Renewable and Sustainable Energy Reviews 82 (2018) 80–102

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

A review on the chemistry, production, and technological potential of bio- MARK

based lubricants
⁎ ⁎
N.A. Zainala, , N.W.M. Zulkiflia, , M. Gulzarb, H.H. Masjukia
a
Centre for Energy Sciences, Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
National University of Sciences and Technology (NUST), 44000 Islamabad, Pakistan

A R T I C L E I N F O A B S T R A C T

Keywords: The possible scarcity of oil and gas resources in the future (whether in quantity or areas of availability) is a major
Vegetable oils concern throughout the world. For this reason, governments all over the world are working on reducing their
Bio-based lubricants dependence on imported energy resources. Alternative energy resources such as bioethanol, biodiesel and
Physicochemical properties biomass have gained prominence over the years in order to substitute petroleum-derived products. Bio-based
Chemical modification
lubricants have also gained importance as alternatives to conventional petroleum-based lubricants in various
Tribological properties
applications, especially the automotive industry. Despite the benefits of bio-based lubricants, these lubricants are
Biodegradable lubricant
still far from being practical substitutes. Since bio-based lubricants are typically produced from raw vegetable
oils, these lubricants have poor cold flow properties as well as low thermo-oxidation and hydrolytic stability.
However, these shortcomings can be addressed by modifying the vegetable oils chemically or incorporating
additives into the oils. This review provides a detailed treatment on bio-based lubricants, the various vegetable
oils used as the feedstocks for the production of bio-based lubricants, the physicochemical properties of bio-
based lubricants, the processes used for chemical modification of vegetable oils, the lubrication properties of bio-
based lubricants, as well as the various additives used to improve the properties of bio-based lubricants. It is
believed that this review paper will provide useful insight to researchers and practioners in the field regarding
bio-based lubricants.

1. Introduction explore alternative sources of energy.

Energy plays an essential role in our lives in order to carry out our
daily activities as well as to boost the nation’s economic growth. In one
study conducted by the European Commission [1], the consumption of
energy in the world is predicted to reach 22.3 Gtoe (Giga-tonnes of oil
equivalent) in 2050 from the current 10 Gtoe. Coal, oil and natural gas
provides 5.7, 5.9 and 4.1 Gtoe of energy whereas renewable and nu-
clear energy contributes 3.4 and 3.2 Gtoe of energy, respectively. Fossil
fuels play a major role in fulfilling global energy demands for centuries.
However, fossil fuels are depleting over the years due to the increasing
energy demands resulting from industrialization and population
growth. The ever-increasing consumption of these energy sources is
alarming since the depletion of fossil fuels will have a serious impact on
people’s lives [2]. According to Owen et al. [3], the demand for mineral
oils will likely surpass its supply by 2015 – however, this is constrained
by strong recession pressures caused by the decrease in demand and
thus, the demand for mineral oils is parallel with its supply. The de-
pletion of fossil fuels and the growing concern on the detrimental im-
pact of fossil fuels on the environment has led to the critical need to
The use of vegetable oils for lubrication purposes has been in
practice for many years. However, this idea was scrapped due to the
discovery of petroleum and the availability of low-cost oils. To date,
fossil fuel-based crude oils are used as the raw materials to produce
fuels and lubricants. However, there is new interest in the use of lu-
bricants from vegetable oils due to growing concern over the environ-
mental impact of fossil fuels. Bio-based lubricants have been produced
and marketed by a number of companies [4]. Bio-based lubricants are
promising alternatives for mineral oils since they retain the technical
specifications of conventional lubricants. Bio-based lubricants are bio-
degradable lubricants, derived from edible and non-edible vegetable
oils and they have high lubricity, viscosity index and flash point [5].
However, bio-based lubricants also have several disadvantages. For
instance, these lubricants have poor cold flow properties and oxidation
stability, which will lead to polymerization and degradation. This
problem can be overcome by chemical modifications of vegetable oils in
order to eliminate the β-hydrogen atoms in glycerol. The main factors
which influence the tribological properties of vegetable oils are the
carbon chain length, the type of fatty acids as well as polarity.

⁎
Corresponding authors.
E-mail addresses: adzlinzainal@gmail.com (N.A. Zainal), nurinmz@um.edu.my (N.W.M. Zulkifli).

http://dx.doi.org/10.1016/j.rser.2017.09.004
Received 15 June 2016; Received in revised form 4 June 2017; Accepted 3 September 2017
Available online 15 September 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.
N.A. Zainal et al.
In order to determine a suitable renewable feedstock for specific
lubrication requirement, a comprehensive review is required while fo-
cusing on their physicochemical properties, methods to enhance phy-
sicochemical properties and variety of additives to improve lubrication.
In this regard, recent reviews provide an excellent overview of the bio-
based lubricants with applications however lacks significant informa-
tion on the role of physicochemical properties and additives and the
related linkages with lubrication behaviours of such lubricants [6–10].
The main purpose of this review paper is to highlight the key works
pertaining to bio-based lubricants. In this regard, the objectives of this
review involve the overview of various renewable feed stocks on the
basis of their physicochemical properties and the literature survey of
chemical modifications and additivation which is being used for im-
proving the lubrication performance of vegetable oils for various ap-
plications. This paper is organized as follows. A brief overview of this
paper is given in Section 1. A detailed description on lubricants and the
functions of lubricants is given in Section 2. The various vegetable oils
used to produce bio-based lubricants are presented in Section 3 while
the physicochemical properties of vegetable oils are detailed in Section
4. The processes used to modify the vegetable oils chemically (i.e.
transesterification, hydrogenation, and epoxidation) are described in
Section 5. The lubrication characteristics of bio-based lubricants in
comparison with conventional lubricants are presented in Section 6.
The various types of additives used to enhance the performance of bio-
based lubricants (i.e. antioxidants, detergents and dispersants, viscosity
modifiers, nanoparticles, corrosion inhibitors, pour point depressants
and extreme pressure and anti-wear additives) are detailed in Section 7.
Lastly, the key findings of this review are summarized in Section 8.
2. Bio-based lubricants
2.1. Historical development of bio-based lubricants
Animal fats and vegetable oils have lubricated every type of ma-
chine and moving parts for thousands of years. Ancient Egyptians used
greases based on calcium soaps of olive oil as wheel axis lubricants in
carriages [11]. By the of the 18th century, the Industrial Revolution
began and this pushed the demand for natural oils such as sperm oil,
lard oil, olive oil, rapeseed oil and ground-nut oil [12]. More oil was
required for lubrication of machinery as the Industrial Revolution
started to bloom. Less than 100 years later, in the mid-19th century, the
exploitation of petroleum-based lubricants started due its lower price
and capabilities and thus, animal and vegetable oils could not compete
with petroleum. The beginning of the petroleum industry during this
period is important to support the industrial expansion in the 19th and
20th centuries. However, due to a growing awareness regarding the
effect of petroleum-based oil on the environment, several companies
have been involved in the development of bio-based lubricants in the
past few years. For example, Shell and British Petroleum collaborated
with French National Railways in the development of biodegradable
railway track grease. Mobil Chemicals implemented a clean lubricant
production line as part of the Agriculture for Chemicals and Energy
(AGRICE) programme [4]. The manufacturers of bio-based lubricants,
the trade names of these lubricants and their applications are listed in
Table 1 [13].
2.2. Background of lubricants and bio-based lubricants
Lubricants are essential for almost all aspects of modern machinery.
As the name implies, lubricants are substances used to lubricate sur-
faces that are in mutual contact in order to facilitate the movement of
components as well as to reduce friction and wear. Lubricants are used
for various purposes, as shown in Fig. 1. Choosing the suitable lubricant
for the application helps extend the lifespan of machinery and its
components as well as increase their efficiency and reliability. Lu-
bricants can be used for open systems and closed systems, as shown in
81
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
Table 2. In open systems, lubricants such as power saw chain oils and
drill fluids are expelled to the environment. In closed systems, the lu-
bricants are not exposed directly to the environment. In practice, lu-
bricants are expelled to the environment through leakages, blown pipes
as well as due to human errors. It has been reported that more than 50%
of the lubricants used throughout the world are the contributors of
environmental pollution due to total-loss lubrication, spillage and
evaporation [13]. It has been estimated that 40% (i.e. 400,000 t/a) of
lubricants is used annually and a significant amount of lubricants is lost
to the environment each year [14]. For this reason, it is highly desirable
that lubricants are biodegradable and produced from renewable and
sustainable sources. In general, a good lubricant should have high
viscosity index (VI), high flash point, low pour point, good corrosion
resistance and high oxidation stability, as shown in Fig. 2.
In general, bio-based lubricants can be defined as products with low
toxicity and excellent biodegradability. Bio-based lubricants are not
necessarily derived from vegetable based oils but they are usually de-
rived from these oils. Thus, it can be classed as renewable because
plants can be regrown. Bio-based lubricants may also be synthetic es-
ters, which are partially derived from various natural sources such as
solid fats, waste materials and tallow. The Unites States Secretary of
Agriculture defined the term ‘bio-based product’ as ‘a commercial or
industrial product (other than food or feed) that is composed, in whole
or in significant part, of biological products or renewable domestic
agricultural materials (including plant and animal) or forestry mate-
rials’ [15]. Bio-based lubricants can be categorized as sustainable be-
cause it is derived from renewable raw materials. As mentioned by
Andreas Willing [14], the sustainability of the application of raw ma-
terials can be classified into two aspects; the origin of the resources and
the pollution caused by it. In the case of bio-based products (oleo-
chemicals), it is discharged via several pathways at the end of their
lifespan and the organic chemicals are disintegrated into carbon dioxide
and water. The carbon cycle of oleochemicals is closed because the
amount of carbon dioxide released equals to the carbon dioxide that
was originally taken up by the plants from the atmosphere. Therefore, it
has zero effect with regard to the carbon dioxide balance of the at-
mosphere. On the other hand, the mineral oil-based products increase
the atmospheric carbon dioxide and therefore lead to global warming,
which can be referred to as indirect environment pollution. The life
cycle of lubricants derived from renewable sources is shown in Fig. 3.
The main component of vegetable oils is triacylglycerols (98%) as
well as a variety of fatty acid molecules attached to a single glycerol
structure. The minor components of vegetable oils are diglycerols
(0.5%), free fatty acids (0.1%), sterols (0.3%), and tocopherols (0.1%)
[13]. The triglyceride structure consists of three hydroxyl groups es-
terified with carboxyl groups of fatty acids, as shown in Fig. 4. The
triglyceride structure gives these esters a high viscosity (and thus, high
viscosity index) because of their high molecular weight. The trigly-
ceride structure is also responsible for the structural stability of the
esters over a reasonable operating temperature range [16–19]. The
carbon chain of a fully saturated fatty acid is almost straight. The
carbon atoms share a double instead of a single bond when the hy-
drogen atoms are missing from the adjacent carbon atoms. This type of
fatty acid is known as unsaturated fatty acid. In contrast, the fatty acid
is known as polyunsaturated fatty acid if the double bonds occur at
multiple sites. In general, fatty acids can be classified as saturated,
mono-, di- and tri-unsaturated fatty acids. Excessive amounts of long-
chain saturated long chain fatty acids lead to poor low-temperature
behaviour whereas excessive amounts of certain polyunsaturated fatty
acids lead to unfavourable oxidation behaviour as well as resignation at
high temperatures [17,19–21]. The flash point of the lubricant is also
higher due to the very low vapour pressure and volatility. This reduces
potential fire hazards of the lubricant during use [22–24]. It should be
noted that even monounsaturated fatty acids with long chains will
deteriorate the low-temperature behaviour of the lubricant. Even
though bio-based lubricants have poor oxidation stability compared to
N.A. Zainal et al. Renewable and Sustainable Energy Reviews 82 (2018) 80–102

Table 1
Manufacturers, trade names, manufacturing regions and applications of bio-based lubricants.

Manufacturer Trade Name Manufacturing region Applications

Total Bio-Mold-7 UK Concrete demolding oil

Fuchs Locolub eco USA/Europe Grease, hydraulic fluid, gear oil, bar and chain oil
Castrol Castrol Biolube 2T UK Two-stroke engine oil
Mobil Mobil EAL USA/Europe Grease, hydraulic fluid and refrigeration oil
Shell Ecolube USA Hydraulic fluid
Houghton Plc. Cosmolubric/Hydrodrive UK Hydraulic oil
Morris Lubricants Supergreen Air-O-Lube UK Air mist lubricant
Selenia Arbor 46 Bio-V UK Hydraulic oil
Solar Lubricants Arborol UK Chain and bar lubricant
Rock Oil BD-Rock Drill Oil UK Hydraulic oil and rock drill oil
Aztec Oils Biohyd & Biochain UK Hydraulic and chainsaw oil
Teklube TS Safra Range UK Metalworking fluid
Cargill Industrial Oils & Lubricants Novus USA/Europe/Japan Hydraulic fluids, cutting oil, gear oil, metalworking oil, bar and chain oil
International Lubricants Inc Lubegard USA/Europe Hydraulic fluid, gear oil and metalworking oil
Bioblend Lubricants International Bioblend USA/Europe Grease, hydraulic fluid, gear oil, bar and chain oil
Karlshamns-Binol AB Binol USA/Europe Hydraulic fluid, metalworking oil, bar and chain oil
Renewable Lubricants Biogrease/oil USA Grease, hydraulic fluid, cutting oil, transmission oil, gear oil, metalworking oils, bar
and chain oil, turbine drip oil, vacuum pump oil and crankcase oil
Chevron Texaco Biostar (Rando) USA/Belgium Hydraulic fluid
Environmental Lubricants SoyTrak, SoyEasy USA Grease, hydraulic fluid, cutting oil, gear oil, metalworking oils, bar and chain oil
Manufacturing Inc.
Moton Chemicals Biolube Europe Grease, turbine drip oil, bar and chain oil

mineral oils and these lubricants are unable to withstand reservoir Table 2
temperatures more than 80 °C [20,25], these issues can be addressed by Possible scenarios of direct pollution of the environment by lubricants [14].
the use of antioxidants. Bio-based lubricants are also less hydrolytically
Exposure to the Areas of use Examples
stable such that these lubricants create more foam and they reduce environment
filterability compared to mineral oils. Thus, vegetable oil products are
ideally suited for applications such as lubrication of sawmill blades or Open systems Continuous exposure Forestry Power saw chain
chain drives, whereby the lubricant is used on a single use basis. These oils
Traffic Switch lubricants
lubricants are also more suitable for applications where low toxicity is Loss of lubrication Construction Slab oils
required [16,26–28]. Oil production Drill fluids
Closed systems Accidental exposure Forestry Harvester
3. Types of vegetable oils used to produce bio-based lubricants hydraulics
Blown pipes Traffic Engine and gear
oils
Vegetable oils can be generally classified as edible and inedible oils, Leakage Construction Hydraulic oils
as shown in Table 3. The vegetable oils used to produce bio-based lu- Human error Metal industry Metal working
bricants may differ from one country to another due to climatic and fluids
geographical factors. For example, rapeseed and sunflower oils are
often used in Europe whereas soybean oils are mainly used in the US. In
only favourable if there is sufficient land area for both edible and in-
contrast, the main feedstocks of bio-based lubricants in Asia are palm
edible crops. In addition, economic factors may also be a reason which
and coconut oils. Nowadays, it is more desirable to use inedible oils to
will lead farmers to switch from producing food crops to biofuel crops
produce bio-based lubricants since these oils are derived from waste
even if the latter is inedible. This scenario will create an unbalanced
crops [30] and this eliminates the use of food crops for lubricant pro-
market since food prices will increase if food production decreases [31].
duction. However, the use of inedible oils for bio-based lubricants is

Fig. 1. Functions of lubricants.

82
N.A. Zainal et al.
Fig. 3. Life cycle of bio-based lubricants.
Fig. 4. Triglyceride structure [29].
Table 4 shows the fatty acid composition available in major vegetable
oils.
3.1. Sunflower oil
Sunflowers grow in fertile, moist, well-drained soils containing
heavy mulch. Sunflower oil is extracted from sunflower seeds and this
oil is commonly used for cooking as well as to produce margarine and
biodiesel Sunflower oil is cheaper compared to olive oil [51]. Sunflower
varieties vary in their fatty acid content [52] – some ”high oleic” types
contain a higher level of monounsaturated fatty acids in their oil
compared to olive oil. High oleic sunflower oils has many qualities that
render it suitable for lubricants such as good oxidation stability and
lubricity [53,54]. One study showed that high oleic sunflower oil
(HOSO) can be used to substitute for mineral oils in textile and tannery
applications without technical problems or modification of facilities
[55]. A properly formulated sunflower is comparable to that of mineral
oil and it is therefore a promising alternative lubricant for chain saws
83
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
Fig. 2. Properties of a good lubricant.
[56].
3.2. Rapeseed oil
Rapeseed is a bright yellow flowering member of the mustard family
and it contains high levels of erucic acid (~ 45%). Rapeseed oil was first
produced in the 19th century as a base for steam engine lubricant.
Rapeseed contains four major components (i.e. oil, water, protein and
fibre) but it also contains several minor constituents for lubricating
applications such as- free fatty acids, phosphatides (gum), enzymes
(particularly myrosinase) and glucosinolate [57]. Rapeseed oil is not
suitable for human and animal consumption because it has a bitter taste
which is due to the high levels of glucosinolates [58]. However, there
are new varieties of rapeseed with lower glucosinolate content and
therefore, they are more edible.
3.3. Canola oil
Canola is a genetically modified variant of rapeseed which has
gained prominence commercially due to its nutritional quality (low-
erucic acid and low-glucosinolate rapeseed oil). Both canola and ra-
peseed oils are primarily composed of unsaturated fats, there is a sig-
nificant difference in the composition of these oils, whereby the amount
of erucic acid in canola oil is nearly negligible (< 1%) [44].
3.4. Soybean oil
Soybean is a species of legumes which is native to East Asia. It is
widely cultivated for its edible beans, which have numerous uses. The
cultivation of soybean is successful during hot summers in which the
optimum mean temperature is within a range of 20 to 30 °C. Soybean
can be grown on a wide range of soils but the optimum growth is
achieved on moist, muddy soils with good organic content. Soybean oil
has been successfully used to produce dielectric liquids for transformers
[59,60], since it increases the fire point and service life of the trans-
former by extending the life of the insulating paper. Soybean-based oil
has also been used as the hydraulic fluid for the lift of the famous Statue
of Liberty in New York Harbour [61].
3.5. Palm oil
Palm oil is an edible oil which is derived from the mesocarp of the
oil palm fruit. Oil palm thrives in hot, humid tropical regions with an
annual rainfall within a range of 1500–2000 mm. Oil palm will grow
well provided that there is no more than three months of drought. The
optimum temperature range is 26–32 °C, and 5–7 h of direct sunlight
per day is beneficial. One hectare of oil palm is sufficient to produce
almost 10 times as much oil compared to other vegetable oil [62].
Hence, palm oil has great potential to fulfil the demand for vegetable
oil-based lubricants. A large number of experiments have been carried
out on the use of palm oil as an additive in engines [63,64] as well as a
lubricant for cold forward extrusion [65], and minimum quantity lu-
brication (MQL) [66].
N.A. Zainal et al. Renewable and Sustainable Energy Reviews 82 (2018) 80–102

Table 3
Types of vegetable oils used to produce bio-based lubricants, their requirements and major producers.

Vegetable oils Requirements Major producers References

Sunflower oil (Edible)
Rapeseed oil (Edible)
Soybean oil (Edible)
Palm oil and palm kernel oil
(Edible)
Coconut oil (Edible)
Canola oil (Edible)
Olive oil (Edible)
Jatropha oil (Non-Edible)
Callophyllum inophyllum oil
(Non-edible
Neem oil (Non-edible)
Karanja oil (Non-edible)
Castor oil (Edible)
Sunflowers need full sun and highly tolerant to drought. They grow best in fertile, moist Russia, Europe, Ukraine, Argentina [32]
well-drained soils with heavy mulch.
Rapeseed grows best in mild maritime climates. The growth of rapeseed is most vigorous in European Union, Canada, United [33–37]
temperatures from 10 to 30 °C. However, the optimum temperature is 20 °C. States, Australia, China, India
Cultivation is successful in climates with hot summers as well as optimum growing United States, Argentina, Brazil, [38,39]
conditions. The recommended mean temperature is within a range of 20–30 °C. China, India
Temperatures less than 20 °C and more than 40 °C will retard growth significantly.
Oil palm is a tropical palm tree and therefore, it can be cultivated easily in Malaysia. Oil Malaysia, Indonesia [40,41]
palm in Malaysia originates from West Africa where it typically grows in the wild but it is
later cultivated as an agricultural crop.
This plant thrives well on sandy soils and it is highly tolerant of salinity. It colonizes Indonesia, India, The Philippines, Sri [42]
shorelines of the tropical regions since it prefers areas with abundant sunlight and regular Lanka
rainfall (1500–2500 mm annually). This plant achieves good growth when the temperature
is within a range of 28–37 °C.
This plant is well-adapted to the cool extremes of temperate zones and it grows well on European Union, Canada, China, [32,43]
medium-textured, fertile and well-drained soils. Canola requires about 406–460 mm of India, Australia
water during its growing season.
The olive plant prefers hot weather and sunny areas without any shade. This plant tolerates Spain, Italy, Greece [44]
drought conditions well due to its firm and extensive root system.
Jatropha is a drought-resistant shrub or tree with low fertility and moisture demands. This Mexico, Nicaragua, Thailand, India, [45,46]
is able to grow in a number of climatic zones where the amount of rainfall ranges from 250 Indonesia, Nepal, Malaysia,
to 1200 mm.
Callophyllum inophyllum is widely cultivated in all tropical regions of the world. This plants India, Hawaii, Australia, Malaysia, [30,47]
requires annual rainfall within a range of 750–5000 mm in order to grow. Indonesia, The Philippines
Neem is an evergreen tree that is endemic to the Indian subcontinent. This tree can be India, Burma, Bangladesh, Malaysia, [30,48]
found in various countries within Asia, Africa as well as Central America and South Sri Lanka, Cuba
America. It grows in tropical and sub-tropical regions
Karanja grows in the Indian subcontinent and has been introduced successfully to humid, Northern Australia, Fiji, India [49,50]
tropical regions of the world. This plant grows quickly and it is drought-resistant with high
tolerance to salinity.
This plant is a tropical crop and the seed is sown in hot weather. Consistent rainfall is Cuba, Brazil, China, India, Italia, [30]
required for good growth. The soil should be well-drained, deep and moderately fertile. France

3.6. Coconut oil
It is rare to find coconut trees in dry regions because these trees are
unable to grow without frequent irrigation. These trees are mostly
found in tropical regions. The fruits of coconut trees are light, buoyant
and highly water-resistant and these fruits have evolved to disperse at
significant distances via sea currents [42]. Coconut oil is rich in satu-
rated fatty acids (91%) and therefore, it does not oxidize easily. Co-
conut oil has been widely used as a lubricant in rickshaws and scooters
in Southern India. This oil has been shown to improve vehicle mileage,
engine pick up and operations. In addition, coconut oil produces less
smoke when it is burned [67].
3.7. Jatropha oil
Jatropha curcas is a drought-resistant shrub or tree which belongs to
the family Euphorbiaceae and it is widely cultivated in Central America
and South America, as well as Southeast Asia, India and Africa. Even
though Jatropha oil is one of the common feedstocks for biodiesel
production [68,69], its function as a lubricant is not really known.
Jatropha oil has potential for lubricant production due to its high fatty-
acid content (61–64%) [70]. The production techniques and optimum
parameters needed to produce high yields of lubricant from Jatropha oil
are still investigated to date [71–73].
[74]. Therefore, castor oil is desirable to be used as a lubricant in jet,
diesel and race car engines. Castor oil, with its 80% ricinoleic acid
content, has unique characteristics and it is the only source of C18:1-
OH. This gives the oil a unique combination of physical properties such
as relatively high viscosity and specific gravity as well as solubility in
alcohol in any proportions. However, castor oil has limited solubility in
aliphatic petroleum solvents.
3.9. Calophyllum inophyllum L
Calophyllum inophyllum L. is commonly known as polanga or honne,
and this plant can be found largely in abundance along the seashores of
The Philippines. This plant is native to tropical Asia [75]. This medium
to large-sized tree has a height within a range of 8–20 m (25–65 ft) with
a broad spreading crown of irregular branches. Calophyllum inophyllum
L. is an evergreen sub-maritime tree which grows best on deep soils or
exposed sea sands [30]. The seeds of Calophyllum inophyllum L. contain
a high percentage of oil within a range of 65–75%. Calophyllum in-
ophyllum oil is not only used for medicinal purposes and as hair grease,
but this oil is also used to produce biodiesel with physicochemical
properties which fulfil ASTM D 6751 and EN 14214 standards.
3.10. Karanja oil

3.8. Castor oil
Ricinus communis (castor) is a fast-growing, suckering perennial
shrub which can reach the size of a small tree (around 12 m) and it is
not a cold-hardy plant. This plant also known as castor beans. The seeds
contain around 40–60% of oil that is rich in triglycerides, particularly
ricinolein. Castor oil has better low-temperature viscosity and high-
temperature lubrication properties compared to most vegetable oils
Pongamia pinnata L. is medium-sized evergreen tree which belongs
to the Millettieae family. This plant takes 4 to 7 years to reach maturity
and it is regenerated through direct sowing, transplanting and root
cutting. Karanja oil has been used for traditional medicines, timber,
pesticides and fuel in India as well as neighbouring regions. The seeds
are rich in oleic acid with an oil content within a range of 30–40 wt%
[30].

84
N.A. Zainal et al. Renewable and Sustainable Energy Reviews 82 (2018) 80–102

4. Physicochemical properties of bio-based lubricants

Olive oil

11.7

77.9
0.8
3.0

7.2
It is imperative to gain an understanding on the physicochemical
-
-
-
-

-
-
-
-
-
-
-
properties of bio-based lubricants. The properties of vegetable oils are
Palm oil

closely associated with the structural parameters of the fluid particles.

0.46
1.22
47.9

4.23
37.0
9.07
0.26

0.31
The physicochemical properties of several crude vegetable oils are
-
-

-
-
-
-
summarized in Table 5. In general, vegetable oils possess low toxicity,
Castor oil

high biodegradability, high lubricity, high flash point and good visc-

82.80
2.63

1.51
4.74
8.36
osity index, as well as low friction and wear characteristics compared to
-
-
-
-

-
-
-
-
-
mineral oils. Even though vegetable oils have many advantages com-
Canola oil

pared to mineral oils, they also have a few disadvantages such as low
pour point and poor oxidation stability. The effect of unsaturation,
60
30
3

7
-
-
-
-

-
-
-
-
-
-
chain length and branching on the viscosity index, low-temperature
Rapeseed oil

properties and oxidation stability of vegetable oils are shown in Table 6.

62.7
19.5

4.1. Viscosity
4.8

1.8

8.6

1.7

1.0
-
-
-
-

-
-

-
Soybean oil

Viscosity is a measure of the substance’s resistance to flow and it

corresponds to the informal concept of ‘thickness’. High viscosity means
11.28

24.39
56.28
2.70

5.34

that the substance has high resistance to flow and low viscosity means
-
-
-
-

-
-
-
-
-
-

low resistance to flow and vice versa [5]. Viscosity plays a vital role in
Sunflower oil

the lubricant’s ability to reduce friction and wear [82]. A very high
viscosity will increase the oil temperature and drag whereas a very low
26.13
65.52

viscosity will increase the metal-to-metal contact friction between the

6.18

2.16

moving parts. The carbon chain length is one of the factors which af-
-
-
-
-

-
-
-
-
-
-
-
Coconut oil

fects the viscosity of the lubricant. It is believed that the degree of

random intermolecular interactions increases when the length of the
51.0
18.5

fatty acid chain increases, which increases the viscosity [83]. However,
9.5
4.5

7.5

3.0
5.0
1.0
-

-
-
-
-
-
-
-

in chemically modified vegetable oils, the introduction of branching

Jatropha curcas L. oil

results in a more compact molecular configuration [13]. The degree of

unsaturation is also another factor which affects the viscosity of the
lubricant. According to Rodrigues et al. [84], one double bond will
increase the viscosity, but two or more double bonds will decrease the
viscosity of the lubricant. Epoxidized soybean oil has high viscosity
15.6

40.8
32.1
1.4

9.7

0.4

compared with commercial lubricants and therefore, it is suitable for

-
-
-

-
-

-
-
-
-
Karanja oil

high-temperature applications [85].

11.65

51.59
16.64
7.50

1.35

4.45

1.09

4.2. Viscosity index

-
-
-
-

-
-

Viscosity index (VI) is a measure of the change in the substance’s

Pongamia pinnata Pierre

viscosity with a change in temperature. A high VI indicates a small

variation in the viscosity with respect to a change in temperature and
vice versa. A high VI is an essential characteristic of good lubricant since
it is an indication that the lubricant can be used over a wide range of
temperatures by maintaining the thickness of the oil film. In contrast, a
10.6

49.4
19.0
6.8

4.1
2.4
5.3

2.4
oil

low VI indicates that the viscosity of the lubricant is less stable at high
-
-
-
-

-
-

temperatures and hence, the film thickness of the oil tends to be thinner
and becomes less viscous at elevated temperatures. Vegetable oil-based
Calophyllum inophyllum L.
Fatty acid composition of various vegetable oils [30,48,50,76–81].

lubricants generally have higher VI than mineral oils. For instance, it

was shown that castor oil has good VI with very high viscosity com-
pared to super-refined mineral oil, which can be attributed to the hy-
drogen bond of the hydroxyl monounsaturated triglycerides [86]. In
addition, it was shown that a bio-based lubricant produced from canola
17.9

18.5
42.7
13.7

biodiesel has a high VI of 204, which is due to the polyunsaturated fatty

2.5

2.1

2.6
oil

-
-
-
-

-
-
-
-
-

acid chains of the canola biodiesel [87]. Since vegetable oils contain
Neem oil

triglycerides that sustain intermolecular interactions when temperature

0.26
14.9

20.6
43.9
17.9

is increased, the VI of palm oil-based lubricant is higher than that for

0.1

0.4

1.6

0.3

0.3
-
-
-

mineral oils [88].

Fatty acid composition (%)

4.3. Flash point

Ricinoleic C18:1:OH

Lignoceric C24:0
Palmitoleic 16:1

Arachidic C20:0
Linolenic C18:3

The flash point refers to the lowest temperature at which lubricant

Gondoic C20:1
Palmitic C16:0
Myristic C14:0

Linoleic C18:2

Behenic C22:0
Caprylic C8:0

Stearic C18:0
Capric C10:0

Erucic C22:1
Lauric C12:0

Oleic C18:1

must be heated before it vaporizes. Lubricants will ignite (not burn)

when they are mixed with air. This property is useful to determine the
Table 4

volatility of a lubricant. Lubricants should have high flash point to

ensure safe operation and minimum volatilization at the maximum

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N.A. Zainal et al. Renewable and Sustainable Energy Reviews 82 (2018) 80–102

Table 5
Physicochemical properties of various vegetable oils.

Vegetable Oil Viscosity at 40 °C (mm2/s) Density (×103kg/m3) Flash Point (°C) Pour Point (°C) Viscosity index

Sunflower oil [89] 31.3 0.920 315 −12.0 –

Sunflower oil [56] 47.6 0.917 245 −20.0 218
Rapeseed oil [90] 34.8 0.917 323 -15.0 218
Rapeseed oil [91] < 36.0 0.900–0.930 > 220 – –
Rapeseed oil [92] 35.0 – 320 -10.0 220
Palm oil [93] 39.6 0.918 267 – –
Jatropha oil [94] 35.4 0.918 186 – –
Castor oil [91] 240-300 0.95-0.974 229-260 – –
Soybean oil [95] 29.0 0.913 328 −10.0 246
Soybean oil [16] 31.5 – – −9.0 –
Karanja oil [50] 40.2 0.924 225 −3.0 –
Calophyllum inophyllum oil [30,96] 71.9 0.896 221 4.3 –
Corn oil [97] 34.9 0.910 277 −40 –
Safflower oil [97] 31.3 0.914 260 −6.7 –
Coconut oil [98] 28.1 0.920 – – –
Neem oil [99] 20.5–48.2 0.912–0.965 34–285 – –

Table 6
Effect of chain length, chain branching and degree of unsaturation on the viscosity index,
low-temperature properties and oxidation stability of vegetable oils.
Viscosity Kinematic Low
index viscosity temperature
properties
Increase of chain Positive Positive – –
length
Increase of chain Negative Viscosity Positive
branching
Higher degree of Positive Negative Positive
unsaturation
operating temperature [82].
4.4. Low temperature properties of bio-based lubricants
Low-temperature performance is the main constraint when it comes
to using vegetable oils as lubricants. Even though vegetable oils have
strong intermolecular interactions which provide a durable lubricating
film, these interactions also result in poor low-temperature properties
[17]. The pour point is the most vital low-temperature property for
lubricants since it is the lowest temperature at which the lubricant
becomes semi-solid and loses its flow characteristics. In general, lu-
bricants with low pour points are desirable since these lubricants pro-
vide good lubrication at extremely low temperatures [100] as well as
during cold starts [5]. If the pour point is not sufficiently low, the lack
of lubricant flow will lead to excessive friction, wear and heat in the
system, which will lead to equipment damage or failure. The risk of
equipment failure is significantly greater if the lubricant does not flow
properly during start-up. Several studies have been carried out over the
years to determine the low-temperature properties of vegetable oils and
these studies revealed that most vegetable oils will become cloudy as
well as precipitate and solidify at −10 °C upon long-term exposure to
cold temperatures, resulting in poor flow and pumpability
[77,101–103]. This is due to the fact that vegetable oils tend to form
macro-crystalline structures at low temperatures through uniform
stacking of the ‘bend’ triglyceride backbone. These structures restrict
the ease of flow of the system through the loss of kinetic energy of the
individual molecules during self-stacking [20]. The pour point of ve-
getable oils decreases with an increase in the number of double bonds
in the molecules. According to Jayadas and Nair [76], vegetable oils
that have a high percentage of unsaturated fatty acid chains will have
lower pour points because the fatty acid chains in a bent configuration
prevents close packing of the molecules during cooling. It was shown in
[79] that rapeseed oil has lower pour point (−21 °C) compared to olive
oil (−15 °C) which is clearly due to the high unsaturated fatty acid
content of rapeseed oil. However, the introduction of branched or
aromatic hydrocarbon molecules with high molecular weight can gen-
Oxidation erally reduce the pour point of vegetable oils by preventing of molecule
stability packing during cooling [20,76]. In general, a high degree of un-
saturation is favourable for low-temperature properties of the lubricant
but it is unfavourable for the oxidation stability.
Positive
4.5. Oxidation stability
Negative
Oxidation is a chemical reaction that occurs when the lubricant
combines with oxygen. Oxidation stability indicates the ability of the
lubricant to withstand oxidation. The rate of oxidation of lubricants is
influenced by several factors such as temperature, pressure as well as
the presence of water and contaminants [5]. In addition, the service life
of lubricants decreases with an increase in temperature. High oxidation
stability is an important criterion for lubricants since a low oxidation
stability will cause the lubricant to oxidize rapidly if it is untreated.
Consequently, the lubricant thickens and polymerizes into a plastic-like
consistency. Numerous studies have been carried out to investigate the
oxidation stability of vegetable oils [20,23,104]. The oxidation stability
of vegetable oils is generally lower than that for synthetic esters be-
cause of higher degree of unsaturation in vegetable oils [13]. Oxidation
is undesirable since it results in polymerization and degradation of the
lubricant. Polymerization of vegetable oil increases the viscosity and
decreases the functionality of the lubricant [105–107]. Degradation
results in breakdown of the product, which is undesirable since the
lubricant becomes volatile and corrosive, and its structure and prop-
erties weaken. The oxidation stability is determined based on the
dominant fatty acids in the vegetable oils [13]. The main factor that
affects the oxidation of vegetable oils is the presence of unsaturated
fatty acids particularly polyunsaturated compounds such as linoleic and
linolenic acids [90]. The double bonds in the alkenyl chains easily react
with oxygen to form free radicals which then degrade to form peroxides
and acids [17]. This leads to polymerization and fragmentation.
Therefore, oxidation is dependent on the degree of unsaturation of the
fatty acid chains. Linolenic, linoleic and oleic acids are the main fatty
acids with double bonds and the oxygen absorption rate is 800:100:1
[33,108]. Thus, a higher degree of unsaturation leads to higher rate of
oxidation [109]. According to Gryglewicz et al. [79], rapeseed oil,
which is rich in polyunsaturated fatty acids, is less resistant to the ac-
tion of oxygen as well as high temperature. It has been shown that the
kinematic viscosity of Jatropha oil increases drastically due to its poor
oxidation stability. The presence of the β-CH group removes easily from
the molecular structure and this weakens the middle carbon-oxygen
bond. This results in the formation of carboxylic acid which will

86
N.A. Zainal et al.
Fig. 5. Plant oil-glycerine ester which consists of different fatty acids. The critical points
are β-CH group and unsaturated fatty acid residues [111].
degrade the lubricant [110].
5. Chemical modification of vegetable oils
The low-temperature fluidity and chemical stability (oxidation and
thermal stabilities) of vegetable oils are due to their fatty-acid structure,
as shown in Fig. 5. The unsaturated structural ‘double bond’ elements in
the fatty acid component and the β-CH group of the alcohol compo-
nents results in oxidation and thermal instability since the double bonds
in the alkenyl chains are reactive and readily react with oxygen in the
air [111]. The β-hydrogen atom in glycerol removes easily from the
molecular structure, cleaving the esters into acid and olefin. However,
it shall be noted that some unsaturation is necessary in order to
maintain the low-temperature properties of the lubricant.
Attempts to improve the low-temperature properties and oxidation
stability of vegetable oils include transesterification of trimethylolpro-
pane and methyl ester from vegetable sources [112–117], selective
hydrogenation of polyunsaturated C=C bonds of fatty acid chains
[118–120] and conversion of C=C bonds into oxirane rings via epox-
idation [90,121]. There are a number of advantages of modifying ve-
getable oils chemically which include stability of the lubricant over a
wide temperature range as well as excellent wear and friction char-
acteristics [122].
5.1. Transesterification
Transesterification is a reaction whereby the triglyceride molecule
reacts with three moles of methanol in the presence of an acid or base
catalyst [123,124], resulting in glycerol and mixtures of fatty acid
methyl esters, as shown in Fig. 6 [124].
The presence of hydrogen atoms in position β relative to the hy-
droxyl group in the glycerol molecule can be solved using transester-
ification. In this process, glycerol is replaced with polyol which does not
contain β-hydrogen atoms, namely neopentyl glycol (NPG), trimethy-
lolpropane (TMP), or pentaerythritol (PE) [87,125]. This enhances the
thermal stability of the lubricant at high temperatures by preventing
self-polymerization to form free fatty acids [123]. Polyol esters usually
contain more ester groups compared to others and the added polarity
further reduces volatility and enhances lubricity of the lubricant [115].
Gryglewicz et al. [79] discovered that polyol esters have better thermal
stability compared to other vegetable oils. Transesterification has been
Fig. 6. Chemical reaction of the transesterification process.
87
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
carried out on various vegetable oils including soybean oil [126,127],
canola oil [87], olive oil [79], Jatropha oil [72,125], palm oil and palm
kernel oil [112,115,116,128–130] and rapeseed oil [79,131] in order to
produce fatty acid methyl esters (FAME). NPG and TMP esters were
prepared from olive oil and rapeseed oil in [79,131], whereby calcium
methoxide was used as the catalyst. The results showed that the olive
oil-based esters have the highest thermo-oxidative resistance due to
their low polyunsaturated acids content whereas the NPG esters have
higher stability in thermo-oxidative conditions. TMP esters were pro-
duced from palm kernel oil in [116], whereby sodium methoxide was
used as the catalyst and the results showed that 98% of the feedstock
was converted successfully into palm kernel TMP triesters. The same
researchers then produced TMP esters from palm oil with high oleic
acid content as an extension of their previous work and the results
showed that the palm oil has a pour point between −32 and 10 °C
[130]. The palm oil methyl esters were fractioned within a temperature
range of 150–180 °C and pressure of 0.1 mbar prior to synthesis to
ensure that the pour point of the palm oil with high oleic acid content is
less than −30 °C. The concentration of the C16:0 methyl ester in the
starting material should be less than 10%. Sripada et al. [87] synthe-
sized bio-based lubricants from methyl oleate and canola biodiesel by
transesterification with TMP. Sodium methoxide was used as catalyst.
The bio-based lubricant produced from methyl oleate and canola bio-
diesel has a good pour point with a value of −51 and −66 °C, re-
spectively. These desirable low-temperature properties are attained due
to the high degree of unsaturation and polyunsaturation in the bio-
based lubricant derived from methyl oleate biodiesel and canola bio-
diesel, respectively. In addition, it was shown that the oxidation sta-
bility of TMP ester (Jatropha) increases by 100% compared to Jatropha
oil due to the elimination of β-CH groups [110]. The introduction of
branching into methyl ester reduces the pour point by disturbing the
alignment and stacking of hydrocarbon chains. This allows the oil to
solidify at lower temperatures. The position of branching also plays an
important role – for instance, branching in the middle further reduces
the pour point compared to branching at the end of chain [13].
The polyols commonly used during the transesterification process
are NPG, TMP and PE. Each of these polyols contains a different number
of hydroxyl functional groups (-OH), as shown in Fig. 7. In general, the
viscosity of ester-based lubricants increases with the functionality of the
polyol. According to Eychenne and Mouloungui [132], the number of
hydroxyl groups affects the viscosity of the esters according to the
following order: PE > TMP > NPG. Similarly, the viscosity of vegetable
oil-based TMP esters is higher than that of equivalent NPG esters [79],
which may be due to the presence of three acid groups in the structure
of TMP esters and the existence of only two groups in the molecules of
NPG esters.
It has been shown that TMP esters have better thermo-oxidative
stability compared to NPG esters, which is evident by the increase in
acid number and viscosity [79]. Padmaja et al. [136] also obtained a
similar finding, whereby the PE esters have greater thermal stability,
followed by TMP and NPG esters. Konishi and Perez [137] investigated
the oxidation stability of polyol esters and the results showed that the
N.A. Zainal et al.
PE esters have better stability compared to TMP esters. In contrast, the
NPG esters have the lowest oxidation stability. The pour point decreases
with a decrease in the number of hydroxyl groups in the polyol. It was
found in a previous study that for the erucic acid esters, the NPG ester
has the lowest pour point (−17 °C), followed by TMP −5.6 °C) and PE
(9.5 °C) [132]. Similarly, Gryglewicz et al. [79] discovered that the
NPG esters have lower pour points than TMP esters which is due to the
type of triglycerides from which the esters are synthesized. Apparently,
the molecular configuration of NPG and TMP esters is capable of dis-
turbing the molecule packing compared to PE esters [136]. In addition,
the results obtained from a four-ball tribotest showed that the NPG ester
has a larger wear scar diameter compared to the PE ester, which is
attributed to the existence of carboxylate groups in the ester [138]. The
NPG ester only has two groups of carboxylate esters whereas the PE
ester has four groups. The NPG ester is not stable at high temperatures
and breaks down easily due to the smaller structure of the NPG. The
steady-state wear rate is higher for the NPG-8L ester, followed by TMP-
8L and PE-8L [137].
5.2. Hydrogenation
Hydrogenation is a process in which hydrogen is added to the C=C
bonds in the triglycerides of an oil molecule [139]. The hydrogenation
process of vegetable oils involves three simultaneous chemical reac-
tions: (1) saturation of double bonds, (2) geometric (cis-trans) iso-
merization and (3) positional isomerization. The quality and physical
properties of hydrogenated oils are greatly influenced by the number of
double bonds present and the cis-trans-isomers of fatty acids. In in-
dustrial processes, hydrogenation is conducted in the presence of a
support or Raney Ni catalyst within a temperature range of 150–225 °C
and pressure range of 69–413 kPa [139,140]. However, the toxicity of
the Ni traces remaining in the oil raises concerns and this leads to the
development of a new catalyst, i.e. palladium (Pd). The use of Pd cat-
alyst is attractive due to the higher catalytic activity of Pd compared to
Ni. Moreover, Pd catalyst can be used in softer conditions [140]. The
selectivity of a catalyst refers to the ability of the catalyst to favourably
reduce linolenic acid before linoleic acid and oleic acid. Selectivity also
refers to the ability of a catalyst to reduce by hydrogenation only to
form monoenes, without reducing to full saturation. This is called
partial hydrogenation, which is important to prevent deterioration of
the low-temperature properties of the lubricant such as the pour point
[111,139]. The selective hydrogenation of ethyl esters of sunflower oil
at low temperatures was studied in the presence of a supported catalyst
containing Pd, Pt and Ru [141]. The Pd catalyst has the best catalytic
performance and it was proven that the selectivity of n-cis C18:1 ester is
improved by the modification of Pd catalysts using copper and lead or
by the addition of amines into the reaction medium. The oleic acid
C18:1 in the ‘cis’ isomer form has the advantage of being stable in
oxygen atmosphere, which prevents polymerization and remains liquid
at low temperatures. It was shown in [142] the use of various oxide
supports (α-Al2O3, γ-Al2O3, TiO2, MgO, ZnO, CeO2, CeZrO2) does not
enhance the selectivity of the reaction towards the cis C18:1 in the Pd
88
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
Fig. 7. Structures of neopentyl glycol (NPG), tri-
methylolpropane (TMP) or pentaerythritol (PE)
polyol esters [133–135].
catalyst. Fig. 8 shows the selective hydrogenation of sunflower oil
studied by Nohair et al. [142]. In addition, one study [139] was con-
ducted to improve the oxidation stability of palm oil via partial hy-
drogenation using Pd/γ-Al2O3 catalyst. The unsaturated fatty acids
were transformed into a single unsaturated fatty acid without in-
creasing the saturated component of the substance. This improves the
oxidation stability of the lubricant in optimum reaction conditions.
Several studies have been carried out to determine the increase in the
percentage of hydrogenation of multiple unsaturated fatty acids
through heterogeneous and homogeneous catalytic systems [143–146]
with a successful conversion rate of more than 80% [33,147,148].
5.3. Epoxidation
Epoxidized vegetable oils are produced by the reaction of double
bonds by peroxy acids [10] and removal of the C=C bonds. Conven-
tional epoxidation methods include acid ion exchange resins, enzymes
and metal catalyst [149]. In general, alkene is reacted with peroxy acid
in order to synthesis epoxide groups or oxirane rings, as shown in Fig. 9.
Wu et al. [90] epoxidized rapeseed oil using the conventional epox-
idation method (i.e. in situ peracetic acid generation), whereby car-
boxylic acid is reacted with concentrated hydrogen peroxide. They
found that the oxidation stability of the epoxidized rapeseed oil en-
hances significantly in the presence of antioxidants. The epoxidized
rapeseed oil has better friction-reducing characteristics and extreme
pressure capabilities compared to the rapeseed oil. This is due to the
formation of a polyester or polyether material film by the three-member
ring of oxirane created by tribo-polymerization.
Epoxidation has received much attention because a wide range of
reactions can be performed in moderate conditions by modification of
the C=C bonds to the oxirane ring. The epoxidation reaction is fol-
lowed by ring-opening of the epoxidized oil as well as the esterification
process. Hwang and Erhan [21] used sulphuric acid as the catalyst
during the ring-opening reaction of epoxidized soybean oil with various
linear and branched alcohols. This was followed by esterification of the
resulting hydroxyl group with acid anhydride. The results showed that
there is improvement in the oxidation stability and the pour point is
reduced significantly by the introduction of branching. A one step
process was used to prepare a bio-based lubricant [151], which involves
simultaneous epoxy ring-opening and esterification of epoxidized ca-
nola oil in the presence of acetic anhydride using a novel sulphated Ti-
SBA-15 catalyst. The results revealed that the epoxidized canola oil has
good tribological properties and therefore, it is a promising bio-based
lubricant. Bio-based lubricants were produced from epoxidized vege-
table oils via cationic ion-exchange resins [28]. The process involves
ring-opening reactions with different alcohols followed by esterification
of the resultant hydroxyl group. The epoxidized rapeseed oil produced
by Arumugam et al. [150] has a lower pour point (−15 °C) compared to
that raw rapeseed oil (−11 °C). The results obtained from the rotary
bomb oxygen test method showed that the oxidation stability of the
epoxidized rapeseed is twice the value for raw rapeseed oil. In addition,
the possible reactions during the epoxy ring-opening lead to a large
N.A. Zainal et al.
Fig. 8. Hydrogenation reaction pathway of ethyl esters produced from conventional sunflower oil.
number of interesting products for biodegradable lubricant as shown in
Fig. 10. For example, the conversion of epoxidized vegetable oils to
diesters results in excellent properties at low temperatures due to the
branching effect [13].
5.4. Comparison of technologies for various lubrication applications
Despite the lubrication properties of natural oils, direct use of ve-
getable oils is not suitable for prolonged use in IC engines because of
their low thermal and oxidation stability [13]. Research has shown that
chemically modified vegetable oils-based biolubricants exhibit ex-
cellent oxidation stability and low-temperature flow properties
[23,152]. Such chemically functionalized esters are produced from re-
latively pure raw materials to produce predetermined molecular
structures formulated for high performance lubrication. Synthetic esters
have improved thermo-oxidative stability, high viscosity indices, and
advantage of absence of the undesirable impurities found in conven-
tional petroleum based oils [7].
Similar to neat natural oils, synthetic esters maintain an affinity for
metal surfaces due to their high degree of polarity which affords them
the ability to establish monolayers that minimize the surface contact
and enhance the tribological properties. Due to their sensitivity towards
hydrolysis and thermal degradation, thermal properties of esters have
been improved by replacing the glycerol with other polyols such as
neopentylglycol (NPG), pentaerythritol (PE), trimethylolpropane
(TMP), trimethylolhexane (TMH), and trimethyoloethane (TME)
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Renewable and Sustainable Energy Reviews 82 (2018) 80–102
[79,117,131,153–155]. Esters such as the NPG were originally devel-
oped for the lubrication of aircraft jet engines whereas PE esters have
found use in gas turbines. TMP esters have attained considerable im-
portance in applications which include engine lubricants, gear oils,
hydraulic oils, compressor oils, pump and turbine oils [7]. For engine
use in automotive and marine engine lubrication, TMP esters have
found widespread use [156]. High viscosity index (VI) with moderate
thermo-oxidative stability make TMP esters attractive lubricants for
reciprocating engine applications.
6. Lubrication characteristics of bio-based lubricant
Tribology is the science and engineering of the interactions between
two surfaces in relative motion. Tribology includes the study of friction,
lubrication and wear, and it has become the foundation for selecting the
suitable lubricant for a particular application. Examining the effects of
tribological system parameters on the chemistry of the lubricant can
help one to identify the lubrication requirements for a given applica-
tion. It is known that vegetable oils provide good lubrication through
their ester functionality [157]. The polar head of the fatty acid chain
attaches to the metal surface by a chemical process which results in the
formation of a monolayer film. The non-polar end of the fatty acid chain
sticks away from the metal surface, which reduces the coefficient of
friction [22,67,88,158]. Fig. 11 shows the effect of fatty acid un-
saturation, chain length and branching on the lubrication character-
istics of vegetable oils. Most studies have shown that even though the
Fig. 9. Reaction of double bonds with peracids [150].
N.A. Zainal et al.
Fig. 11. Key factors which will lead to better lubricity of lubricant.
crude vegetable oils improve the coefficient of friction, the surface wear
increases. A number of studies pertaining to the tribological properties
of various vegetable oils are summarized in Table 7. The triglyceride
structure provides desirable qualities for boundary lubrication because
of their long polar fatty acid chains. This results in a high-strength lu-
bricating film. The film interacts strongly with the metal surface, re-
ducing friction and wear [159].
6.1. Carbon chain length
In general, studies have shown that the boundary friction coefficient
decreases with an increase in the carbon chain length [27,160]. A long
hydrocarbon chain of fatty acids provides a great molecular barrier
[122]. The increase in the adsorbed film thickness is contributed by the
length of the fatty acid chains, which increases the protected surface
area [27,110,161]. The friction transition temperature increases for
fatty acids with an increase in molecular weight and the minimum
chain length for effective lubrication is n = 9 (pelargonic acid) [162].
However, it has been shown that short fatty acid chains with n ≤ 8 does
not improve lubrication. For instance, it was shown that the viscosity
and flash point of polyol ester decrease by the introduction of short-
chain fatty acids into the synthesis of esters [132]. The lubricity can
also be improved by decreasing the degree of branching (to be more
linear) in the base oil. The steady-state wear rate of TMP and PE linear-
chain acids decreases as the chain length increases. In contrast, the
steady-state wear rate is higher for branched-chain acids compared to
90
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
Fig. 10. Reactions possible with epoxidized vegetable oils [121].
linear-chain acids having the same carbon number [137]. The polyol
ester with a longer linear structure shows better scuffing resistance.
6.2. Types of fatty acids
The presence of fatty acid chains in vegetable oil-based esters fa-
cilitates the formation of a monolayer film on the sliding surfaces. The
boundary lubrication mechanism by the vegetable oil may have some
impact on the effectiveness of various fatty acids. It is possible that the
stearic acid molecules will align themselves as a straight chain since
they do not contain double bonds. The stearic acid is closely packed on
the surface, which contributes towards a strong protective layer.
However, a couple of studies have shown that increasing the degree of
unsaturation has a negative effect on the performance of fatty acids as
boundary-wear reducers [163,164]. Unsaturated acids, in the cis form,
unable to establish straight chains and therefore, it is more difficult for
these fatty acids to pack themselves close together, resulting in a weak
protective layer [163], as shown in Fig. 12.
6.3. Polarity
Polarity means that a molecule is asymmetrical with a different
chemical affinity at either end of the molecule. Polarity is particularly
important for lubrication. It is believed that the existence of a polar
structure, which disperses the non-polar molecules or base lubricant,
provides a great boundary layer [110]. Fatty acid has a carboxyl group
at one end (i.e. COOH), which is strongly attached to a metallic surface.
The other end is an alkyl group (i.e. CH3) which has no affinity for
almost all of its molecules (Fig. 13). It shall be noted that different
molecular species have different polarities and there is a hierarchy for
its adsorption onto a surface.
The polar functional groups in the molecule create physical contact
and interact chemically with a metal surface, with the non-polar end
forming a molecular layer or barrier that separates the rubbing surfaces
and thereby preventing direct contact [138,166]. For this reason, ve-
getable oils have good boundary lubrication properties [122]. The high
degree of polarity in chemically modified vegetable oils is due to the
ester linkage in the molecules, and therefore, these oils are more ef-
fective than mineral oils [13]. The wear protection is improved by in-
creasing the polar functionality of the vegetable oil structure, which
results in stronger adsorption on the metal surface as well as greater
 Table 7
Tribological properties of vegetable oil-based lubricants.

Vegetable oils Test specifications Operating conditions Findings Reference

N.A. Zainal et al.

Thermally modified soybean oil (TMSBO) Ball-on-disk Duration: 15 min; Sliding speed: 5 rpm; Load: 1778 N; The lower CoF for TMSBO compared to that for soybean oil’s is due to [122]
and chemically modified soybean oil Ball (52100 steel): 12.7 mm Temperature: room temperature heat induced intermolecular polymerization (dimers and trimers). There
(CMSBO) diameter, 64–66 Rc is no major improvement in the wear characteristics since there are no
Disc (1018 steel): 25.4 mm outer changes in the polar functional groups in this molecule.
diameter, 15–25, 0.26–0.46 µm The CoF for CMSBO is less than half of the CoF for SBO. In addition,
roughness there is a reduction in the wear characteristics. The polar functional
group in the triacylglycerol molecule form physical and chemical
interactions with the metal surface and create a stable lubricant film.
Palm oil Bench wear test Duration: 5 h; Sliding speed: 150 rpm; Normal load: 10 N; The wear performance of palm oil-based lubricant is better compared to [88]
Temperature: 24–26 °C; Contact pressure: 3.0 MPa; Stroke length: mineral oil-based lubricant due to the presence of fatty acids in the palm
80 mm oil. The fatty acids usually have thicker molecular layers. However, the
palm oil-based lubricant has lower friction performance compared to
the mineral oil-based lubricant, which is probably due to boundary
effect and/or breakdown of boundary lubrication due to the lower
viscosity of the palm oil.
Coconut oil Four-ball tester ASTM D4172-94 and ASTM D2783 Even though the CoF is lower for coconut oil than that for SAE 20W50 [67]
oil, the WSD is larger. The reaction between the oil and the metal
surface during sliding results in continuous removal of the soap film
formed on the metal surface. The soap film has low shear strength and
therefore, the CoF is low. The CoF and WSD improved significantly
upon the addition of 2 wt% of AW/EP additive. The weld point also
increases as this additive concentration.
Epoxidized rapeseed oil Four-ball wear test ASTM D4172 The epoxidized rapeseed oil has better friction-reducing and extreme [90]
Ball (AISI Standard Steel No. Duration: 30 min; Rotational speed: 1450 ± 50 rpm; Load: 392 N; pressure ability compared to that for rapeseed oil. Polyester or
E52100): 12.7 mm diameter Room temperature polyether material is being formed by the three-member oxirane ring

91
Soybean oil (SO), high oleic soybean oil Sequential four-ball wear test
(HOSO) and epoxidized soybean oil Ball (AISE 52100): 12.7 mm
(ESO) diameter
Jatropha oil-based TMP ester Four-ball wear test
Ball (AISI 52–100): 12.7 mm
diameter, 64–66 HRC
Sunflower oil Ball on plate reciprocating wear test
rig
Ball (SKF G20 carbon chromium
steel): 6 mm diameter
Plate (mild steel): 700 Vickers
Jatropha oil Four-ball wear test
Ball (AISI E-52100 steel): 12.7 mm
Duration: three sequential 30 min; Rotational speed: 600 rpm;
Load: 40 kg; Temperature: 75 °C
Anti-wear test (IP 239)
Duration: 60 min; Rotational speed: 1200 rpm; Load: 392 N;
Temperature: Room temperature
Extreme pressure test (ASTM 2783)
Rotational speed: 1770 rpm; Load: 196 N for every 10 s
ASTM G133-95
Revolution speed: 100 rpm; Stroke of the rig: 12 mm; Ball
velocity: 0.04 m/s; Load: 33.4 N; Average pressure: 1.4 GPa;
Temperature: 50 °C, Sliding distance: 360 m
ASTM D4172
Duration: 60 min; Rotational speed: 1200 rpm; Load: 40 kg;
due to tribo-polymerization.
The SO results in less wear compared to the ESO. SO is also more prone [169]
to oxidation and the formation of HMW products since it has high
polyunsaturated fatty acid content. This provides some wear protection.
The HOSO has good anti-wear properties due to the formation of a
stable polymeric film. This oil has a long, straight non-polar chain that
orients itself perpendicularly to the surface and forms a thick film.
However, the film is not a permanent, stable film.
The ESO results in high wear scar diameter, which may be due to the
existence of oxirane rings. The oxirane rings reduce the binding to the
surface when rigidifying the molecules, which prevents the film-forming
ability of the molecules at the metal surface. However, the ESO gives the
lowest CoF compared to SO and HOSO.
The Jatropha oil-based TMP ester improves the CoF by around 40% [110]
compared to paraffin oil, which is due to the length of the fatty acid
chains. In contrast, the WSD is higher for this oil, which may be due to
the decomposition of the which releases acid, resulting in corrosion.
Based on the extreme pressure test, the CoF increases when the load is
increased. The TMP ester improves the function of the lubricant at high
loads, whereby the maximum load bearing capacity is 1373 N.
The addition of 1.0% stearic acid into the sunflower oil reduces wear by [163]
90% wears and improves the CoF. This is due to the fact that the
addition of unsaturated fatty acids are similar to those that are already
present in the oil and this is likely to have an insignificant effect. This is
why the addition of stearic acid, which is present in small quantities in
the sunflower oil (3.5%), has such a dramatic effect on wear compared
with oleic and linoleic acids.
Jatropha oil has high unsaturated hydrocarbons (C18:1). It is known [170]
that the polar head of the fatty acid tends to attach itself to the metal
(continued on next page)
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
 Table 7 (continued)
Vegetable oils
Palm oil-based ester
Canola oil-based TMP ester
Calophyllum inophyllum (CI)-based TMP
ester
92
Methyl esters of sunflower oil (SME), palm
oil (PME), rapeseed oil (RME) and
crude rapeseed oil
Double fractioned palm oil (DFPO)
Rapeseed oil and high oleic sunflower oil
Rice bran oil, sunflower oil and coconut oil
Test specifications
diameter, 64 HRC
Four-ball wear test
HFRR apparatus
Four-ball tribotester
Ball (Carbon-chromium steel SKF):
12.7 mm diameter, 62 HRC
Four-ball wear test
Pin-on-disc
Pin (pure aluminium A1100): 6 mm
diameter, 30 mm length
Disc (alloy tool steel SKD 11):
165 mm diameter, 10 mm thickness
SRV high frequency test
Steel ball (AISI 52100 or 100Cr/6)
and disc (100Cr6)
Four-ball wear test
Ball: 12.7 mm diameter
Four ball tester
Ball (chrome alloy steel): 12.7 mm
diameter, 61 Rockwell hardness
Operating conditions
Temperature: 75 °C
IP 239
Duration: 30 min, rotational speed: 1200 rpm, load: 40 kg,
temperature: 50, 60, 70, 80, 90 and 100 °C
ASTM D6079-04
Frequency: 50 Hz; Duration: 75 min
Duration: 60 min; Rotational speed: 1200 rpm; Load: 40 kg;
Temperature: 50, 60, 70, 80, 90, 100 °C
ASTM D4172
ASTM G99-05a
Load: 50 and 100 N; Sliding speed: 300, 600, 800, 900 and
1000 rpm; Duration: 60 min; Temperature: 27 °C
DIN 51 834
Frequency: 50 Hz; Duration: 2 h; Load: 27 N
Temperature: 65 °C, Duration: 60 min; Load: 392 N; Rotational
speed: 1500 rpm
ASTM D4172-94
Duration: 60 min; Rotational speed: 1200 rpm; Temperature:
75 °C, Contact pressure: 2574 MPa
Findings Reference
surface. It is believed that the polar head of the fatty acids in the
N.A. Zainal et al.
Jatropha oil reacts with the steel surface and forms soapy layer which
helps protect the surface against wear.
The CoF increases with increasing temperature for NPG. However, the [138]
CoF decreases with increasing temperature for PE and formulated PE,
which indicates that the PE gives better protection to the surfaces at
high temperatures due to its thermal stability. In addition, the scar
produced increases with increasing temperature. This is due to the fatty
acids present in the ester, which can accelerate the formation of scar
due to its corrosive nature. The acidic compound causes instability of
the oil, which increases the wear rate.
The WSD reduces to 223 µm (pure diesel: 380 µm) with 10% dilution of [87]
canola (B. napus) biodiesel-derived bio-based lubricant in diesel. The
canola-derived bio-based lubricant gives better performance compared
to the methyl oleate-derived bio-based lubricant.
The CoF for the CI TMP ester is lowest compared to that for paraffin oil [96]
and commercial lubricant. The CoF decreases with an increase in
temperature. The presence of long-chain fatty acids in the CI TMP ester
improves the boundary lubrication properties and the film is effective
even at high temperatures. The WSD is lower for the CI TMP compared
to that for paraffin oil but the WSD is larger than that for commercial
lubricant since it contains additives which give protection to the ball
surface. The fatty acid chains in the CI TMP ester create a less stable
film, resulting in higher wear. The WSD also increases as the
temperature increases. The steel ball used in the CI TMP ester is
subjected to adhesive wear.
The bio-based lubricants reduce the WSD significantly compared to that [150]
for SAE20W40 (0.68 mm). The WSD for SME, PME, RME and crude
rapeseed oil is 0.62, 0.58, 0.55 and 0.66 mm, respectively. The anti-
wear properties improve due to the polar structure and long fatty acid
chains in the methyl ester, which causes the oil to stick between the
worn surfaces.
Comparison between DFPO with SAE 40 engine oil and hydraulic oil [171]
shows that the DFPO bio-based lubricant gives the lowest CoF at 50 and
100 N at various sliding speeds. The CoF is higher at higher load and
sliding speeds. The fatty acids in the DFPO create multi and mono layers
on the rubbing surfaces, forming a stable film which prevents direct
contact. However, the wear rate is higher for the DFPO since the film
lowers its ability to protect metal-to-metal contact and maintains its
consistency throughout the operation. Lower surface roughness of pin
and disc lubricated by DFPO proved that it is able to maintain the
surface finish of rubbing materials.
Both rapeseed and high oleic sunflower oils result in good CoF. [108]
However, the WSD is higher for these oils compared to mineral oil. This
is due to the formation of organic acids which attack the uncovered
metal surfaces and form an easily sheared, soft oxide layer. This oxide
layer decreases friction and forbids seizure, but also quickens the wear
rate.
The rice bran oil and sunflower oil each has lower CoF, with a value of [81]
0.073 and 0.060, respectively. In contrast, the coconut oil and
SAE20W40 have higher CoF, with a value of 0.101 and 0.117,
respectively. The existence of long carbon chain length (C18) in rice
bran oil and coconut oil may affect the CoF, considering that coconut oil
generally has lower carbon chain length (C8–C14). On the other hand,
the WSD is higher for the rice bran oil (0.585 mm) compared to that for
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Renewable and Sustainable Energy Reviews 82 (2018) 80–102
N.A. Zainal et al. Renewable and Sustainable Energy Reviews 82 (2018) 80–102

Reference lateral interaction between the ester chains. Vegetable oils have high
solubilizing power for polar contaminants and additive molecules
[167]. However, this causes competition between the additive mole-
cules and other molecules. The presence of additives may interfere with
the ability of the ester to attach to the metal surface. Such interactions
SAE20W40 (0.549 mm), which may be due to chemical or oxidative

can lead to synergistic and antagonistic effects. Since most of the ad-
ditives contain oxygen and nitrogen (each having its own polarity),
these additives will compete with the surface-active compounds.
Choosing a suitable additive will have a positive effect on the lubricity
of the lubricants. However, an incompatible boundary lubricity agent
sticking will significantly reduce lubricity [168].

7. Additives used in bio-based lubricants

The limitations of vegetable oils such as poor thermo-oxidative

stability and cold flow behaviour may also be enhanced by the use of
additives. The manufacturers of various vegetable oils can use the same
base stock for each formulation and choose different additives in order
to fulfil the requirements of a specific application. Additives may con-
stitute up to 5% (by weight) for some oils. The presence of additives
help improves the properties of lubricants and bio-based lubricants in
Findings

terms of corrosion inhibition as well as friction and wear character-

wear.

istics. In general, esters with biodegradable additives are more superior

compared to pure oils or vegetable oil blends in terms of its wear re-
sistance [172]. The effect of additives on the friction and wear char-
acteristics of bio-based lubricants is summarized in Table 8.

7.1. Antioxidants

Antioxidants are additives that are used to delay or prevent the

oxidation process by slowing down the lubricant from oxidative de-
gradation while ensuring that the lubricant fulfils industrial require-
ments [173]. These additives interfere with the autoxidation process in
many ways according to their structure and mechanism. Most of these
additives act as primary antioxidants (chain-breaking radical sca-
vengers) or secondary antioxidants (oxygen scavengers and peroxide
Operating conditions

decomposers) or through a combination of the functionalities of these

antioxidants [174]. The chain breaking antioxidants react with the ra-
dicals to form stable compounds and prevent propagation of the oxi-
dation reaction [17]. Commonly used chain-breaking antioxidants in-
clude butylated hydroxy anisole (BHA), butylated hydroxy toluene
(BHT), mono-tert-butyl-hydroquinone (TBHQ), propyl gallate (PG) and
the naturally occurring tocopherol (TCP). Secondary antioxidant are
essentially oxygen scavengers. The main difference between chain-
breaking radical scavengers and oxygen scavengers is that the latter
does not convert free radicals into stable molecules [173,174]. Ascorbyl
palmitate (AP) is an example of an antioxidant showing this type of
mechanism. Several studies have reported the application of anti-
Test specifications

oxidants in vegetable oils in order to improve their oxidation stability.

It was shown that zinc diamyl dithiocarbamate (ZDDC) has the best
antioxidant activity when it is added into soybean oil, followed by BHT
and alkylated phenol/dithiophosphoric acid ester/diphenylamine
(APDD) [175]. ZDDC shows better performance than diphenylamine,
whereby it hinders phenol in vegetable oils since it acts as both a radical
scavenger and hydroperoxide decomposer. This reduces the hydroper-
oxides formed during the oxidation process into non-radical products
such as alcohol while the oil is oxidized in a sacrificial manner, which
prevents chain propagation [175]. α-TCP has been widely used as an
antioxidant in vegetable oils with varying degrees in its performance. It
was shown in one study [176] that the use of TCP on its own as well as
Table 7 (continued)

the combination of TCP with butylated hydroxyanisole enhances the

Vegetable oils

stability of trimethylolpropane fatty acid triester (TFATE). However,

this finding contradicts the results obtained by Tang et al. [177]
whereby TCP shows the smallest increase in the induction period for the
soybean biodiesel, which may be due to the relative effect of each an-
tioxidant on the different feedstocks. In addition, TCP also does not

93
N.A. Zainal et al.
seem to be an effective antioxidant of both high-oleic sunflower oil and
castor oil since it results in higher consumption of oxygen [174]. The
effectiveness of PG (which is a natural antioxidant) in delaying the
oxidation of HOSO and CO is proven to be comparable to that for 4,4′-
Methylenebis (2,6-di-tert-butylphenol) synthetic antioxidant (MBP)
[174]. Since conventional additives such as zinc dialkyldithiophosphate
(ZDDP) contain harmful substances such as phosphorus, chlorine and
some heavy metals [178,179], eco-friendly additives such as acylated
chitosan schiff base have been developed as substitutes and these ad-
ditives are used as antioxidants in N-butyl palmitate/stearate bio-based
lubricant [178].
7.2. Detergents and dispersants
Detergent and dispersant additives (DDA) are essential to improve
engine efficiency, prolong the lifespan of the lubricant, as well as ensure
cleanliness of the engine [180]. Carbonaceous sludge forms in the
combustion chamber due to incomplete combustion and this sludge
accumulates, forming an oil-insoluble substance. In such cases, de-
tergents are very effective to prevent the accumulation of sludge par-
ticles. Dispersant additives disperse the sludge particles and keep them
suspended in the oil. Multi-functional additives are presently in use,
acting both as detergents and dispersants. The DDAs commonly used
are: metal sulfonate, ash-less sulfonate, overbased sulfonate, salicy-
lates, alkyl phenolates, overbased carboxylate, polyisobu-tylene succi-
nimides, glycidol modified succinimides, Mannich adducts, poly-
ethylene glycol esters, polyol poly- (12-hydroxy stearic acid),
Fatty acid
molecule
Protected layer
Strong bonding between carboxyl
form
group and metal surfaces
94
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
Fig. 12. Structure of saturated and unsaturated fatty acids [165].
phosphates and phosphonates. However, vegetable oils have a high
level of solvency and therefore, they act as detergents in various ap-
plications. Biodegradability and toxicity are the main properties which
need to be considered when it comes to choosing detergents for vege-
table oils. Phenates and sulfonates should be avoided since they are
toxic and therefore, they are not for environmentally safe. However,
low amounts of phosphates and phosphate esters are acceptable for
vegetable based oils since these detergent additives give desirable
performance without compromising the environmental benefits of ve-
getable based oils [181]. To date, most of the dispersants are for-
mulated to act in the presence of mineral base oil. However, several
studies have been conducted to evaluate the performance of dispersants
in vegetable oils. The use of dispersant polymers in vegetable oils has
been shown to improve the dispersant characteristics of the lubricant
without compromising other significant properties of the lubricant. The
dispersant polymers keep the amount of non-biodegradable products to
a minimum level [181].
7.3. Viscosity modifiers
Vegetable oils typically have a high viscosity index (VI), which in-
dicates that these oils maintain their designed viscosity over a wider
range of temperatures compared to the mineral oils [181]. Viscosity
modifiers contain polymers which help lubricants maintain their lu-
brication capabilities at high temperatures. These additives increase
association with the oil by increasing their molecule size so that they do
not flow away from the surface [182]. Viscosity modifiers increase both
Fig. 13. Polarity of vegetable oils.
Alkyl tail
Carboxyl group
 Table 8
Effect of additives on the performance of bio-based lubricants.
Additive
ZnO and CuO nanoparticles (0.5 wt%)
Nanoscale and microscale TiO2 particles
95
Synthetic thiophosphates (tri-n-octyl
thiophosphate (TOTP) and tri-n-octyl
tetrathiophosphate (TOTTP))
Concentration: up to 3 wt%
S-[2-(acetamido) thiazol-1-yl] dialkyl
dithiocarbamate
Concentration: 0.0, 0.5, 1.0, 1.5, 2.0 and
2.5 wt%
Bio-based lubricants
Sunflower and soybean oil
Chemically modified rapeseed
oil
Rapeseed oil (RO)
Rapeseed oil
Test specifications Operating conditions Findings Reference
N.A. Zainal et al.
High frequency Temperature: 50 °C; Duration: 60 min; Load: 10 N; Stroke There is a small increase in the CoF of the sunflower [186]
reciprocating test rig length: 1 mm; Frequency: 20 Hz and soybean oils upon the addition of nanoparticles,
(HFRR) indicating that the nanoparticles do not function as
Ball (AISI 52100 steel): anti-wear additives. This may be due to the chemical
6 mm (570–750 HV) nature of these oils since they contain polar groups
Disk (AISI 52100 steel): that adhere to the surface. The nanoparticles behave
10 mm diameter as a third body which increases friction. Hence, the
(190–210 HV) presence of the nanoparticles actually worsens the
formation of lubricating film for the sunflower and
soybean oil-based lubricants. However, the
sunflower oil-based lubricant shows better film-
forming ability in absence of additives due to the
higher number of polar functional groups. The
lubricating film is observed to be stronger and stable
for the sunflower oil-based lubricant.
Pin-on-disc tribometer ASTM G99 There is a gradual decrease in the COF for the [92]
Disc: 87 HRB Temperature: 120 °C: Duration: 2 h; Load: 100 N; Sliding chemically modified rapeseed oil when the sliding
Pins: 54 HRC distance: 1000 m; Track diameter of disc: 20 mm; Rotational speed is increased. The lubrication performance of
speed: 1.4–5.6 m/s the chemically modified rapeseed oil is higher upon
the addition of TiO2 nanoparticles compared to that
for TiO2 microparticles. The nanoparticles efficiently
act as ball bearings, which reduce direct contact
between surfaces. The CoF is reduced by 15.2%
(nanoscale) and 6.9% (microscale) relative to the
base oil alone. The WSD is reduced by 11 and 6.1%
upon the addition of the TiO2 nanoparticles and
microparticles, respectively. The TiO2 nanoparticles
create a third-body rolling effect between the
surfaces, which decreases the wear rate. The wear
scar is also observed to be smoother for the lubricant
containing TiO2 nanoparticles.
Four-ball wear tester Temperature: 50 °C; Duration: 30 min; Load: 196, 294, 392, These additives result in good anti-wear behaviour [34]
Ball (AISI 52100 steel): 490 and 588 N; Rotational speed: 1450 rpm for the RO. However, there is an increase in the CoF
12.7 mm diameter, for the RO at certain concentrations. At a load of
59–61 HRC 392 N, both of the synthetic thiophosphates improve
the anti-wear behaviour of RO at concentrations ≥
1.5 %. The optimum concentration which gives the
best lubrication performance for the TCP/RO, TOTP/
RO and TOTTP/RO is 2.0, 1.0 and 2.0%,
respectively. As the load increases, the anti-wear
ability of all additives in the base stock also
increases. The balls lubricated with 2.0% TOTTP/RO
have the lowest WSD. The TOTTP/RO also shows
better friction-reducing ability compared to other
lubricants investigated in this study. The role of
synthetic thiophosphates as anti-wear additives can
be explained by the tribochemical adsorption and
reactions on the rubbing surfaces, which results in
the creation of a boundary, protective layer.
Four-ball wear tester GB3142-82/ASTM D2783 The presence of additive in the rapeseed oil results in [35]
Ball (GCr15 bearing Temperature: 15 °C; Duration: 30 min; Load: 392 N (Extreme smaller WSD compared to that for the base oil. This
steel): 12.7 mm diameter, pressure: 200, 300, 400, 500, 600 N) indicates that the additive increases the wear
59–61 HRC resistance of the lubricant. The optimum
concentration of the additive which minimizes the
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Renewable and Sustainable Energy Reviews 82 (2018) 80–102
 Table 8 (continued)
Additive
CuO nanoparticles
Concentration: 0.1, 0.2, 0.3 and 0.4%
Phosphorus-free triazine derivatives (ZOO,
ZOS and ZDION)
Concentration: 0.0, 0.5, 1.0, 1.5, 2.0, 2.5
and 3.0 wt%
96
Boron-containing additive (boric acid +
monoethanolamine), BMEA
Copper(II) oxide (CuO) and molybdenum
disulfide (MoS2) nanoparticles
Concentration: 1 wt%
Zinc borate ultrafine powder (ZBUP)
Concentration: 0.5, 1.0 and 2.0 wt%
Bio-based lubricants
Coconut oil
Rapeseed oil
Complex ester derived from
glycerol and oleic acid
Chemically modified palm oil
(CMPO)
Sunflower oil
Test specifications Operating conditions Findings Reference
WSD is 1.0 wt%. As the load increases, there is a
N.A. Zainal et al.
steady decrease in the CoF upon the addition of
1.5 wt% additive. A higher load promotes the
formation of chemical reaction film, which leads to a
lower shear force between the frictional surfaces.
The formation of a protective film is proven by XPS
analyses on the worn surface.
Pin-on-disc tribometer ASTM G99. The CoF of the coconut oil decreases gradually with [187]
Pin (aluminium alloy): Sliding distance: 1000 m; Track diameter of disc: 90 mm; an increase in the sliding speed. At the following
8 mm diameter, 27 mm Normal load: 1–2 MPa; Rotational speed: 1.4–5.6 m/s conditions (rotational speed: 1.5 m/s, load: 2 MPa),
length the CoF of the coconut oil decreases when the
Disc (steel): 60 HRC concentration of CuO nanoparticles in the base oil
increased, which may be due to the fact that the
nanoparticles create a third body rolling effect
between the surfaces. In addition, the specific wear
rate decreases when the concentration of CuO
nanoparticles is increased, regardless of the
rotational speed. The optimum concentration of CuO
nanoparticles are 0.34%.
Four-ball wear test Temperature: Ambient temperature; Duration: 30 min; Load: The phosphorus-free triazine derivatives result in [37]
Ball (CCr15 bearing 392 N (extreme pressure: 196, 294, 392, 490, 588 N); excellent tribological behaviour for the rapeseed oil.
steel): 12.7 mm diameter, Rotational speed: 1450 rpm The ZOS additive gives good anti-wear and friction-
59–61 HRC reducing properties at a concentration of 1.5 wt% for
all loads, followed by ZOO and ZDION. This is
attributed to the rank of the active element S, which
is dependent on the adsorbed amount of active S
during the rubbing motions.
Four-ball wear tester Extreme pressure (ASTM D2783) There is no improvement in the load-wear index [190]
Ball (AISI 52100 steel): Load: 294 N; Rotational speed: 1760 ± 40 rpm; Duration: upon the addition of the boron-containing additive
12.7 mm diameter, 64–66 30 min; Temperature: 18–35 °C into the complex ester derived from glycerol and
HRC oleic acid. However, there is an improvement in the
load-wear index for the lubricant when it is mixed
with dibutyl phosphite and/or DMTD. This is
probably due to some kind of interaction, whereby
the boron acts as a coordinating atom.
Four-ball test Extreme pressure (ASTM D2783) The addition of MoS2 and CuO nanoparticles into [188]
Ball (AISI 52100 steel): Load: 40 kg (initial) –varied every 10 s; Rotational speed: CMPO reduces the WSD for all loading conditions.
12.7 mm diameter, 64–66 1770 ± 30 rpm; Duration: 10 seconds; Temperature: The average reduction in WSD is 16.6% for loads
HRC 25 ± 5 °C more than 80 kg, indicating that both of these
nanoparticles have excellent resistance to extreme
pressure. The CMPO mixed with MoS2 nanoparticles
has better AW/EP properties compared to the CMPO
mixed with CuO nanoparticles, which may be
attributed to the good dispersability of MoS2 in
CMPO. The effectiveness of the nanoparticles as AW/
EP additives is evidenced from the smooth worn
surfaces of the tested balls, which is related to the
precipitation of nanoparticles on the contact
surfaces.
Four-ball wear tester ASTM D4172 The sunflower oil has the lowest CoF upon the [189]
(anti-wear property) Load: 294 N; Rotational speed: 1200 rpm; Duration: 30 min; addition of ZBUP at a concentration of 0.5%, with a
Ball (AISI 52100 steel): Temperature: 22 °C (ambient) percentage reduction of 13% relative to the CoF for
12.7 mm diameter, 59–61 pure sunflower oil. The WSD is reduced by 10% upon
HRC the addition of 0.5% of ZBUP. The substrates formed
Pin-on-disc tester Sliding speed: 50 mm/s; Duration: 30 min; Load: 50 N; on the worn surfaces lubricated with sunflower oil
(continued on next page)
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
 Table 8 (continued)

Additive Bio-based lubricants Test specifications Operating conditions Findings Reference

(friction-reducing Temperature: 22 °C (ambient) mixed with ZBUP additive have higher hardness
N.A. Zainal et al.

property) compared to the surface lubricated with pure

Molybdenum disulfide (MoS2) nanoparticles
Concentration: 0.25, 0.5, 0.75 and 1.0 wt
% 8 mm diameter, 27 mm
Graphene nanoplatelets (GNPs)
Ball (AISI 52100 steel): sunflower oil This is due to the tribochemical
5 mm diameter, 59-61 reactions between the additive and substrates.
HRC
Disc (steel): 27 mm
diameter, 3 mm thickness
Coconut oil Pin-on-disc tribometer ASTM G99-05 The friction and wear rate at the sliding interface [197]
Pin (aluminium alloy): Sliding distance: 1000 m; Track diameter of disc: 90 mm; decrease for the coconut oil mixed with MoS2
Sliding speed: 0.47–1.414 m/s; Normal load: 2–4 MPa nanoparticles relative to those for the base oil. The
length optimum concentration of MoS2 nanoparticles in the
Disc (steel EN-31): 60 coconut oil is 0.53%. Moreover, the surface
HRC roughness of the pin decreases upon the addition of
Four-ball tester ASTM D5183-05 MoS2 nanoparticles in the coconut oil. The
Ball (GCr15 steel): 12.7 Load: 392 N; Rotational speed: 600 rpm; Duration: 60 min; researchers also conducted the experiment using
mm diameter, 61 HRC Temperature: 75 ± 2 °C MoS2 nanoparticles in surfactant-modified form at
the optimum concentration. There is a further
decrease in the CoF and WSD for the lubricant in this
case, which indicates that the modification made
improves the dispersability of the MoS2
nanoparticles in the coconut oil. The existence of
nanoparticle elements (Mo and S) in the wear tracks
of the lubricated surfaces prove that the
nanoparticles occupy the asperity contacts and create
a nano tribofilm.
5 vol% palm oil-based TMP Four-ball wear test Load: 392 N; Rotational speed: 1200 rpm; Duration: 60 min; The presence of GNPs in the base oil at diluted (0.01 [198]

97
Concentration: 0.01, 0.03, 0.05, 0.1, 0.2, ester + 95 vol% Ball (AISI 52100 steel): Temperature: Room temperature and 0.03 wt%), intermediate (0.1, 0.2 and 0.5 wt%)
0.5, 1 and 3 wt% polyalphaolefin (PAO) 12.7 mm diameter, 64–66 and concentrated (1 and 3 wt%) concentrations
HRC results in higher CoF (from 3 to 16%) compared to
that for the base oil alone, except for 0.05 wt% with
a percentage of reduction of 5%. At low
concentration, the low coverage of GNPs fail to
create protective layer. Meanwhile, at high
concentration, large aggregates forms due to
agglomeration of GNPs. The WSD is also observed to
be smaller for the base oil containing 0.05 wt% GNPs
(416 µm) compared to that for base oil alone
(486 µm).
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
N.A. Zainal et al.
the low-temperature and high-temperature viscosity of the oil. Chiu
et al. [183] formulated engine oils using blends of triglyceride base oil,
synthetic ester and mineral oil. They added olefin copolymer to im-
prove the VI and the results showed that the formulated engine oil is
60% biodegradable with a gelation index less than 12. Gelation index
refers to largest rate of viscosity increase when the oil is cooled slowly
from −5 °C to the lowest test temperature [184]. Ethylene-vinyl acetate
(EVA) copolymer was tested previously as a viscosity modifier for ve-
getable oils and the results showed that this additive increases the
viscosity of vegetable oils, particularly those with a low viscosity such
as sunflower oil, high-oleic sunflower oil and soybean oil [185]. The
EVA copolymer increases the viscosity up to 420% with respect to the
base oil at 40°C. Other commonly used polymers include poly-
methacrylates, styrene-diene copolymers, and styrene-ester copoly-
mers.
7.4. Nanoparticles
It has been reported extensively in the literature that nanoparticles
are great additives for lubricants and bio-based lubricants in order to
reduce friction and wear. Nanoparticles are regarded as attractive
candidates compared to conventional extreme pressure and anti-wear
additives due to their environmental properties [186]. The properties of
bio-based lubricants are dependent on the properties of the nano-
particles such as the size, shape and concentration of the nanoparticles
[92]. The effects TiO2 [92], CuO [186–188] and ZnO [186] nano-
particles on the properties of bio-based lubricants have been in-
vestigated in several studies. It was shown in one study that the CoF of a
chemically modified rapeseed oil is reduced by 15.2% upon the addi-
tion of TiO2 nanoparticles. This may be due to the fact that spherical
TiO2 act as ball bearings, which reduce contact between frictional
surfaces [92]. In addition, the WSD is reduced by 11% and the wear
scar is observed to be smoother. In another study, the results showed
that the tribological properties of coconut oil are enhanced upon the
addition of CuO nanoparticles at the optimum concentration (0.34 wt
%) [187]. There is also less scuffing on the surface of the pin subjected
to sliding during the pin-on-disc tribometer tests. The zinc borate ul-
trafine powder (2ZnO.3B2O3 3.5H2O) shows outstanding friction re-
duction and anti-wear properties when it is used as a lubricant additive
in sunflower oil, particularly at a concentration of 0.5% which reduces
the CoF and WSD by 14 and 10%, respectively [189]. This is due to the
formation of tribofilms resulting from tribochemical reactions on the
worn surface, as well as increased hardness of the substrate. However,
both ZnO and CuO do not show good anti-wear characteristics when
they are used as additives in epoxidized sunflower oil and soybean oil
[186]. This is due to the chemical nature of these vegetable oils,
whereby the polar groups adhere to the surface and they have a third
body behaviour, which in turn, increases friction.
7.5. Corrosion inhibitors
Corrosion inhibitors are additives that help protect metal from
oxygen, water, acid, base and salt attacks. Corrosion inhibitors act by
physically adsorbing on the metal surfaces via their polar functional
groups and maintaining a resilient protective film on the surface by
associating with the lubricant. Several studies have been carried out
over the years in order to determine the effects of corrosion inhibitors
on the corrosive effect of bio-based lubricants. One study [190] showed
that boron-containing additives increase the corrosion of steel, but
these additives are less corrosive on copper. This is due to the chemical
reaction between boron monoethanolamine (BMEA and 2,5-di-
mercapto-1,3,4-thiadiazol (DMTD), which forms dust-preventing solids
that adsorb onto the copper surface. This adds weight to the copper
surface. The performance of borated and non-borated overbased car-
boxylates as corrosion inhibitors has been studied [191] and the results
showed that both borated and non-borated carboxylates are good
98
Renewable and Sustainable Energy Reviews 82 (2018) 80–102
corrosion inhibitors, particularly in the presence of borate. It was also
shown that the lubricant containing an effective amount of N-acyl-N-
hydrocarbonoxyalkyl aspartic acid ester gives good corrosion inhibition
and anti-wear properties [192]. The application of N-acyl-N-hydro-
carbonoxyalkyl aspartic acid ester is found to be suitable for both mi-
neral and non-mineral oils (including vegetable oils). Hence, it is sui-
table for use as a lubricant additive.
7.6. Pour point depressants
Pour point depressants (PPDs) are developed to overcome the for-
mation of large crystals during solidification and ensure oil flow at low
temperatures. PPDs function as wax-crystal modifiers and they work by
altering the crystal size either by absorption onto the surface of the
newly formed crystals or crystallizing with the precipitating wax [182].
Commercial PPDs are generally composed of a polymethacrylate
backbone with a certain type of branching, which permits inclusion of
the PPD molecules into the growing crystals [103]. In general, the pour
point of the lubricant decreases with an increase in the chain length of
the ester branching. It has been shown that ester branching groups with
a chain length of at least six carbons are the most effective to impose the
desired molecular spacing, resulting in the most desirable pour point
properties. The addition of 1% PPD (i.e. LubrizolTM 7670 made from
sunflower and mineral oils) reduces the pour point of soybean oil-based
lubricant from −9 °C to −45 °C [21]. Besides PPD, diluents such as 2-
ethylhexyl oleate, isobutyl oleate, trimethylolpropane trioleate, pen-
taerythritol tetraoleate and diisodecyl adipate have also been used and
the effect of their dilution on the pour point of vegetable oils have been
determined [21].
7.7. Extreme pressure and anti-wear additives
Friction is primarily dependent on the shearing forces necessary to
divide the adhering asperities. Friction and wear can be reduced by the
addition of anti-wear and extreme pressure additives into the lubricant.
These additives create a durable, protective films over the metal surface
by reacting thermo-chemically with the metal surface. Extreme pressure
and anti-wear additives typically contain chlorine, phosphorus and
sulphur [193]. These elements protect the metal surface with easily
sheared layers of sulphides, chlorines or phosphides, which forbid se-
vere seizure and wear. However, it should be noted that the use of these
‘active’ elements are controlled due to environmental concerns -since
these elements lead to corrosion of metal specimens as well as pollution
[194]. Dermawan et al. [195] found that dibutyl phosphite reduces
wear on rubbing bodies. However, 2,5-dimercapto-1,3,4-thiadiazol
(DMTD) needs to be added at extreme pressure conditions in order to
obtain the same result as that for normal conditions. In another study,
used four-ball test to test lubricants with boron-containing additives.
They concluded that dibutyl phosphite is a better additive than DMTD
in the absence of boron monoethanolamine (BMEA) at extreme pressure
conditions. However, DMTD is a better additive in the presence of
BMEA. However, the dibutyl phosphite + DMTD + BMEA additive
mixture is less effective compared to the DMTD + BMEA additive
mixture, which may be due to the insignificant amount of phosphorus.
Phosphorus plays a vital role in reducing greenhouse gas (GHG) emis-
sions to the environment [196].
8. Discussion
The detailed literature review has shown that significant informa-
tion of lubricant-related properties of vegetable oils is required to
compare them with baseline lubricants. The efficacy of vegetable oils is
determined by their chemical composition, where they predominantly
consist of mixtures of fatty acid esters derived from glycerol. The in-
formation of lubricant-related properties of vegetable oils is required to
compare them with baseline lubricants. As different applications consist
N.A. Zainal et al.
of different ambient as well as operating condition, therefore vegetable
oils should be used in applications where their properties and lubrica-
tion performance are best matched. In this regard, lubricants properties
like viscosity, low temperature fluidity, oxidation stability and tribo-
logical behavior have been majorly focused. To improve thermo-oxi-
dative stability, chemical modification of the vegetable oils is a subject
under active investigation.
9. Conclusions
The ever-increasing demand for energy, the depletion of fossil fuels
as well as the increase in global awareness regarding the environmental
impact of fossil fuels has led to much research and development in
search of renewable and sustainable sources of energy. Unlike con-
ventional petroleum-derived lubricants, bio-based lubricants are clean
lubricants having the chemical structure of a fatty acid. To date, many
vegetable oils from edible and non-edible sources have been used to
produce bio-based lubricants – however, those derived from non-edible
sources are more attractive since they do not rely on edible feedstocks
which can be used for food production. Climate and geographical fac-
tors both play a critical role in determining whether vegetable oils
should be used to produce bio-based lubricants.
This review provides a systematic overview of the key properties of
bio-based lubricants, role of chemical functionalization and additives
and their link with the lubrication performance. Vegetable oils offer a
number of advantages over conventional mineral oils since these oils
are highly biodegradable and environmentally safe. Even though the
thermo-oxidative stability of vegetable oils can be a problem, this issue
can be overcome by modifying the vegetable oils chemically via
transesterification, epoxidation or selective hydrogenation. The prop-
erties of bio-based lubricants can also be improved by the addition of
additives such as antioxidants, detergents and dispersants, viscosity
modifiers, nanoparticles, corrosion inhibitors, pour point depressants
and extreme pressure and anti-wear additives, depending on the spe-
cific requirements of the application. With the significant improvement
of vegetable oils by chemical modification or incorporation of ad-
ditives, bio-based lubricants appear to be promising alternatives to re-
place petroleum-derived lubricants in the future. Even though a large
number of studies have been carried out over the years regarding the
application of vegetable oils as bio-based lubricants, more research is
needed to obtain a detailed understanding on the lubrication mechan-
isms of these lubricants, their blends and their compatibility with a
variety of additives. It can be expected that there will be a significant
market shift if it is possible to produce bio-based lubricants on a com-
mercial scale within the next few years since manufacturers will be
focused on developing materials that are compatible with bio-based
lubricants.
Acknowledgements
The authors gratefully acknowledge the financial support by
University of Malaya under the UM Grand Challenge grant (Project
title: Tribological characteristics of bio-based lubricants, Project no.:
GC001E-14AET).
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