The thermal stability of rapeseed oil as a base stock for environmentally friendly lubricants/Aplinkai draugisku baziniu alyvu, gaminamu is rapsu aliejaus, terminis stabilumas.
Kreivaitis, R. ; Padgurskas, J. ; Gumbyte, M. 等
1. Introduction
The annual lubricant consumption of the world is rising annually.
Recently, there has been a growing concern about pollution reduction.
This concern has increased the pressure on research and industry to find
environmentally friendly, biologically based lubricants to replace
materials of petrochemical origin, and this is now considered a research
priority in the fuel and energy sectors [1].
High-level automotive lubricants are required to have high quality
and high performance, and to be multipurpose. In addition, primary
lubricant additive compounds such as sulphur, phosphorus and zinc are
restricted. In some cases, their use is completely forbidden [2]. In
particular machinery applications such as forestry, agriculture, and
water treatment, the use of environmentally friendly bio-based
lubricants is determined by Eco Labels. In these cases, the use of
readily biodegradable base stocks of vegetable origin is required. This
includes pure and modified vegetable oils and animal fats, as well as
various esters sintered from vegetable oils. The sintered esters have
excellent properties but are also expensive, which leads to limited
usage for such esters [2]. Vegetable oils have good natural lubricity
together with environmental compatibility and a low price [1].
Unfortunately, they are susceptible to oxidation and have problems at
low temperatures. Despite these issues, vegetable oils remain the most
attractive base materials for environmentally friendly lubricants.
The lifetime of vegetable based lubricants is predominantly limited
by thermal oxidation. This problem has been discussed in many works of
research [3-5]. Oxidation causes a decrease in the oil's
tribological properties. As was shown by Fox and Stachowiak [6], the
oxidation of sunflower oil has a strong influence on its boundary
lubrication properties. They conclude that the decrease in lubrication
properties when oxidation begins is related to the destruction of
triglycerides and an increase in the level of peroxides. Additionally,
severely oxidised sunflower oil demonstrates an improved friction
coefficient. Mano et al. [7] observed that the oxidation of rapeseed oil
could improve both the wear and friction reduction properties, depending
on the lubricated surface material. The influence of oxidation time on
the tribological properties of rapeseed oil was studied by Kreivaitis et
al. [8]. It was found that the worst tribological properties are seen
when rapeseed oil is in the oxidation propagation stage, while oxidation
products formed in the final stage soften the negative effects. The
tribological properties in the above study were evaluated by using only
the oxidation time to represent the oxidation rate. The literature
survey shows that more comprehensive relationship, between tribological
and physicochemical properties, should be found. The present study was
performed to further investigate the physicochemical changes of the oil
and elucidate the relationship between the main physicochemical
parameters and the tribological properties. Visible light spectroscopy
is suggested as an easy and fast method for determining the oxidation
rate.
2. Testing procedures
Conventionally refined, bleached, and deodorised rapeseed oil (RO)
was obtained from an oil manufacturer (SV Obeliai, Lithuania). Rapeseed
oil was used without any additional preparation. The reagents used to
determine the peroxide and acid numbers were procured from (Penta, Czech
Republic). All of the solvents used were analytical grade.
Oxidation was carried out with reference to the standard method ISO
6886:2006 "Animal and vegetable fats and oils--Determination of
oxidative stability". Oxidation was performed using a Rancimat 743
(Metrohm AG) apparatus. A 20 ml oil sample was placed into a glass tube
and heated to 100[degrees]C. A stream of dried and purified air (10
litres/h) was passed through the sample, intensifying the oxidation. To
reach the different stages of oxidation the samples were oxidised for 5,
10, 15, 18, 20, 30, 35 and 40 hours. After the oxidation, they were
cooled to -10[degrees]C and held until the appropriate test.
The kinematic viscosity of all samples, at temperatures of 40 and
100[degrees]C, was measured according to standard LST EN ISO 3104+AC:
2000. Kinematic viscosity measurements were performed in a Stabinger
Viscometer, model SVM 3000 (Anton Paar). The viscosity index was
calculated using the ISO 2909:2002 method. The acid and peroxide numbers
were measured using methods LST EN ISO 660:2000 and LST EN ISO
3960:2001, respectively. The acid number measurements were performed in
a potentiometric titrator, model 877 Titrino plus (Metrohm AG). The
density was measured according to LST EN ISO 12185:1999.
Tribological properties were investigated using a four-ball type
test rig in accordance with standard DIN 51 350, part 3. The 12.7 mm
diameter balls were made of 100Cr6 bearing steel. A load of 150 N was
used. The test duration was 1 h. At least three repetitions were
performed to determine the mean wear and friction.
The lubricity evaluation parameters were the relative wear and the
mean friction coefficient. Wear was measured using an optical microscope
with 160X magnification.
An Ocean Optics USB4000 visible light spectrometer (1 nm
resolution) together with a pulsed xenon visible light lamp PX-2 was
used to determine transmission of the samples from all oxidation
periods. An integration time of 100 ms and a total of 10 scans to
average were chosen. Non-oxidised rapeseed oil was used as a 100%
transparent reference.
3. Results and discussion
The oxidation stability of rapeseed oil depends on its fatty acid
profile as well as the presence of natural antioxidants in the oil. The
rapeseed oil used for experiments in this study contained 4.7%
saturated, 61.2% monounsaturated and 34.1% polyunsaturated fatty acids.
Due to the comparatively high polyunsaturated fatty acid content,
rapeseed oil is sensitive to thermal degradation when compared with
other types of vegetable oil or animal fat containing a lower
unsaturated fatty acid content. The oxidation stability of oil also
depends on the content of natural antioxidants in the oil. A large
amount of natural antioxidants are found in cold-pressed and unrefined
oils. Natural antioxidants are removed during the oil refining
procedure, but natural and synthetic antioxidants are added to the oil
after refining to increase its storage stability. Our tested rapeseed
oil contained 70 mg/kg of carotenoids and 583 mg/kg of tocopherols and
tocotrianols.
Stimulated by temperature and oxygen, the primary oxidation
products are formed in rapeseed oil at the beginning of the oxidation
process. Initially, antioxidants present in the oil slow down formation
of the products, but the antioxidants do not have sufficient
effectiveness to maintain oil stability for an extended period of time.
This fact is of special importance in cases when oxidation is stimulated
by a high temperature and/or oxygen in the air. For this reason, after a
particular time, which is specific to each type of oil, the oil becomes
unstable, i.e., the oxidation development stage begins. The period
preceding the beginning of the development stage is called the induction
period [6, 9].
Under experimental conditions the IP of oxidised oil is
approximately 18 h. In the primary oxidation stage (0-18 h) an
increasing number of peroxides indicate the growing quantity of
alkylradicals (Fig. 1, a). A slight increase in acidity makes it
possible to assume that almost no free fatty acids are formed in this
stage (Fig. 1, a). They typically form during hydrolysis, which most
often occurs simultaneously with oxidation. Because hydrolysis requires
water, it is assumed that the examined rapeseed oil contains a small
amount of water, and thus formation of the free fatty acids is unnoticed
[6].
By analysing the processes at the end of the induction period, it
can be assumed that this period ends between 15 and 18 h. During this
stage, the natural antioxidants in rapeseed oil are no longer capable of
blocking the oxidation process because of their self-consumption.
Therefore, when the alkylradicals react with oxygen, the formation of
alkylperoxyradicals and hydroperoxides begins. At the end of the
induction period, the acidity slightly increases. This may indicate the
formation of free fatty acids due to the decomposition of triglyceride
fatty acid chains during the formation of short chain volatile
(short-chained hydrocarbons and alcohols) and non-volatile (epoxides,
high molecular weight compounds, and fatty acids) compounds [10].
The thermal oxidation of rapeseed oil preceding the end of the
induction period does not affect the oil's kinematic viscosity
because the compounds responsible for increasing the viscosity have not
yet formed (Fig. 1, b).
[FIGURE 1 OMITTED]
As rapeseed oil oxidises further from the end of the induction
period to a time of 20 h, the number of peroxides increases almost 3
times (Fig. 1, a). This sudden increase in peroxides is stimulated by
both the absence of a natural antioxidant effect and a sufficient amount
of oxygen entering with the ambient air, which increases the formation
of alkylperoxyradicals and hydroperoxides [9, 10].
To estimate the kinematic viscosity changes that occur in this
stage, the assumption can be made that following the end of the
induction period a complex oil decomposition process occurs and the
formation of new compounds begins. The growing viscosity implies the
formation of epoxides and polymer compounds [11]. The formation of these
compounds is initiated by a number of reactions beginning with the
formation of hydroperoxides and finishing with their decomposition; it
is then that short chain volatile and non-volatile compounds develop.
Water released during the decomposition of hydroperoxides initiates
triglyceride hydrolysis, i.e., the possibility of free fatty acid
formation. This process could explain the increase in acidity during
this stage, though the possibility of an impact by short chain compounds
on the acidity cannot be rejected.
As rapeseed oil oxidation proceeds further, the number of peroxides
grows more slowly and reaches a maximum by approximately 30 h. From this
point forward, the number of peroxides begins to decline. Other
researchers' analysis of sunflower oil and other oil methyl esters
shows similar changes in the peroxide value [6, 11].
The number of acids increases intensively from 20 to 40 h. It is
influenced by the decomposition of fatty acid chains that form low
molecular weight compounds. In addition, free fatty acids have been
forming during this period. In the late oxidation stages, it should be
mentioned that the value of acidity is exceptionally sensitive to the
end of the induction period. When oxidation was repeated, the position
of the induction period slightly changed, and it resulted in substantial
variation in the acidity value at times from 30 to 40 h.
In the final stage of oxidation, the kinematic viscosity of
rapeseed oil continues to grow. Its growth rate even increases between
30 and 35 h. This phenomenon may be related to the number of peroxides,
which starts to decrease from its maximum value after 30 h. In this
stage, because of the great quantity of hydroperoxides, the formation of
large molecular weight compounds is taking place and the viscosity
increases. Thus, the quantity of peroxides is reduced due to their
decomposition [6].
The increase in viscosity is also assisted by the evaporation of
volatile low molecular weight compounds associated with the operation of
a particular unit of oxidation equipment [12]. This is confirmed by an
increase in the density of the oxidised oil; after 40 h, oxidised
rapeseed oil has approximately a 5% higher density than nonoxidised oil.
When oil-dissolving compounds of low molecular weight evaporate, the
viscosity must increase.
One of the important parameters that determines the
temperature-viscosity relationship of lubricants is the viscosity index.
The variation in the viscosity index in oxidised oil is presented in
Fig. 1, b. Generally, triglycerides have a very high viscosity index
[13]. The rapeseed oil used in our research is no exception. Its initial
viscosity index value was 213, and during the first 18 hours of
oxidation, this value remained nearly unchanged. Furthermore, in the
oxidation process, the rapeseed oil's viscosity index decreased.
The decomposing triglyceride structure and a growing quantity of low
molecular weight compounds are assumed to have an impact on this
process. At the end of the experiments, the viscosity index value
stabilizes and remains steady between 35 to 40 h during the final
oxidation stage. It seems likely that the viscosity index is stabilised
by the great quantity of large molecular weight polymeric compounds
formed during this stage.
Usually when oils oxidise due to the processes taking place within
them, their colour changes and they emit a specific odour. In this
research, from the onset of oxidation to the end of the induction
period, the oxidised oil changed from a specific (yellowish) oil colour
at the beginning to a sharply yellow colour at the end of the induction
period. The yellow colour is likely caused by the primary oxidation
products (peroxides). After the induction period, primary oxidation
compounds split, and the oxidised rapeseed oil becomes transparent. This
hypothesis is supported by Yamane et al. [11] in their investigation of
the oxidative properties of oil methyl esters. They suggested that the
peroxide compounds formed during the induction period have a yellow
pigment. After the induction period, the sample becomes colourless as a
result of decomposition [11].
The change in the colour of oxidised rapeseed oil is measured by
optical spectroscopic analysis (Fig. 2). Prior to the induction period,
the compounds formed in oxidised rapeseed oil form two peaks (Fig. 2,
a). One peak, which is assumed to correspond to materials exhibiting a
yellow oil colour, is at a wavelength of 450-460 nm. The second, more
intensive peak forms at a wavelength of 380 nm. The large area of these
peaks supports the expectation that a great variety of compounds are
formed during oil oxidation, and their intensity correlates fairly well
with oxidation time. Until an oxidation time of 15 h, the intensifying
peaks likely indicates an increasing quantity of oxidation products.
After 15 h, the peak at a wavelength of 450 nm decreases, signalising
the change in material formation. This also confirms that the induction
period starting point is between 15 and 18 hours of oxidation.
After the end of the induction period, the peak at a wavelength of
450 nm disappears (Fig. 2, b), as does the yellow colour of the oxidised
rapeseed oil. The aforementioned sudden changes in the optical
properties of oxidised rapeseed oil perfectly correlate with the sudden
growth in the number of peroxides and acids during this period (1820 h)
(Fig. 1, a). These fast and drastic changes could occur due to the
conversion of alkylradicals to alkylperoxyradicals. In the literature,
this process is said to be rapid [9].
After the IP, the oxidised oil becomes more transparent. In a
transmission spectrum, the bright peak corresponding to a transmission
of 140% forms at a wavelength of 420 nm. Processes that occur during the
further oxidation of rapeseed oil (up to 40 h) reduce the intensity and
position of this peak, i.e., its maximum moves towards a longer
wavelength. After the induction period, the peak at a wavelength of 380
nm remains unchanged.
After 18 hours of oxidation, a small peak at a wavelength of 660 nm
forms in the rapeseed oil (Fig. 3). This peak is assumed to indicate the
high molecular weight compounds formed after the induction period. The
increase in kinematic viscosity after 18 h of oxidation may confirm this
(Fig. 1, b). The position and intensity of the peak formed by oxidising
rapeseed oil up to 40 h have not changed.
It was observed after tribological testing that the colour of the
sample also changes. To find the factors affecting the colour change in
the oil after the tribological test, the oil was spectrally analysed and
compared with non-oxidised rapeseed oil and oil after certain times of
oxidation (Fig. 4).
[FIGURE 2 OMITTED]
[FIGURE 3 OMITTED]
Rapeseed oil samples oxidised for 18 and 40 hours and tested in the
four-ball tribometer show different changes in their transmission
spectra. After the tribological test, rapeseed oil oxidised for 18 h has
become more yellowish --the peak at a wavelength of 450-460 nm has
increased (Fig. 4, a). Meanwhile, after the tribological test of
rapeseed oil oxidised for 40 h, especially distinct changes are
observed--the peak at a wavelength of 420 nm disappears, and the former
peak at 450-460 nm that was present before the induction period is
observed to become broader and more intense (Fig. 4, b).
[FIGURE 4 OMITTED]
During the tribological test, the oil is directly in contact with
the metal surfaces of machine elements, especially with interacting
surfaces where it is subjected to a high temperature. Therefore, it is
assumed that, during the tribological test, the decomposition of
hydroperoxides into alkyl and peroxyradicals under the action of metals
causes changes in the transmission spectrum. The greater changes in the
oil oxidised for a longer time can be explained by the greater amount of
decomposable hydroperoxides formed after the induction period. It is
also possible that the oil with a greater number of acids intensively
acting on the metal surfaces forms metal ions, which intensifies the
decomposition of the hydroperoxides.
As was observed in a previous study by Kreivaitis et al. [8], the
tribological properties of oxidised rapeseed oil change, but the impact
is not significant (Fig. 5). In this case the tribological properties of
rapeseed oil are assumed to be influenced by both the decomposing
structure of triglycerides and the newly forming compounds. At the end
of the induction period (18 h), the lubricating properties of the
oxidised rapeseed oil are worse than that of fresh oil. This change
could be caused by the increasing quantity of peroxides. Friction at
this point is also higher compared with non-oxidised rapeseed oil;
however, its increase is not as high as the increases in wear that were
observed.
Both the wear and the friction coefficient decrease at the end of
oxidation (40 h). The wear reduction properties of rapeseed oil oxidised
for 40 h are improved compared with those of oil oxidised for 18 h, but
the wear remains higher than that observed by lubricating with fresh
rapeseed oil. Meanwhile, the friction of oil oxidised for 40 h is
significantly lower than that of fresh oil and rapeseed oil oxidised for
18 h.
[FIGURE 5 OMITTED]
As mentioned above, the number of peroxides in and the acidity of
rapeseed oil was the highest at the end of the oxidation test. It seems
most likely that high molecular weight compounds formed in the final
oxidation stage had the greatest impact on wear and friction reduction.
High molecular weight polymeric compounds could form friction polymers,
which are known to be friction reduction materials [6]. The layers
formed by friction polymers are characterised by very low friction. This
was the case in both this and previous studies [8]. Nevertheless,
friction polymers act by covering and separating the surfaces by a thin
layer. If the surfaces are separated, the wear also should be very low.
The reason for high wear in this case could be the presence of
peroxides, which disturb this layer and increase wear.
The high viscosity can also influence the friction. The viscous
oxidised oil can easily separate the surfaces, reducing the friction.
The free fatty acids can also have an influence on such lubrication
properties [7].
4. Conclusions
The change in physicochemical properties has undisputed influence
on lubricity of the oil. The physicochemical and tribological properties
of rapeseed oil change substantially during its thermal oxidation. This
change particularly intensifies after the induction period. The results
show that the measured physicochemical properties of oxidised rapeseed
oil do not directly reflect the lubrication properties. In the oxidation
initiation stage, the tribological properties of rapeseed oil slightly
decrease. After the induction period, during the propagation stage, the
tribological properties of rapeseed oil are poorest. In the final stage
of rapeseed oil oxidation, high molecular weight compounds are formed,
which decreases the wear and friction between the contacting surfaces.
All of the oxidation stages can be observed using visible light
spectroscopy. The light transmission of rapeseed oil changes
substantially with the oxidation stage.
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Received September 24, 2013
Accepted May 09, 2014
R. Kreivaitis *, J. Padgurskas **, M. Gumbytc ***, V. Makareviciene
****
* Aleksandras Stulginskis University, Studentu 15, LT-53362
Akademija, Kauno r., Lithuania, E-mail: raimondaskreivaitis@gmail.com
** Aleksandras Stulginskis University, Studentu 15, LT-53362
Akademija, Kauno r., Lithuania, E-mail: juozas.padgurskas@asu.lt
*** Aleksandras Stulginskis University, Studentu 15, LT-53362
Akademija, Kauno r., Lithuania, E-mail: milda.gumbyte@asu.lt
**** Aleksandras Stulginskis University, Studentu 15, LT-53362
Akademija, Kauno r., Lithuania, E-mail: violeta.makareviciene@asu.lt
cross ref http://dx.doi.org/10.5755/j01.mech.20.3.5278