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Abstract
Vegetable oils are being investigated as a potential source of environmentally favourable lubricants, due to a combination of
biodegradability, renewability and excellent lubrication performance. Low oxidation and thermal stability, poor low-temperature
properties and narrow range of available viscosities, however, limit their potential application as industrial lubricants. This review
addresses oxidation as a limitation of vegetable oil-based lubricants. The basic mechanism of vegetable oil autoxidation is presented,
along with methods used to monitor and analyse the products of oxidation. The potential impact of such oxidation products on
lubrication performance is discussed. A brief discussion of methods used to assess and improve oxidation stability completes the review.
r 2006 Elsevier Ltd. All rights reserved.
Keywords: Vegetable oil; Lubricant; Oxidation; Oxidation stability; Review
1. Introduction
Stronger environmental concerns and growing regulations over contamination and pollution will increase the
need for renewable and biodegradable lubricants. An
annual growth rate of 710% for environmentally favourable lubricants is expected on the US market over the next
few years compared to a rate of only 2% for the overall
lubricant market [1]. Vegetable oils are a viable and
renewable source of environmentally favourable oils.
The majority of vegetable oils consist primarily of
triacylglycerides. Triacylglycerides, also termed triglycerides, are glycerol molecules with three long chain fatty
acids attached at the hydroxy groups via ester linkages. A
three-dimensional representation of a triglyceride molecule
is displayed in Fig. 1. The fatty acids in vegetable oil
triglycerides are all of similar length, between 14 and 22
carbons long, with varying levels of unsaturation. Some
particularly interesting variations to the normal vegetable
oils are castor and jojoba oil. Castor oil is a triglyceride,
but the fatty acids are almost exclusively ricinoleic acid, an
18-carbon monounsaturated fatty acid with a hydroxy
branch at the 12th carbon. Jojoba oil is a monoester
Corresponding author.
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Fatty acid %
Palm
Soybean
Sunower
High oleic
sunower
Castora
C 14:0
C 16:0
C 16:1
2
C 18:0
C 18:1
C 18:2
C 18:3
C 20:0
C 20:1
C 22:0
Visc mm2/s, 40 1C
Visc mm2/s, 100 1C
Viscosity index
Pour point, 1C
1.5
43
11
Trace
2.5
Trace
5
40
10
4.5
23
55
Trace
3
17
74
6
2
89.5
6
4
86
0.5
40
8.3
190
0.5
31
7.4
218
9
Trace
33
8.3
242
15
Trace
41
8.8
202
12
252
20
90
24
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3. Oxidation compounds
Vegetable oils will decay during the lifetime of
the lubricant either in storage or during application.
The physical and chemical changes that occur within the
oil during oxidation are likely to have an impact on
the lubrication performance. The following section outlines the major compounds produced during vegetable
oil oxidation, methods that can be used to monitor
and analyse the compounds and their potential impact
on lubrication. A summary of the section is displayed in
Table 2.
R + H
Initiation
RH
Propagation
R + O2
ROO
ROO + RH
Branching
Termination
ROOH + R
RO + OH
ROOH
RO + RH + O2
ROH + ROO
H2O + ROO
OH + RH + O2
ROO + ROO
ROO + R
R +R
1037
ROOH + O2
ROOH
R-R
Peroxide decomposition
ROOH
Polymerisation
ROOH
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Table 2
Summary of vegetable oil oxidation compounds, analytical techniques and lubrication impact
Stage
Compound
Analytical techniques
Lubrication impact
Primary
Hydroperoxide
Secondary
Volatile
Titration [31]
Chemiluminescence [32,33]
Electron spin-resonance spectroscopy [32]
Infra-red Spectroscopy [3437]
Combined techniques [33]
Likely negligible
[4648]
Non-Volatile
High-performance liquid
chromatography [56]
High-performance size-exclusion
chromatography [57,58]
Titration [68]
Capillary gas chromatography [68]
High-performance liquid
chromatography [69]
Supercritical uid chromatography [70]
Nuclear magnetic resonance spectroscopy
[71]
Increased viscosity
Uncertain impact on lubrication
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3.2.1.1. Analysis. Volatile compounds are primarily responsible for the rancid avours and odours of oxidised
vegetable oils. The food industry is particularly interested
in the avour and quality of vegetable oils and as such,
techniques for analysing volatile organic compounds are
well established along with knowledge of the major volatile
components of oxidised vegetable oils. Volatile components of oxidised vegetable oils are generally analysed via
gas chromatography (GC) and gas chromatography-mass
spectrometry (GC-MS) [4648]. Common gas chromatographic methods for measuring the volatile organic
compounds in fats and oils are described in AOCS
Recommended Practice Cg 4-94 [49].
During the oxidation of vegetable oils polyunsaturated
fatty acids in the triglyceride breakdown rst and produce
the greatest amount of volatiles. Linolenic acid (C18:3)
decomposes primarily into 2,4-heptadienal and propanal,
with linoleic acid (C18:2) producing mainly pentane,
pentanal, hexanal and 2 heptenal. Monounsaturated fatty
acids in the triglyceride decompose at a much slower rate
and release minimal levels of volatile compounds when
compared to their polyunsaturated counterparts. Oleate
(C18:1) rich oils primarily produce octanal and nonanal,
with some heptanal [47,48].
3.2.1.2. Impact on lubrication. Volatiles formed during
vegetable oil oxidation are primarily short-chained hydrocarbons and alcohols. Polarity and chain length are critical
factors to consider for wear/friction modiers [50]. The low
polarity and short chain length of these volatile compounds
means they are unlikely to have any impact on lubrication
performance. With a study suggesting long chain alcohols,
1218 carbons, to have virtually no effect on the wear
resistance and load-carrying capacity of vegetable oils [51], it
becomes even less likely that short chain volatile compounds
will signicantly impact lubrication performance.
3.2.2. Non-volatiles
Decomposition of hydroperoxides leads to short chain
volatile compounds along with the corresponding chainshortened, non-volatile compounds.
3.2.2.1. Analysis. A method to analyse the non-volatile
organic compounds formed during the oxidation of
vegetable oils has been developed by SteenhorstSlikkerveer et al. [52]. Normal phase HPLC was used to separate
the oxidation products and a mass spectrometer (MS) was
used for identication. Vast ranges of non-volatile organic
compounds were identied in the oxidised oil, but they
could be separated into three major categories.
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stable compounds and prevent propagation of the oxidation reaction. The most effective of the type quench the
initial peroxy and hydroperoxy radicals as well as the
alkoxy and hydroxy radicals formed during the branching
stages. Some less effective free radical scavengers only
quench the alkoxy and hydroxy radicals formed during
the branching stages. Commonly utilised chain-breaking
antioxidants include butylated hydroxy anisole (BHA),
butylated hydroxy toluene (BHT), mono-tert-butyl-hydroquinone (TBHQ), propyl gallate (PG) and the naturally
occurring tocopherols. Amine-based antioxidants, such as
diphenylamine, are not very effective in vegetable oils.
Bond dissociation energies can be used for the selection
and design of chain-breaking antioxidants. Zhu et al.
discussed a method used to determining the bond
dissociation energy of acidic HA bonds, along with the
potential benets to predicting antioxidant effectiveness
[93]. Bond dissociation energies inuence the effectiveness
of hydrogen atom transfer reactions from the antioxidant
molecules to the reactive radical intermediates such as
hydroxyl, alkoxyl, peroxyl and hydroperoxyl radicals
formed during the degradation reactions. For an antioxidant to efciently quench all destructive radical intermediates its bond dissociation energy would have to be
lower than that of the peroxyl and hydroperoxyl radicals.
Peroxide decomposers are the other major class of
antioxidant. The role of peroxide decomposers is to react
with and decompose hydroperoxides. Generally hydroperoxide decomposition produces more free radicals that
propagate and branch the oxidation process. Hydroperoxide decomposition by peroxide decomposers, however,
results in stable compounds and thus limiting oxidation.
Common examples of peroxide decomposers used in
vegetable oils are catalase and glutathione.
Some antioxidants display multiple functionality. Zinc
dithiophosphates (DTP) and dithiocarbamates (DTC), for
example, act as both radical scavenger and peroxide
decomposer. Ascorbic acid, a natural antioxidant, acts by
scavenging oxygen, getting preferentially oxidised to water
and dehydroascorbic acid. Reaction with reduced glutathione can then regenerate the ascorbic acid. Ascorbic
acid can also acts as a metal chelator.
Metal-chelating agents and UV absorbers are not strictly
antioxidants, but can assist in the prevention of oxidation.
UV absorbers, such as phenylsalicylate and hydroxybenzophenone, prevent decomposition of hydroperoxides by
UV exposure. Metal-chelating agents, such as citric acid
and ethylene diamine bind metal ions that can catalyse
hydroperoxide decomposition. These compounds often
complement the action of antioxidants.
Certain combinations of antioxidants can result in
synergism, where the result of the whole is better than
the two parts. Butylated hydroxy anisole with butylated
hydroxy toluene or propyl gallate is a synergistic combination of antioxidants for storage at ambient conditions, but
combining butylated hydroxy toluene and propyl gallate
results in negative synergism. At higher temperatures
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Table 3
Summary of methods used to assess the oxidation stability of vegetable oil formulations
Oxidation trial
Description
Advantages
Disadvantages
Excellent representation of
Field trials
Active oxygen
method/Rancimat
[98]
peroxides
Large variations in acidity/peroxides
signies end point
Differential scanning
calorimetry
[25,82,99,100]
Penn State
microreactor [2,4,59]
temperatures
Monitor products of oxidation
period of time
Oxidised sample washed with
THFTHF/oxidation solution analysed
by gel permeation chromatography
storage
Simple experimental
conditions
Excellent representation of
lubricant service lifetime
Long-term trials
Complex
Expensive
Rapid loss of volatiles or degradation
automated variation
Small volume
Accelerated trials
Characterises oxidation
compounds
Small volume
Accelerated trials
Accurate thermodynamic
information
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