21 0.48 mm
9-hydroxy-10-stearoxyoctadecanoic acid, 0.833 g/cm3 c 0.18 0.35 mm
9-hydroxy-10-behenoxyoctadecanoic acid, 0.836 g/cm3 c 0.14 0.28 mm
diester
octyl 9-hydroxy-10-octyloctadecanoate, 0.841 g/cm3 c 0.46 0.66 mm
octyl 9-hydroxy-10-nonanoxyoctadecanoate, 0.843 g/cm3 c 0.40 0.59 mm
octyl 9-hydroxy-10-lauroxyoctadecanoate, 0.846 g/cm3 c 0.33 0.53 mm
octyl 9-hydroxy-10-myristoxyoctadecanoate, 0.851 g/cm3 c 0.23 0.46 mm
octyl 9-hydroxy-10-palmitoxyoctadecanoate, 0.855 g/cm3 c 0.17 0.39 mm
octyl 9-hydroxy-10-stearoxyoctadecanoate, 0.858 g/cm3 c 0.13 0.34 mm
octyl 9-hydroxy-10-behenoxyoctadecanoate, 0.862 g/cm3 c 0.09 0.25 mm
Triester
octyl 9-(lauroyloxy)−10-(octyloxy)octadecanoate, 0.905 g/cm3 c 0.35 0.61 mm
octyl 9-(lauroyloxy)−10-(nonanoxy)octadecanoate, 0.913 g/cm3 c 0.31 0.53 mm
octyl 9-(lauroyloxy)−10-(lauroxy)octadecanoate, 0.920 g/cm3 c 0.25 0.49 mm
octyl 9-(lauroyloxy)−10-(myristoxy)octadecanoate, 0.925 g/cm3 c 0.20 0.42 mm
octyl 9-(lauroyloxy)−10-(palmitoxy)octadecanoate, 0.931 g/cm3 c 0.14 0.31 mm
octyl 9-(lauroyloxy)−10-(stearoxy)octadecanoate, 0.939 g/cm3 c 0.08 0.22 mm
octyl 9-(lauroyloxy)−10-(behenoxy)octadecanoate, 0.946 g/cm3 c 0.06 0.14 mm
(continued on next page)

150
C.-H. Chan et al. Renewable and Sustainable Energy Reviews 93 (2018) 145–157

Table 1 (continued)
a a
Ref. Tribosystem Lubrication Base stock, viscosity (40 °C) COF WSD / WCV
conditions

[30] Ball-on-disk test (HFRR): ball (AISI 52100 steel, 200 g, 50 Hz (1 mm low lubricity diesel fuel (LLDF), n/a 0.400 0.656 mm
570–750 HV hardness, 6 mm diameter); disk stroke), 60 °C blend of LLDF and ring opening products of epoxidized canola oil 0.119 0.179 mm
(AISI 52100 steel, 190–210 HV, 10 mm diameter, with n-butanol at ratio 95:5 w/w, 251.7 cSt d
#1200 polished surface) blend of LLDF and ring opening products of epoxidized canola oil 0.099 0.142 mm
with amyl alcohol at ratio 95:5 w/w, 190.5 cSt d
blend of LLDF and ring opening products of epoxidized canola oil 0.081 0.120 mm
with 2-ethylhexanol at ratio 95:5 w/w, 85.5 cSt d
[35] Ball-on-three-plates test: plate (45° inclined, 20 N, 400 rpm, 25 °C oleic acids-estolides with degree of polymerization of 6.33 (O1), n/a 0.247 mm
C45E-1.1191 steel, 25–30 HRC hardness); ball 415.59 cSt
(100Cr6 steel, 12.7 mm diameter) ricinoleic acids-estolides with degree of polymerization of 6.92 (R1), n/a 0.174 mm
6712.98 cSt
blend of high-oleic sunflower oil (HOSO) and O1 at ratio: 85:15 w/ n/a 0.332 mm
w, 51.31 cSt
blend of HOSO and R1 at ratio: 85:15 w/w, 69.15 cSt n/a 0.242 mm
HOSO, 41.94 cSt n/a 0.357 mm
[42] Ball-on-disk test (HFRR): ball (detail n/a); disk 1 kg, 50 Hz (1 mm Lunaria annua oil-based TMP ester, 29.97 cSt 0.079 0.269 mm
(detail n/a) stroke), 25 °C mineral oil, 28.10 cSt 0.149 0.344 mm
[38] Four-ball test: ball (AISI 52–100 steel, 12.7 mm 40 kg, 1200 rpm, palm oil-based TMP ester (POTMP), 40.03 cSt 0.081 0.8053 mm
diameter, 64–66 HRC hardness) 75 °C ordinary lubricant (OL), 101.86 cSt 0.068 0.3511 mm
blend of OL and POTMP at ratio: 99:1 v/v, 108.75 cSt 0.064 0.3441 mm
blend of OL and POTMP at ratio: 97:3 v/v, 107.21 cSt 0.052 0.2789 mm
blend of OL and POTMP at ratio: 95:5 v/v, 101.42 cSt 0.056 0.3125 mm
blend of OL and POTMP at ratio: 93:7 v/v, 102.15 cSt 0.053 0.3631 mm
blend of OL and POTMP at ratio: 90:10 v/v, 97.637 cSt 0.065 0.3898 mm
[37] Four-ball test: ball (AISI 52–100 steel, 12.7 mm 1000 N, 1770 rpm, palm oil-based TMP ester, 40.03 cSt 0.25 2.47 mm
diameter, 64–66 HRC hardness) 25 °C palm oil-based PE ester, 68.40 cSt 0.06 2.54 mm
mineral oil, 30.61 cSt welded welded
commercial fully formulated lubricant, 101.86 cSt 0.08 0.54 mm
[36] Four-ball test: ball (AISI 52–100 steel, 12.7 mm 40 kg, 1200 rpm, palm oil-based NPG ester, 27.92 cSt 0.092 0.659 mm
diameter, 64–66 HRC hardness) Temperature (T) palm oil-based PE ester, 72.78 cSt 0.094 0.669 mm
T= 50 °C palm oil-based PE ester with anti-wear and anti-corrosion additives, 0.063 0.377 mm
75.37 cSt
commercial fully formulated lubricant, 131.76 cSt 0.087 0.218 mm
T= 100 °C palm oil-based NPG ester, 27.92 cSt 0.093 1.213 mm
palm oil-based PE ester, 72.78 cSt 0.050 0.584 mm
palm oil-based PE ester with anti-wear and anti-corrosion additives, 0.046 0.338 mm
75.37 cSt
commercial fully formulated lubricant, 131.76 cSt 0.101 0.434 mm

a
Values obtained at steady state or after sufficiently long sliding duration
b
Viscosity at 20 °C
c
Density is given instead since viscosity data is not available
d
Kinematic viscosity of the ring opening products at 40 °C rather than the mixture

physical properties above, excessive molecular branching puts the tri-
bological properties at risk, as the adhesion of the molecule on the
sliding surface could be disrupted and the probability of asperity con-
tact increased [98]. Molecular branching is nonetheless still beneficial
in lubrication involving high contact loads or extreme pressure. Indeed,
in extreme cases, as observed in polyol esters; particularly TMP and PE
ester [38], molecular branching actually improves the load-carrying
capacity of the base stocks when benchmarking against mineral oils.
This is because molecular branching helps to stabilize the tribofilm
from breaking apart [122].
4. Tribological performances of biolubricant base stocks
Base stock is the primary element which determines the final
properties of a lubricant product. Even with the best additives, a poorly
performing base stock can only be improved with difficulty. The se-
lection of suitable base stock either in its neat form or in a combination
of various types of base stocks (blend or emulsion) is usually based on a
list of properties, viz. physical properties, material compatibility, re-
newability, degradability and so on. As one of these properties, tribo-
logical performance is the most critical criterion. Recognizing its im-
portance, Table 1 tabulates the tribological performances of various
types of lubricant base stocks. Their key tribological behaviors will be
elucidated subsequently.
A biolubricant base stock with ester functional groups such as VO is
more efficient in terms of its frictional properties and wear protection
than mineral oils [18]. VOs with a low degree of unsaturation such as
avocado oil (0.985 unsaturation), olive oil (0.948 unsaturation), and
peanut oil (1.102 unsaturation) exhibit superior frictional properties
compared to high unsaturation VOs such as soybean oil (1.451 un-
saturation), corn oil (1.381 unsaturation) and sesame oil (1.232 un-
saturation) [16]. Their wear protection effects, nonetheless, are not
promising, particularly under extreme pressure conditions in a four-ball
test [17]. It is interesting to note that VOs derived from the breeding of
genetically-modified organisms (GMOs) such as safflower oil (1.010
unsaturation) in work [16] do not follow the trends of other natural
oils, probably due to their distinct structures in terms of their fatty
acids. On the other hand, short-chained VOs such as coconut oil are not
efficient as far as frictional properties are concerned [17]. Should a
thicker fluid be required for an application such as hydraulic fluid,
epoxidized VO may be considered, as it has about twice the viscosity
value of the original VO [26]. It also performs better in COF and WSD
relative to commercial hydraulic oils within the same viscosity range
[26]. Another alternative to resolve the low viscosity problem is to
incorporate estolide as a thickening agent, as seen in the case whereby
oleic acid-based and ricinoleic acid-based estolides can be blended into
a low viscosity fluid to improve wear performance [35]. When lu-
bricating at extreme operating temperatures and enduring a heavy

151
C.-H. Chan et al.
contact load, biolubricant base stocks with significant molecular
branching and steric hindrance, namely the ring-opened products from
epoxidized oil and the polyol ester, can be employed. The molecular
branching resists crystallization at a low temperature and degradation
at an elevated temperature and pressure, producing stable tribofilm
which are versatile and may be used for various applications [53,116].
According to the data tabulated in Table 1, it is suggested that the
dominant molecular structure criteria affecting lubricity and wear
protection at boundary lubrication is the degree of molecular
branching, followed by molecular chain length, and number of ester
functional groups, in descending order. The latter two parameters are
more profound in mixed/EHL and hydrodynamic regimes as they affect
the viscosity of the fluid and the adhesion of tribofilm, respectively
[101]. It should be noted that the effect of viscosity on friction is not
significant in boundary lubrication [98]. The above observation is ob-
tained based on the following cases: The triester product of ring-
opening of epoxidized oleic acid produced lower COF and smaller WSD
in boundary lubrication as compared to the monoester and the diester
[29]. This comparison was done at the basis of similar chain lengths
attached to the ester functional group. In addition, the ring-opened
product of epoxidized canola oil with branched alcohol such as 2-
ethylhexanol exhibits better wear protection when blended into a low
lubricity oil, compared with that blended with other more viscous
products derived from linear alcohols [30]. In the studies involving
polyol esters, PE ester gives better lubricity than TMP and NPG esters,
especially at an elevated temperature (e.g. 100 °C) and under extreme
pressure (e.g. 100 kg load). This is because PE possesses a higher
branching degree and therefore a much more stable molecular structure
[36,37]. TMP and NPG esters may perform better at mild operating
conditions, or in mixed/EHL lubrication regimes. In actual fact, it is
difficult to isolate and investigate the tribological performances of NPG,
TMP and PE esters, since their molecular weight and degree of steric
hindrance are varying, giving rise to different viscosities, thermal sta-
bility, and cold flow property [36,37]. Each type of ester has its own
advantages: they can be designed and tailored to give specific physical
properties and tribological advantages to suit a specific application.
5. Tribological enhancement using biolubricant additives
In the current scenario, environmental concerns continue to drive
original equipment manufacturers to change their specifications for
lubricant performances. Lubricant formulation has been developed in
such a way that the elements of chlorine, phosphorus, sulfur, and me-
tals in the formulation are already reduced [47]. This helps to mitigate
environmental impact, as it is well known that the toxic and not readily
degradable additives may accumulate in the environment and harm the
ecosystem [127]. There are various types of additives available nowa-
days, but most of them are not environmentally friendly. For instance,
zinc dialkyl dithiophosphate (ZDDP) has been used in engines both as
an anti-wear and antioxidant additive for decades, despite its non-de-
gradability and toxicity in nature [3,98]. As far as environmental
friendliness is concerned, the tribological additives for biolubricant
which are currently receiving most attention from researchers are
plant-derived compounds and polymers, particulate and layered mate-
rials and ionic liquids. Their tribological performances are tabulated in
Table 2. These additives will be briefly discussed in the following
subsections.
5.1. Plant-derived compounds and polymers
Plant-derived compounds such as cystine schiff base ester are po-
tential anti-friction, anti-wear and anti-corrosion additives [51]. They
are comprised of disulfide groups, along with amine and carboxylic
functionalities, which are capable of forming a surface-complex film,
particularly when metal-to-metal contact is involved [51]. As this type
of additive is relatively new, its tribological properties are yet to
152
Renewable and Sustainable Energy Reviews 93 (2018) 145–157
achieve what the current conventional additives can offer. On the other
hand, ethylene-vinyl acetate copolymer (EVA) and ethyl cellulose (EC)
are known as viscosity modifiers. Even when constituting only a slight
weight percentage of the additives in a base stock, they are able to boost
the viscosity of base stock at least by two-fold [15,48]. They are also
able to form a thicker film for better frictional, wear, and load-carrying
properties [15,50]. In fact, both polymers excel in different applica-
tions. EVA helps to reduce friction and wear mainly in the mixed lu-
brication regime, whereas EC is more effective in extreme boundary
lubrication [15]. In view of other improvements [50], EC is able to
sustain tribofilm at a high temperature, in addition to acting as an ex-
cellent pour point depressant, which is proven to be more effective than
EVA and mineral oil additives with a polymethacrylate backbone. The
above advantages are nonetheless dependent on the solubility of the
additives in the base stock. In one study [50], blending high oleic
sunflower oil with a more polar oil, e.g. castor oil, can boost the solu-
bility of EC. This blend became a potentially eco-friendly base stock
which was suitable for various applications due to a wide range of
viscosity, good low-temperature properties and low degree of tem-
perature-viscosity dependency.
5.2. Particulate and layered materials
Nano-sized particulates such as CuO, TiO2 and ZnO are non-toxic
anti-wear additives for biolubricants. With their sizes ranging from
around 2 to 120 nm [3], these materials are able to coalesce in asperity
valleys, creating a thin, smooth and solid lamellar film between con-
tacting surfaces [52,57]. As a result, these solid particulates provide
superior frictional and wear properties [52,57]. Their performance
depends very much on the surface roughness of the sliding materials. If
the particulate size is slightly smaller than the surface roughness, the
wear volume decreases with the decrease of particulate size [54,57].
When the particulate size is extremely small (e.g. five-fold smaller)
relative to the surface roughness, the wear volume increases with the
decrease in the particle size [57]. In the case whereby particulate size is
larger than the surface roughness, grooves from abrasions are produced
[57]. Another parameter affecting frictional and wear behavior is the
concentration of the additive. The presence of excessive additive par-
ticles in the asperities valleys could either give insignificant improve-
ment in tribological performance [56], or produce abrasive wear
(ploughing effects) by increasing the shear-concentration at the contact
surface [60]. The latter may be due to the interference of the additive
particles causing poor adsorption of base stock at the contact area re-
sulting in inadequate lubrication, as observed in the case of nano-
particles in polar oils such as ester-based oil [56] and VO [128]. The
above relationships are also applicable for two-dimensional (2D)
layered materials, including hexagonal boron nitride (hBN), boric ni-
tride and graphene [54,60]. The nature of 2D layered materials and the
particulates is different, whereby the former are known for their low
interlayer friction ability and the ability to accommodate relative sur-
face velocity to produce low COF during sliding [57,58]. Taking gra-
phene as an example [58], its atoms lying on the same layer are closely
bonded together by strong covalent bonds, while the layers are attached
together by weak Van der Waals. When employing nanoparticles and
layered materials additives, replenishment of the solid additives is re-
quired as the additive may be molten, welded or forced out of the tri-
bosystem after a certain time. Therefore, an effective suspension or
colloidal system that is stable and compatible with the solid additives is
crucial.
5.3. Ionic liquids
Ionic liquids have been applied in almost every field, including lu-
brication, due to their limitless pool of structural variations and prop-
erties. Among the variety of ionic liquids, imidazolium-based ionic li-
quid is claimed to have a great potential and to be a versatile lubricant
C.-H. Chan et al. Renewable and Sustainable Energy Reviews 93 (2018) 145–157

Table 2
Tribological enhancement of biolubricants using additives.
a a
Ref. Tribosystem Lubrication conditions Base stock, viscosity (40 °C) COF WSD / WCV

[15] Ball-on-disk test (HFRR): ball (AISI 52100 4 N, 50 Hz (1 mm stroke), T high-oleic sunflower oil (HOSO), 38.5 cSt 0.049 0.18 mm
steel, 800 VPN hardness, 6 mm diameter); HOSO with 4% w/w ethylene-vinyl acetate copolymer (EVA), 0.047 0.19 mm
disk (AISI 52100 steel, 750 VPN, 10 mm 168.14 cSt
diameter) HOSO with 1% w/w ethyl cellulose (EC), 50.6 cSt 0.075 0.20 mm
T = 40 °C castor oil (CO), 242.5 cSt 0.087 0.34 mm
CO with 4% w/w EVA, 427.1 cSt 0.057 0.16 mm
CO with 1% w/w EC, 546.7 cSt 0.050 0.17 mm
T = 100 °C HOSO, 9.9 cSt b 0.085 0.20 mm
HOSO with 4% w/w EVA, 29.6 cSt b 0.067 0.22 mm
HOSO with 1% w/w EC, 15.1 cSt b 0.071 0.41 mm
CO, 21 cSt b 0.043 0.14 mm
CO with 4% w/w EVA, 50.9 cSt b 0.085 0.55 mm
CO with 1% w/w EC, 40.3 cSt b 0.034 0.16 mm
[50] Ball-on-disk test (minitraction machine 30 N, entrainment speed HOSO, 39.0 cSt 0.034 n/a
(MTM)): ball (AISI 52100 steel, 19.05 mm (50% slide-to-roll ratio), T HOSO with 1% w/w EC, 51 cSt 0.028 n/a
diameter 11 nm roughness); disk (AISI 52100 T = 40 °C CO, 242 cSt 0.033 n/a
steel, 50 mm diameter, 11 nm roughness) Entrainment speed = CO with 1% w/w EC, 547 cSt 0.030 n/a
0.01 m/s blend of HOSO and CO at ratio 1:1 w/w, n/a 0.027 n/a
blend of HOSO and CO at ratio 1:1 w/w with 1% w/w EC, 174 cSt 0.028 n/a
T = 40 °C HOSO, 39.0 cSt 0.021 n/a
HOSO with 1% w/w EC, 51 cSt 0.031 n/a
Entrainment speed = CO, 242 cSt 0.034 n/a
0.1 m/s CO with 1% w/w EC, 547 cSt 0.030 n/a
blend of HOSO and CO at ratio 1:1 w/w, n/a 0.025 n/a
blend of HOSO and CO at ratio 1:1 w/w with 1% w/w EC, 174 cSt 0.026 n/a
T = 40 °C HOSO, 39.0 cSt 0.021 n/a
HOSO with 1% w/w EC, 51 cSt 0.022 n/a
Entrainment speed = 1 m/s CO, 242 cSt 0.027 n/a
CO with 1% w/w EC, 547 cSt 0.024 n/a
blend of HOSO and CO at ratio 1:1 w/w, n/a 0.024 n/a
blend of HOSO and CO at ratio 1:1 w/w with 1% w/w EC, 174 cSt 0.025 n/a
T = 100 °C HOSO, 10 cSt b 0.052 n/a
HOSO with 1% w/w EC, 15 cSt b 0.016 n/a
Entrainment speed = CO, 21 cSt b 0.051 n/a
0.01 m/s CO with 1% w/w EC, 40 cSt b 0.051 n/a
blend of HOSO and CO at ratio 1:1 w/w, n/a 0.049 n/a
blend of HOSO and CO at ratio 1:1 w/w with 1% w/w EC, 26 cSt b 0.032 n/a
T = 100 °C HOSO, 10 cSt b 0.034 n/a
HOSO with 1% w/w EC, 15 cSt b 0.016 n/a
Entrainment speed = CO, 21 cSt b 0.022 n/a
0.1 m/s CO with 1% w/w EC, 40 cSt b 0.027 n/a
blend of HOSO and CO at ratio 1:1 w/w, n/a 0.016 n/a
blend of HOSO and CO at ratio 1:1 w/w with 1% w/w EC, 26 cSt b 0.016 n/a
T = 100 °C HOSO, 10 cSt b 0.011 n/a
Entrainment speed = 1 m/s HOSO with 1% w/w EC, 15 cSt b 0.013 n/a
CO, 21 cSt b 0.015 n/a
CO with 1% w/w EC, 40 cSt b 0.014 n/a
blend of HOSO and CO at ratio 1:1 w/w, n/a 0.012 n/a
blend of HOSO and CO at ratio 1:1 w/w with 1% w/w EC, 26 cSt b 0.013 n/a
[51] Four-ball test: ball (AISI 52–100 steel, 198 N load, 1200 rpm, 75 °C polyol base oil, n/a 0.068 0.90 mm
12.7 mm diameter, 64–66 HRC hardness) polyol base oil with 1000 ppm cysteine schiff base ester prepared via 0.075 0.91 mm
two step synthesis using 3,5-di-t-butyl-4-hydroxybenzaldehyde
followed by lauroyl alcohol (CySBE), n/a
polyol base oil with 2000 ppm CySBE, n/a 0.068 0.81 mm
polyol base oil with 3000 ppm CySBE, n/a 0.055 1.00 mm
[52] Four-ball test: ball (AISI 52–100 steel, load, 1770 rpm, 25 °C polyol ester oil, 40.03 cSt n/a 0.58 mm
12.7 mm diameter, 64–66 HRC hardness) polyol ester oil with 1% w/w oleic acid, 39.27 cSt n/a 0.58 mm
polyol ester oil with 1% w/w CuO nanoparticles, 40.25 cSt n/a 0.55 mm
load = 40 kg polyol ester oil with 1% w/w MoS2 nanoparticles, 40.96 cSt n/a 0.48 mm
polyol ester oil with 1% w/w CuO nanoparticles and 1% w/w oleic n/a 0.54 mm
acid, 40.17 cSt
polyol ester oil with 1% w/w MoS2 nanoparticles and 1% w/w oleic n/a 0.51 mm
acid, 40.09 cSt
load = 160 kg polyol ester oil, 40.03 cSt n/a welded
polyol ester oil with 1% w/w oleic acid, 39.27 cSt n/a welded
polyol ester oil with 1% w/w CuO nanoparticles, 40.25 cSt n/a 3.26 mm
polyol ester oil with 1% w/w MoS2 nanoparticles, 40.96 cSt n/a 3.04 mm
polyol ester oil with 1% w/w CuO nanoparticles and 1% w/w oleic n/a 3.14 mm
acid, 40.17 cSt
polyol ester oil with 1% w/w MoS2 nanoparticles and 1% w/w oleic n/a 2.88 mm
acid, 40.09 cSt
(continued on next page)

153
C.-H. Chan et al. Renewable and Sustainable Energy Reviews 93 (2018) 145–157

Table 2 (continued)
a a
Ref. Tribosystem Lubrication conditions Base stock, viscosity (40 °C) COF WSD / WCV

[56] Pin-on-disk test: pin (AISI 1020 steel, load, 0.5 m/s, T mineral oil, 103.55 cSt 0.063 n/a
7.92 mm diameter); disk (AISI 52100 steel, T = 40 °C mineral oil with 0.3% w/w Cu nano-additive, 107.10 cSt 0.014 n/a
100 mm diameter, 64–66 HRC roughness) mineral oil with 3.0% w/w Cu nano-additive, 107.98 cSt 0.006 n/a
load = 392 N synthetic ester, 107.54 cSt 0.009 n/a
synthetic ester with 0.3% w/w Cu nano-additive, 108.50 cSt 0.004 n/a
synthetic ester with 3.0% w/w Cu nano-additive, 110.88 cSt 0.008 n/a
T = 40 °C mineral oil, 103.55 cSt 0.067 n/a
mineral oil with 0.3% w/w Cu nano-additive, 107.10 cSt 0.012 n/a
mineral oil with 3.0% w/w Cu nano-additive, 107.98 cSt 0.080 n/a
load = 588 N synthetic ester, 107.54 cSt 0.027 n/a
synthetic ester with 0.3% w/w Cu nano-additive, 108.50 cSt 0.006 n/a
synthetic ester with 3.0% w/w Cu nano-additive, 110.88 cSt 0.090 n/a
T = 100 °C mineral oil, 11.55 cSt b 0.111 n/a
mineral oil with 0.3% w/w Cu nano-additive, 11.87 cSt b 0.106 n/a
mineral oil with 3.0% w/w Cu nano-additive, 12.06 cSt b 0.107 n/a
load = 588 N synthetic ester, 14.70 cSt b 0.077 n/a
synthetic ester with 0.3% w/w Cu nano-additive, 14.81 cSt b 0.074 n/a
synthetic ester with 3.0% w/w Cu nano-additive, 15.05 cSt b 0.078 n/a
Four-ball test: ball (AISI 52100 steel, 12.7 mm 392 N, 1200 rpm, 75 °C mineral oil, 103.55 cSt n/a 0.88 mm
diameter, 64–66 HRC hardness) mineral oil with 0.3% w/w Cu nano-additive, 107.10 cSt n/a 0.70 mm
mineral oil with 3.0% w/w Cu nano-additive, 107.98 cSt n/a 0.74 mm
synthetic ester, 107.54 cSt n/a 0.79 mm
synthetic ester with 0.3% w/w Cu nano-additive, 108.50 cSt n/a 0.86 mm
synthetic ester with 3.0% w/w Cu nano-additive, 110.88 cSt n/a 1.11 mm
[57] Pin-on-disk test: pin (oxygen-free electronic 10 N, 33 mm/s, 25 °C canola oil mixed with 5% w/w of 5μm hexagonal boron nitride (hBN) 0.123 0.132 mm3
copper C101, 6.35 mm diameter, 50 mm particles, n/a
length, hemispherical tip); disk (aluminum canola oil mixed with 5% w/w of 1.5μm hBN particles, n/a 0.078 0.080 mm3
alloy 2024, 70 mm diameter, 6.35 mm canola oil mixed with 5% w/w of 0.5 μm hBN particles, n/a 0.056 0.069 mm3
thickness, Ra roughness) canola oil mixed with 5% w/w of 0.07μm hBN particles, n/a 0.035 0.025 mm3
Ra = 0.22 μm
Ra = 0.43 μm canola oil mixed with 5% w/w of 5μm hBN particles, n/a 0.072 0.359 mm3
canola oil mixed with 5% w/w of 1.5μm hBN particles, n/a 0.073 0.392 mm3
canola oil mixed with 5% w/w of 0.5 μm hBN particles, n/a 0.090 0.465 mm3
canola oil mixed with 5% w/w of 0.07μm hBN particles, n/a 0.093 0.434 mm3
[60] Four-ball test: ball (AISI 52–100 steel, 392 N, 1200 rpm, 75 °C jatropha oil-based TMP triester, 16.87 cSt 0.022 1.280 μm
12.7 mm diameter, 64–66 HRC hardness jatropha oil-based TMP triester with 0.05% w/w of 2–5 μm hBN 0.022 1.238 μm
particles, 17.13 cSt
jatropha oil-based TMP triester with 0.1% w/w of 2–5 μm hBN 0.026 1.514 μm
particles, 17.20 cSt
jatropha oil-based TMP triester with 0.5% w/w of 2–5 μm hBN 0.029 1.590 μm
particles, 17.56 cSt
commercial synthetic ester, 19.05 cSt 0.090 1.553 μm
[63] Four-ball test: ball (GCr15 steel, 61–64 HRC load, 1450 rpm, 75 °C Ionic liquid emulsion consists of 6% w/w I-butyl-3-methyl- 0.079 0.652 mm
hardness) load = 392 N imidazolium tetrafluoroborate [BMIM][BF4], 19% w/w castor oil,
60% w/w Tx-100 surfactant, 15% w/w 1-butanol, n/a
Commercial lubricant base oil, n/a 0.107 0.801 mm
load = 588 N Ionic liquid emulsion consists of 6% w/w [BMIM][BF4], 19% w/w 0.054 0.859 mm
castor oil, 60% w/w Tx-100 surfactant, 15% w/w 1-butanol, n/a
Commercial lubricant base oil, n/a 0.098 0.842 mm
load = 784 N Ionic liquid emulsion consists of 6% w/w [BMIM][BF4], 19% w/w 0.064 0.901 mm
castor oil, 60% w/w Tx-100 surfactant, 15% w/w 1-butanol, n/a
Commercial lubricant base oil, n/a 0.088 0.883 mm
[62] Ball-on-disk test (HFRR): ball (steel); disk 100 N, 25 Hz (1 mm stroke), trimethylolpropane oleate (TMPTO), 49.6 cSt 0.143 0.005 mm3
(steel) 150 °C TMPTO with 3% 1-tetradecyl-3-(2-ethylhexyl)imidazolium bis(2- 0.122 0.0098 mm3
ethylhexyl) phosphate [TDEHIM][DEHP], 51.23 cSt
TMPTO with 5% [TDEHIM][DEHP], 52.5 cSt 0.114 0.0057 mm3
TMPTO with 7% [TDEHIM][DEHP], 53.37 cSt 0.112 0.0095 mm3
[64] Four-ball test: ball (AISI 52–100 steel, 392 N, 1200 rpm, 75 °C polyol ester oil, 45.82 cSt 0.132 0.954 mm
12.7 mm diameter, 64–66 HRC hardness) polyol ester oil with 2% w/w aspartic acid and glutamic acid derived 0.0681 0.750 mm
ionic liquids (ILs) 1, 46.28 cSt
polyol ester oil with 2% w/w ILs 2, 46.38 cSt 0.0681 0.562 mm

a
Values obtained at steady state after sufficient sliding duration
b
Viscosity at 100 °C

which is applicable to various types of sliding materials [129,130]. On
top of its unique properties such as low volatility, non-flammability,
negligible vapor pressure, and superior chemical and thermal stabilities
[130], this ionic liquid possesses excellent lubricating properties, in-
cluding friction reduction, anti-wear and high load-carrying capacity
[130–132]. Nevertheless, the immiscibility of ionic liquid in non-polar
mediums like fatty hydrocarbon and vegetable oil is the major draw-
back. This technical restriction can be overcome with ionic liquid
microemulsion [61,63]. For example, ionic liquid microemulsion
comprising of 1-butyl-3-methyl-imidazolium tetrafluoroborate, [BMIM]
[BF4], a surfactant, and a vegetable oil, produced better tribological
results than conventional base stock [63]. In the latest development, the
dual roles of ionic liquid can been seen in the synthesis of polyol ester
base stocks, whereby ionic liquid, namely 1-tetradecyl-3-(2-ethylhexyl)
imidazolium bis(2-ethylhexyl) phosphate [TDEHIM][DEHP], acts as an
efficient catalyst and at the same time works as an in situ anti-wear

154
C.-H. Chan et al. Renewable and Sustainable Energy Reviews 93 (2018) 145–157

Table 3
Tribological influences of biolubricant base stocks and additives.
Effectsa Base stocksb Additivesc

Increase Increase chain length Increase Increase branching Plant-derived Particulate and Ionic
unsaturation (molecular weight) polarity degree (steric polymer (EC, layered materialse liquid
hindrance) EVA)d

Tribofilm characteristics
Film thickness + + +
Adhesion strength – + – –
Low temperature flow + – – + +
Viscosity index +
Thermo-oxidative stability – – +
Tribological performance
Lubricity – + + + + +
Wear protection – + + + + +
Load-carrying capacity + + +
(extreme pressure)
Application
Boundary lubrication + + + + + +
Mixed lubrication + + + + +
High temperature – – +

a
Positive effect [+ ]; negative effect [-]; unknown or insignificant effect [].
b
Base stocks: vegetable oil (VO), epoxidized VO, ring opening products from epoxidized VO, estolides and polyol esters.
c
Effectiveness depends on solubility and compatibility.
d
EC: ethyl cellulose; EVA: ethylene-vinyl acetate copolymer.
e
Effectiveness depends on topological condition of contact surface.

additive, eliminating the need for catalyst separation from the synthe-
sized ester [62]. In addition, biodegradable and non-toxic amino-acid
based ionic liquids have been synthesized as anti-wear additive and
friction modifier. They are able to form a stable homogeneous disper-
sion with polyol ester base stock [64].
6. Final remarks
It is clear, then, that biolubricants derived from renewable energy
sources like plant oils are becoming more viable with the development
of various types of environmentally friendly base stocks and additives.
They are able to perform as well as conventional lubricants, and can
even be applied and incorporated into broader applications, including
biofuels and bioenergy. A successful formulation of biolubricant relies
on the selection of suitable biolubricant base stocks and additives to
meet a list of specifications required by an application. In terms of the
tribological aspect, a good biolubricant base stock can be ensured by
optimizing two characteristics: the stability and the adhesiveness of its
generated tribofilm within the lubricating conditions, provided that the
viscosity range of the lubricant and the lubrication regime are suitable
and tally with the application requirements. Tribological additives can
be then added to further improve the base stock. In summary, this re-
view offers an in-depth discussion and comprehensive evidence of the
tribological behaviors of biolubricant base stocks and additives. The
influences of biolubricant base stocks and additives on tribological
performance are summarized in Table 3. It is hoped that the tribological
data presented in this review may assist interested parties in preparing
and formulating biolubricants which fulfill basic lubrication require-
ments.
Acknowledgement
The author thanks the Director-General of MPOB for permission to
publish this work.
Declarations of interest
none
References
[1] European Committee for Standardization. Liquid petroleum products-Bio-lu-
bricants-Recommendation for terminology and characterisation of bio-lubricants
and bio-based lubricants. CEN/TR 162272011.
[2] European Committee for Standardization. Liquid Petroleum Products-Bio-
Lubricants-Criteria And Requirements Of Bio-Lubricants And Bio-Based Lubricants.
prEN 168072014.
[3] Rudnick LR. Synthetics, mineral oils, and bio-based lubricants: chemistry and
technology. New York: CRC Press; 2005.
[4] Hinman ML. Environmental characteristics of fuel and lubricants. In: Totten GE,
Westbrook SR, Shah RJ, editors. Fuels and lubricants handbook: technology,
properties, performance, and testing. West Conshohocken: ASTM International;
2003. p. 885–909.
[5] European Commission. Directive 2009/28/EC of the European Parliament and of
the Council of 23 April 2009 on the promotion of the use of energy from renewable
sources and amending and subsequently repealing Directives 2001/77/EC and
2003/30/EC. Official Journal of the European Union; 2009. p. 16-62.
[6] Gill G Slowly, The World’s Lube Thirst Grows. Lubes‘n’Greases; 2014. January
issue. p. 37-42.
[7] Markets And Markets. Lubricants Market by Type (Mineral Oil, Synthetic
Lubricants, Bio-Based, and Greases), by Application (Transportation and Industrial
Machinery & Equipment), and by Region (APAC, EU, NA, MEA, AND SA) - Global
Forecast to 2021.
[8] Infiniti Research Limited. Global Biolubricant Market 2015–2019; 2015.
[9] Grand View Research. Biolubricants Market Analysis By Raw Material (Vegetable
& Animal Oil), By Application (Automotive (Automotive Engine Oils, Gear Oils,
Hydraulic Oils, Transmission Fluids, Greases, Chainsaw Oils), Industrial (Process
Oils, Demolding Oils, Industrial Gear Oils, Industrial Greases, Metal Working
Fluids)), By End-Use (Industrial, Commercial Transportation, Consumer
Automotive) Segment Forecasts To 2024; 2016.
[10] Sethuramiah A, Kumar R. Modeling of chemical wear. Oxford: Elsevier; 2016. p.
185–211.
[11] Srivastava SP. Advances in lubricant additives and tribology. New Delhi: CRC
Press; 2010.
[12] Bart JCJ, Gucciardi E, Cavallaro S. Biolubricants: science and technology. Oxford:
Woodhead Publishing; 2013. p. 351–95.
[13] Chiong Ing T, Rafiq AKM, Azli Y, Syahrullail S. Tribological behaviour of refined
bleached and deodorized palm olein in different loads using a four-ball tribotester.
Sci Iran 2012;19:1487–92.
[14] Syahrullail S, Kamitani S, Shakirin A. Performance of vegetable oil as lubricant in
extreme pressure condition. Procedia Eng 2013;68:172–7.
[15] Quinchia LA, Delgado MA, Reddyhoff T, Gallegos C, Spikes HA. Tribological stu-
dies of potential vegetable oil-based lubricants containing environmentally
friendly viscosity modifiers. Tribol Int 2014;69:110–7.
[16] Reeves CJ, Menezes PL, Jen T-C, Lovell MR. The influence of fatty acids on tri-
bological and thermal properties of natural oils as sustainable biolubricants. Tribol
Int 2015;90:123–34.
[17] Rani S, Joy ML, Nair KP. Evaluation of physiochemical and tribological properties
of rice bran oil - biodegradable and potential base stoke for industrial lubricants.

155
C.-H. Chan et al.
Ind Crops Prod 2015;65:328–33.
[18] Kalam MA, Masjuki HH, Cho HM, Mosarof MH, Mahmud MI, Chowdhury MA,
Zulkifli NWM. Influences of thermal stability, and lubrication performance of
biodegradable oil as an engine oil for improving the efficiency of heavy duty diesel
engine. Fuel 2017;196:36–46.
[19] Ruggiero A, D’Amato R, Merola M, Valašek P, Müller M. Tribological character-
ization of vegetal lubricants: comparative experimental investigation on Jatropha
curcas L. oil, Rapeseed Methyl Ester oil, Hydrotreated Rapeseed oil. Tribol Int
2017;109:529–40.
[20] Fox NJ, Tyrer B, Stachowiak GW. Boundary lubrication performance of free fatty
acids in sunflower oil. Tribol Lett 2004;16:275–81.
[21] Kalin M, Vižintin J. A comparison of the tribological behaviour of steel/steel,
steel/DLC and DLC/DLC contacts when lubricated with mineral and biodegradable
oils. Wear 2006;261:22–31.
[22] Willing A. Lubricants based on renewable resources – an environmentally com-
patible alternative to mineral oil products. Chemosphere 2001;43:89–98.
[23] Salimon J, Salih N, Yousif E. Improvement of pour point and oxidative stability of
synthetic ester basestocks for biolubricant applications. Arab J Chem
2012;5:193–200.
[24] Erhan SZ, Asadauskas S. Lubricant basestocks from vegetable oils. Ind Crops Prod
2000;11:277–82.
[25] Erhan SZ, Sharma BK, Perez JM. Oxidation and low temperature stability of ve-
getable oil-based lubricants. Ind Crops Prod 2006;24:292–9.
[26] Silva MS, Foletto EL, Alves SM, de Castro Dantas TN, Dantas Neto AA. New hy-
draulic biolubricants based on passion fruit and moringa oils and their epoxy. Ind
Crops Prod 2015;69:362–70.
[27] Salih N, Salimon J, Yousif E. Synthetic biolubricant basestocks based on en-
vironmentally friendly raw materials. J King Saud Univ Sci 2012;24:221–6.
[28] Campanella A, Rustoy E, Baldessari A, Baltanás MA. Lubricants from chemically
modified vegetable oils. Bioresour Technol 2010;101:245–54.
[29] Salih N, Salimon J, Yousif E. The physicochemical and tribological properties of
oleic acid based triester biolubricants. Ind Crops Prod 2011;34:1089–96.
[30] Madankar CS, Dalai AK, Naik SN. Green synthesis of biolubricant base stock from
canola oil. Ind Crops Prod 2013;44:139–44.
[31] Kulkarni RD, Deshpande PS, Mahajan SU, Mahulikar PP. Epoxidation of mustard
oil and ring opening with 2-ethylhexanol for biolubricants with enhanced thermo-
oxidative and cold flow characteristics. Ind Crops Prod 2013;49:586–92.
[32] Isbell TA, Cermak SC. Synthesis of triglyceride estolides from lesquerella and
castor oils. J Am Oil Chem Soc 2002;79:1227–33.
[33] Isbell TA, Lowery BA, DeKeyser SS, Winchell ML, Cermak SC. Physical properties
of triglyceride estolides from lesquerella and castor oils. Ind Crops Prod
2006;23:256–63.
[34] Cermak SC, Isbell TA. Synthesis and physical properties of mono-estolides with
varying chain lengths. Ind Crops Prod 2009;29:205–13.
[35] García-Zapateiro LA, Franco JM, Valencia C, Delgado MA, Gallegos C. Viscous,
thermal and tribological characterization of oleic and ricinoleic acids-derived es-
tolides and their blends with vegetable oils. J Int Eng Chem 2013;19:1289–98.
[36] Aziz NAM, Yunus R, Rashid U, Zulkifli NWM. Temperature effect on tribological
properties of polyol ester-based environmentally adapted lubricant. Tribol Int
2016;93:43–9. [Part A].
[37] Zulkifli NWM, Azman SSN, Kalam MA, Masjuki HH, Yunus R, Gulzar M. Lubricity
of bio-based lubricant derived from different chemically modified fatty acid me-
thyl ester. Tribol Int 2016;93:555–62. [Part B].
[38] Zulkifli NWM, Kalam MA, Masjuki HH, Shahabuddin M, Yunus R. Wear prevention
characteristics of a palm oil-based TMP (trimethylolpropane) ester as an engine
lubricant. Energy 2013;54:167–73.
[39] Åkerman CO, Gaber Y, Ghani NA, Lämsä M, Hatti-Kaul R. Clean synthesis of
biolubricants for low temperature applications using heterogeneous catalysts. J
Mol Catal B Enzym 2011;72:263–9.
[40] Sripada PK, Sharma RV, Dalai AK. Comparative study of tribological properties of
trimethylolpropane-based biolubricants derived from methyl oleate and canola
biodiesel. Ind Crops Prod 2013;50:95–103.
[41] da Silva JAC, Soares VF, Fernandez- Lafuente R, Habert AC, Freire DMG.
Enzymatic production and characterization of potential biolubricants from castor
bean biodiesel. J Mol Catal B Enzym 2015;122:323–9.
[42] Dodos GS, Karonis D, Zannikos F, Lois E. Renewable fuels and lubricants from
Lunaria annua L. Ind Crops Prod 2015;75:43–50. [Part B].
[43] Sethuramiah A, Kumar R. Chapter 2 - Lubricants and their formulation. Modeling
of chemical wear. Oxford: Elsevier; 2016. p. 25–39.
[44] Born M, Hipeaux JC, Marchand P, Parc G. The relationship between chemical
structure and effectiveness of some metallic dialkyl- and diaryl-dithiophosphates
in different lubricated mechanisms. Lubr Sci 1992;4:93–116.
[45] Watkins RC. The antiwear mechanism of zddp's. Part II. Tribol Int 1982;15:13–5.
[46] Kim B, Jiang JC, Aswath PB. Mechanism of wear at extreme load and boundary
conditions with ashless anti-wear additives: analysis of wear surfaces and wear
debris. Wear 2011;270:181–94.
[47] Kim B, Mourhatch R, Aswath PB. Properties of tribofilms formed with ashless di-
thiophosphate and zinc dialkyl dithiophosphate under extreme pressure condi-
tions. Wear 2010;268:579–91.
[48] Quinchia LA, Delgado MA, Valencia C, Franco JM, Gallegos C. Viscosity mod-
ification of different vegetable oils with EVA copolymer for lubricant applications.
Ind Crops Prod 2010;32:607–12.
[49] Martín-Alfonso JE, Valencia C. Tribological, rheological, and microstructural
characterization of oleogels based on EVA copolymer and vegetables oils for lu-
bricant applications. Tribol Int 2015;90:426–34.
[50] Delgado MA, Quinchia LA, Spikes HA, Gallegos C. Suitability of ethyl cellulose as
156
Renewable and Sustainable Energy Reviews 93 (2018) 145–157
multifunctional additive for blends of vegetable oil-based lubricants. J Clean Prod
2017;151:1–9.
[51] Singh RK, Pandey S, Saxena RC, Thakre GD, Atray N, Ray SS. Study of cystine
schiff base esters as new environmentally benign multifunctional biolubricant
additives. J Ind Eng Chem 2015;26:149–56.
[52] Gulzar M, Masjuki HH, Varman M, Kalam MA, Mufti RA, Zulkifli NWM, et al.
Improving the AW/EP ability of chemically modified palm oil by adding CuO and
MoS2 nanoparticles. Tribol Int 2015;88:271–9.
[53] Zulkifli NWM, Kalam MA, Masjuki HH, Yunus R. Experimental analysis of tribo-
logical properties of biolubricant with nanoparticle additive. Procedia Eng
2013;68:152–7.
[54] Lovell MR, Kabir MA, Menezes PL, Higgs CF. Influence of boric acid additive size
on green lubricant performance. Philos Trans A Math Phys Eng
2010;368:4851–68.
[55] Tan K-H, Awala H, Mukti RR, Wong K-L, Ling TC, Mintova S, et al. Zeolite na-
noparticles as effective antioxidant additive for the preservation of palm oil-based
lubricant. J Taiwan Inst Chem E 2016;58:565–71.
[56] Guzman Borda FL, Ribeiro de Oliveira SJ, Seabra Monteiro Lazaro LM, Kalab
Leiróz AJ. Experimental investigation of the tribological behavior of lubricants
with additive containing copper nanoparticles. Tribol Int 2018;117:52–8.
[57] Reeves CJ, Menezes PL, Lovell MR, Jen T-C. The influence of surface roughness
and particulate size on the tribological performance of bio-based multi-functional
hybrid lubricants. Tribol Int 2015;88:40–55.
[58] Zhou Y, Dahl J, Carlson R, Liang H. Effects of molecular structures of carbon-based
molecules on bio-lubrication. Carbon 2015;86:132–8.
[59] Hu X. On the size effect of molybdenum disulfide particles on tribological per-
formance. Ind Lubr Tribol 2005;57:255–9.
[60] Talib N, Nasir RM, Rahim EA. Tribological behaviour of modified jatropha oil by
mixing hexagonal boron nitride nanoparticles as a bio-based lubricant for ma-
chining processes. J Clean Prod 2017;147:360–78.
[61] Wang A, Chen L, Jiang D, Zeng H, Yan Z. Vegetable oil-based ionic liquid micro-
emulsion biolubricants: effect of integrated surfactants. Ind Crops Prod
2014;62:515–21.
[62] Zhu L, Zhao Q, Wu X, Zhao G, Wang X. A novel phosphate ionic liquid plays dual
role in synthetic ester oil: from synthetic catalyst to anti-wear additive. Tribol Int
2016;97:192–9.
[63] Wang A, Chen L, Jiang D, Yan Z. Vegetable oil-based ionic liquid microemulsions
and their potential as alternative renewable biolubricant basestocks. Ind Crops
Prod 2013;51:425–9.
[64] Nagendramma P, Khatri PK, Thakre GD, Jain SL. Lubrication capabilities of amino
acid based ionic liquids as green bio-lubricant additives. J Mol Liq
2017;244:219–25.
[65] Blau PJ. The significance and use of the friction coefficient. Tribol Int
2001;34:585–91.
[66] Guezmil M, Bensalah W, Mezlini S. Effect of bio-lubrication on the tribological
behavior of UHMWPE against M30NW stainless steel. Tribol Int 2016;94:550–9.
[67] Maru MM, Tanaka DK. Consideration of stribeck diagram parameters in the in-
vestigation on wear and friction behavior in lubricated sliding. J Braz Soc Mech Sci
Eng 2007;29:55–62.
[68] Zia KM, Noreen A, Zuber M, Tabasum S, Mujahid M. Recent developments and
future prospects on bio-based polyesters derived from renewable resources: a re-
view. Int J Biol Macromol 2016;82:1028–40.
[69] McNutt J, He Q. Development of biolubricants from vegetable oils via chemical
modification. J Ind Eng Chem 2016;36:1–12.
[70] Prerna Singh C, VKC. Non-edible oil as a source of bio-lubricant for industrial
applications: a review. Int J Eng Sci Innov Technol 2013;2:299–305.
[71] Nagendramma P, Kaul S. Development of ecofriendly/biodegradable lubricants: an
overview. Renew Sust Energ Rev 2012;16:764–74.
[72] Lu C, Napier JA, Clemente TE, Cahoon EB. New frontiers in oilseed biotechnology:
meeting the global demand for vegetable oils for food, feed, biofuel, and industrial
applications. Curr Opin Biotechnol 2011;22:252–9.
[73] Schneider MP. Plant‐oil‐based lubricants and hydraulic fluids. J Sci Food Agric
2006;86:1769–80.
[74] Panchal TM, Patel A, Chauhan DD, Thomas M, Patel JV. A methodological review
on bio-lubricants from vegetable oil based resources. Renew Sust Energ Rev
2017;70:65–70.
[75] Syahir AZ, Zulkifli NWM, Masjuki HH, Kalam MA, Alabdulkarem A, Gulzar M,
et al. A review on bio-based lubricants and their applications. J Clean Prod
2017;168:997–1016.
[76] Zainal NA, Zulkifli NWM, Gulzar M, Masjuki HH. A review on the chemistry,
production, and technological potential of bio-based lubricants. Renew Sust Energ
Rev 2018;82:80–102.
[77] Mariprasath T, Kirubakaran V. A critical review on the characteristics of alter-
nating liquid dielectrics and feasibility study on pongamia pinnata oil as liquid
dielectrics. Renew Sust Energ Rev 2016;65:784–99.
[78] Rafiq M, Lv YZ, Zhou Y, Ma KB, Wang W, Li CR, et al. Use of vegetable oils as
transformer oils – a review. Renew Sust Energ Rev 2015;52:308–24.
[79] Kania D, Yunus R, Omar R, Abdul Rashid S, Mohamad Jan B. A review of biolu-
bricants in drilling fluids: recent research, performance, and applications. J Pet Sci
Eng 2015;135:177–84.
[80] Myant C, Cann P. On the matter of synovial fluid lubrication: implications for
Metal-on-Metal hip tribology. J Mech Behav Biomed Mater 2014;34:338–48.
[81] Mobarak HM, Niza Mohamad E, Masjuki HH, Kalam MA, Al Mahmud KAH,
Habibullah M, et al. The prospects of biolubricants as alternatives in automotive
applications. Renew Sust Energ Rev 2014;33:34–43.
[82] Debnath S, Reddy MM, Yi QS. Environmental friendly cutting fluids and cooling
C.-H. Chan et al.
techniques in machining: a review. J Clean Prod 2014;83:33–47.
[83] Berman D, Erdemir A, Sumant AV. Graphene: a new emerging lubricant. Mater
Today 2014;17:31–42.
[84] Lawal SA, Choudhury IA, Nukman Y. Application of vegetable oil-based me-
talworking fluids in machining ferrous metals—A review. Int J Mach Tool Manuf
2012;52:1–12.
[85] Shashidhara YM, Jayaram SR. Vegetable oils as a potential cutting fluid?An evo-
lution. Tribol Int 2010;43:1073–81.
[86] John J, Bhattacharya M, Raynor PC. Emulsions containing vegetable oils for cut-
ting fluid application. Colloids Surf A Physicochem Eng Asp 2004;237:141–50.
[87] Singh Y, Farooq A, Raza A, Mahmood MA, Jain S. Sustainability of a non-edible
vegetable oil based bio-lubricant for automotive applications: a review. Process Saf
Environ Prot 2017;111:701–13.
[88] Wan S, Tieu AK, Xia Y, Zhu H, Tran BH, Cui S. An overview of inorganic polymer
as potential lubricant additive for high temperature tribology. Tribol Int
2016;102:620–35.
[89] Shahnazar S, Bagheri S, Abd Hamid SB. Enhancing lubricant properties by nano-
particle additives. Int J Hydrog Energy 2016;41:3153–70.
[90] Dai W, Kheireddin B, Gao H, Liang H. Roles of nanoparticles in oil lubrication.
Tribol Int 2016;102:88–98.
[91] Saidur R, Kazi SN, Hossain MS, Rahman MM, Mohammed HA. A review on the
performance of nanoparticles suspended with refrigerants and lubricating oils in
refrigeration systems. Renew Sust Energ Rev 2011;15:310–23.
[92] Hudson LK, Eastoe J, Dowding PJ. Nanotechnology in action: overbased nanode-
tergents as lubricant oil additives. Adv Colloid Interface Sci
2006;123–126:425–31.
[93] Maleque MA, Masjuki HH, Sapuan SM. Vegetable‐based biodegradable lubricating
oil additives. Ind Lubr Tribol 2003;55:137–43.
[94] Darminesh SP, Sidik NAC, Najafi G, Mamat R, Ken TL, Asako Y. Recent develop-
ment on biodegradable nanolubricant: a review. Int J Heat Mass Transf
2017;86:159–65.
[95] Xiao H, Liu S. 2D nanomaterials as lubricant additive: a review. Mater Des
2017;135:319–32.
[96] Amiri M, Khonsari MM. On the thermodynamics of friction and wear―a review.
Entropy 2010;12:1021.
[97] (a) Bruce RW. Handbook of lubrication and tribology: theory and design. 2nd ed.
London: Taylor & Francis; 2012;
(b) Bruce RW. Section 1: theory and practice of lubrication and tribology. 2nd ed.
London: Taylor & Francis; 2012.
[98] (a) Stachowiak GW, Batchelor AW. Engineering tribology. 4rth ed. Boston:
Butterworth-Heinemann; 2013;
(b) Stachowiak GW, Batchelor AW. Chapter 8: boundary and extreme pressure
lubrication. 4rth ed. Boston: Butterworth-Heinemann; 2013;
(c) Stachowiak GW, Batchelor AW. Chapter 11: abrasive, erosive and cavitation
wear. 4rth ed. Boston: Butterworth-Heinemann; 2013;
(d) Stachowiak GW, Batchelor AW. Chapter 12: adhesion and adhesive wear. 4rth
ed. Boston: Butterworth-Heinemann; 2013;
(e) Stachowiak GW, Batchelor AW. Chapter 14: fatigue wear. 4rth ed. Boston:
Butterworth-Heinemann; 2013.
[99] Barriga J, Kalin M, Acker KV, Vercammen K, Ortega A, Leiaristi L. Tribological
performance of titanium doped and pure DLC coatings combined with a synthetic
bio-lubricant. Wear 2006;261:9–14.
[100] Menezes PL, Kishore, Kailas SV, Lovell MR. Role of surface texture, roughness, and
hardness on friction during unidirectional sliding. Tribol Lett 2011;41:1–15.
[101] Bayer RG. Mechanical wear prediction and prevention. New York: Marcel Dekker;
1994.
[102] Hamrock BJ, Dowson D. Ball bearing lubrication: the elastohydrodynamics of el-
liptical contacts. New York: Wiley-Interscience; 1981.
[103] Papay AG. Antiwear and extreme-pressure additives in lubricants. Lubr Sci
1998;10:209–24.
[104] Jayadas NH, Prabhakaran Nair K, GA. Tribological evaluation of coconut oil as an
environment-friendly lubricant. Tribol Int 2007;40:350–4.
[105] Lathi PS, Mattiasson B. Green approach for the preparation of biodegradable lu-
bricant base stock from epoxidized vegetable oil. Appl Catal B 2007;69:207–12.
[106] Salimon J, Salih N, Yousif E. Chemically modified biolubricant basestocks from
epoxidized oleic acid: improved low temperature properties and oxidative
157
Renewable and Sustainable Energy Reviews 93 (2018) 145–157
stability. J Saudi Chem Soc 2011;15:195–201.
[107] Cermak SC, Isbell TA. Synthesis and physical properties of cuphea-oleic estolides
and esters. J Am Oil Chem Soc 2004;81:297–303.
[108] Aziz NAM, Yunus R, Rashid U, Syam AM. Application of response surface meth-
odology (RSM) for optimizing the palm-based pentaerythritol ester synthesis. Ind
Crops Prod 2014;62:305–12.
[109] Yunus R, Fakhru’L-Razi A, Ooi TL, Iyuke SE, Idris A. Development ofoptimum
synthesis method for transesterification of palm oil methyl esters andtrimethy-
lolpropane to environmentally acceptable palm oil-based lubricant. J Oil Palm Res
2003;15:35–41.
[110] Choo YM, Cheng SF, Ma AN, Yusof B Lubricant base oil of palm origin. 2012; US
patent 8101560 B2.
[111] Yeong Sk, Ooi TL, Ahmad S. Lubricant base from palm oil and its by-products; US
patent 7781384 B2; 2010.
[112] Adhvaryu A, Biresaw G, Sharma BK, Erhan SZ. Friction behavior of some seed oils:
biobased lubricant applications. Ind Eng Chem Res 2006;45:3735–40.
[113] Briscoe WH. Aqueous boundary lubrication: molecular mechanisms, design
strategy, and terra incognita. Curr Opin Colloid Interface Sci 2017;27:1–8.
[114] Lundgren SM, Persson K, Mueller G, Kronberg B, Clarke J, Chtaib M, et al.
Unsaturated fatty acids in alkane solution: adsorption to steel surfaces. Langmuir
2007;23:10598–602.
[115] Sahoo RR, Biswas SK. Frictional response of fatty acids on steel. J Colloid Interface
Sci 2009;333:707–18.
[116] Mathiesen T. Modified TMP esters as multifunctional additives in metalworking
fluids. J Synth Lubr 1998;14:381–90.
[117] Yunus R, Fakhru'l-Razi A, Ooi TL, Iyuke SE, Perez JM. Lubrication properties of
trimethylolpropane esters based on palm oil and palm kernel oils. Eur J Lipid Sci
Tech 2004;106:52–60.
[118] Kamalakar K, Manoj GNVTS, Prasad RBN, Karuna MSL. Influence of structural
modification on lubricant properties of sal fat-based lubricant base stocks. Ind
Crops Prod 2015;76:456–66.
[119] Havet L, Blouet J, Robbe Valloire F, Brasseur E, Slomka D. Tribological char-
acteristics of some environmentally friendly lubricants. Wear 2001;248:140–6.
[120] Salih N, Salimon J, Abdullah BM, Yousif E. Thermo-oxidation, friction-reducing
and physicochemical properties of ricinoleic acid based-diester biolubricants. Arab
J Chem 2014.
[121] Martins RC, Cardoso NFR, Bock H, Igartua A, Seabra JHO. Power loss performance
of high pressure nitrided steel gears. Tribol Int 2009;42:1807–15.
[122] Martins R, Seabra J, Brito A, Seyfert C, Luther R, Igartua A. Friction coefficient in
FZG gears lubricated with industrial gear oils: biodegradable ester vs. mineral oil.
Tribol Int 2006;39:512–21.
[123] Cardoso NFR, Martins RC, Seabra JHO, Igartua A, Rodríguez JC, Luther R.
Micropitting performance of nitrided steel gears lubricated with mineral and ester
oils. Tribol Int 2009;42:77–87.
[124] Tan CP, Che Man YB. Differential scanning calorimetric analysis of edible oils:
comparison of thermal properties and chemical composition. J Am Oil Chem Soc
2000;77:143–55.
[125] Lundgren SM, Ruths M, Danerlöv K, Persson K. Effects of unsaturation on film
structure and friction of fatty acids in a model base oil. J Colloid Interface Sci
2008;326:530–6.
[126] Hu Z-S, Hsu SM, Wang PS. Tribochemical reaction of stearic acid on copper surface
studied by surface enhanced raman spectroscopy. Tribol Trans 1992;35:417–22.
[127] Hewstone RK. Environmental health aspects of lubricant additives. Sci Total
Environ 1994;156:243–54.
[128] Alves SM, Barros BS, Trajano MF, Ribeiro KSB, Moura E. Tribological behavior of
vegetable oil-based lubricants with nanoparticles of oxides in boundary lubrica-
tion conditions. Tribol Int 2013;65:28–36.
[129] Liu W, Ye C, Gong Q, Wang H, Wang P. Tribological performance of room-tem-
perature ionic liquids as lubricant. Tribol Lett 2002;13:81–5.
[130] Minami I. Ionic liquids in tribology. Molecules 2009;14:2286.
[131] Yao M, Fan M, Liang Y, Zhou F, Xia Y. Imidazolium hexafluorophosphate ionic
liquids as high temperature lubricants for steel–steel contacts. Wear
2010;268:67–71.
[132] Schneider A, Brenner J, Tomastik C, Franek F. Capacity of selected ionic liquids as
alternative EP/AW additive. Lubr Sci 2010;22:215–23.