Modification of rapeseed oil with free fatty acids/Rapsu aliejaus modifikavimas laisvomis riebalu rugstimis.
Padgurskas, J. ; Kreivaitis, R. ; Kupcinskas, A. 等
1. Introduction
At present ecological requirements are in the great importance. A
lot of studies had been made in the field of bio fuels, trying to reduce
pollution by exhausted gases and use renewable resources [1, 2]. At the
same time tribological properties ate important too. Friction and wear
in the machine elements consumes a great part of the energy required.
Various surface treatment technologies and specific lubricants are
suggested [3, 4]. Nevertheless from the ecological point of view
rapeseed oil is remaining as most attractive basis for the production of
environmentally friendly lubricants. This attractiveness is caused by
biodegradable properties together with comparably good lubricating
characteristics [5].
Vegetable oils have naturally good lubricating properties, but the
reliable wear protection forces the use of appropriate additives.
Vegetable oils modified with additives have lubricating properties equal
to those of equivalent mineral oils [6].
Modification of environmentally friendly lubricants is strongly
regulated by different ecological marks: The European Eco-label, The
German "Blue Angel", Nordic countries "White Swan",
Canadian "EkoLogo" a.o. [7, 8]. These standards regulate the
amount of additives, restricted materials and elements etc. In order to
fulfil these requirements, it is necessary to look for the possibility
of using those additives which would be natural, non-toxic and easily
degradable in the environment. One of such additive types is free fatty
acids (FFA).
The effectiveness of free fatty acids in mineral oils has been
known for a long time. Its use for the modification of plant oils has
been investigated too [4, 6, 9, 10].
It is predicated that saturated and unsaturated fatty acids (FA)
effectively improve the lubricating properties of base oils. However its
effectiveness depends a lot on the compatibility of the modified base
oil and free fatty acids. The temperature at the contact zone of the
lubricated surface is very important too [4].
Saturated and unsaturated fatty acids have different operating
mechanisms. The action of saturated fatty acids is based on the
formation of an absorbed layer. Directly and vertically to surface
oriented molecules of saturated fatty acids form the dense layer which
separates the surfaces. This is the reason why such layers have good
friction reducing properties [11]. It is believed that unsaturated fatty
acids can not locate so densely at the surface because of their double
bonds. Therefore the efficiency is lower. It is supposed that
unsaturated fatty acids could oxidize between interacting surfaces and
loose their lubricating properties [4]. However there are opinions that,
at higher temperatures, the unsaturated fatty acids can come between
lubricated surfaces forming the tribo-polymeric layer which reduces the
friction and wear [9].
This investigation shows that free fatty acids ensure good
lubrication at boundary lubrication conditions. However their extreme
pressure (EP) properties are not good enough comparing them to reference
oils. Therefore it is proposed to use it together with poly-atoms of S
and N, which could ensure the EP properties. The combination of sulphur
atoms with fatty acids increases the synergetic effect--fatty acids
reduce the friction and sulphur ensures the EP properties and reliable
wear protection. Additionally, those elements have a low toxicity which
is very important for environmentally friendly lubricants [6].
The aim of this research is the investigation of the influence of
free fatty acids, provided by LUBRIZOL Company, on the lubrication
properties of rapeseed oil. The results should be compared to commercial
environmentally friendly lubricants.
2. Tested materials
Pure rapeseed oil and rapeseed oil modified with free fatty acids
(FA) were investigated. The refined rapeseed oil from the market was
investigated without any processing or modification with inhibitors.
Free fatty acids were received from LUBRIZOL Company as the oil additive
(ADX 18) for improving the lubricating properties of environmentally
friendly oils. Free fatty acid concentrations of 0.5; 1 and 2% were used
for the modification of rapeseed oil. The test results were compared to
the commercially available environmentally friendly lubricant produced
on the basis of rapeseed oil. The physical and chemical properties of
the investigated materials are presented in Table.
3. Testing procedures
Tribological tests were performed using a fourball type
tribotester. The balls of 12.7 mm diameter were made of 100Cr6 bearing
steel (E = 21.98T04 MPa; v = 0.3). The testing procedure was adapted
from the standard method DIN 51 350, Part 3 [12].
Loads of 150 N and 300 N were used. The test runs 1 hour. Prior to
each experiment, all the appropriate parts of the machine, i.e. bottom
and upper ball holders, oil vessel and the test balls were washed in an
ultrasonic bath and then dried.
The diameters of the wear scars on three stationnary balls and the
friction surfaces were measured and analyzed with an optical microscope.
For each run the scar measurements were reported as an average of the
Wear Scar Diameter (WSD) of the three balls in millimetres. The copper
corrosion test was performed using standard method ISO 2160.
[FIGURE 1 OMITTED]
4. Results and discussion
Tribological investigations of rapeseed oil modified by free fatty
acid show the efficiency of this additive for wear and friction
reducing. However the results for operation at the higher load (300 N)
are different to those at the lower loading (150 N) regimen.
Wear of the balls in the higher load regimen decreased 1.4 times
(Fig. 1) when lubricated with rapeseed oil modified with 0.5%
concentration FA. A further increase in additive concentration does not
influence significantly the wear decrease--the use of 1 and 2%
concentration FA reduces the wear by 1.45 and 1.48 times.
There are several theories explaining the influence of FFA on the
lubricating properties of oil [4, 9]. In this case, the adsorption of FA
on the lubricating surfaces is the most likely. Higher protection of
lubricating surface is most probably ensured by the formation of a dense
adsorbed layer of FA [4, 13].
Usually such adsorbed layers have good friction reducing properties
and are known as "friction modifiers" [7]. However, in our
case the friction increased--the using of 0.5% concentration FA additive
slightly increased the average torque, compared to pure rapeseed oil.
Increasing the amount of FA slightly reduces the friction and, at 2%
concentration, it becomes lower than when lubricating with pure rapeseed
oil. The test revealed that average torque is significantly lower when
using the modified and nonmodified rapeseed oil compared to the
reference oil.
FFA additives not only change the average value of friction but
also its variation during the operation (Fig. 2). There is no torque
variation tendency when lubricating with pure rapeseed oil--torque
increases at the beginning, after that decreases and, at the end of
tests, starts again to increase. Such changes in torque are
characteristic for non-stable lubrication of friction pairs and are
followed by high wear. After modification of rapeseed oil with FA, the
friction had a tendency to increase. That is also the sign of bad
lubrication conditions, but it is better than nonstable conditions [4].
The evaluation of torque stability shows that the most stabile
torque occurs when rapeseed oil is modified by FA at 0.5% concentration.
The friction change has a different character when lubricating with
reference oil. In this case, friction torque increases significantly at
the beginning, after that it stabilises and, for the most part of the
investigation, stays constant.
The friction decrease occurs at the beginning of tests at the high
load (300 N) when lubricating with FA modified rapeseed oil (Fig. 2).
This is not usual for rapeseed oil lubrication. This decrease occurs for
longer when the FA concentration is increasing. This phenomenon could be
related to temperature of the contacting surfaces. The oil temperature
at the beginning is usually 30[degrees]C and increases during the test
until 70[degrees]C at the test end. However the oil temperature does not
reflect the temperature in the contact zone. Therefore it is possible
that the FA loses their efficiency and the friction torque starts to
increase when the temperature in the contact zone is much higher that
oil temperature. Other researchers predicate that there are transfer
temperatures which indicate the operation limits of the adsorption layer
which is created by FA. This layer decays when the transfer temperature
is exceeded--the wear intensity and friction increases [4, 9]. Higher
viscosity of FA modified oil could also influence the reduction in
torque (Table).
The temperature of 67[degrees]C, which is recommended by LUBRIZOL
for dissolving the FA mixture, supposes the biggest part of the mixture
consists of saturated long chain fatty acids. After creating mixtures of
rapeseed oil and varying concentrations FA additives, it was detected
that, at 1% concentration, the FA mixture separates at room temperature.
The mixture jells, hardly remaining fluid at the concentration of 2%.
Only a 0.5% concentration of FA does not cause these changes to rapeseed
oil. Therefore, 2% concentration of FA is not appropriate for the
modification for rapeseed oil.
[FIGURE 2 OMITTED]
The evaluation of friction of 0.5 and 1% concentration mixtures at
higher load shows lower friction of the 1% concentration mixture.
Therefore, taking into consideration the reasons mentioned above, it was
decided to investigate only the 1% concentration mixture at lower loads.
Evaluation of wear reducing properties of investigated lubricants
at lower loads (150 N) reveals that a 1% concentration FA mixture
decreases the wear of test balls by 1.75 times (Fig. 3). This is also
1.12 times more efficient than the reference oil. These wear reduction
values show that the modification of rapeseed oil with 1% concentration
FA mixture is sufficient for the wear protection of machine elements
operating at this regime.
Taking into consideration the 1.33 times lower friction coefficient
of FA mixture comparing to reference oil at lower loading, the formation
of absorbic layer is the most probable [7]. Rapeseed oil modified with
1% FA mixture reduces the average torque up to 1.2 times and essentially
changes the process of friction variation (Fig. 4). The friction value
varies considerably during the tests when lubricating with pure rapeseed
oil, the same was as at the higher load. The FA modified oil preserves
regular friction between the lubricated surfaces throughout the test.
Such a torque characteristic is desirable in friction pairs. Friction
torque is also stable when lubricating with the reference oil, but at
the beginning we have a significant rise (Fig. 4).
[FIGURE 3 OMITTED]
The results of wear tests at a higher load regime show that the
wear protection provided by FA modified rapeseed oil is lower than for
reference oil (Fig. 1), but, at the lower load, the FA modified oil is
more efficient (Fig. 3). Despite the lower friction of the modified oil,
the unstable torque at higher load shows that such FA modioperate at
lower loads.
[FIGURE 4 OMITTED]
Fig. 5 presents the wear surfaces after tests with pure rapeseed
oil lubrication and lubrication with FA modified rapeseed oil. Apparent
difference in wear scars is clearly seen for those two types of
lubrication which applies both for lower and higher loading. Wear scar
is very small when lubricating with FA modified oil and applying the
lower loads (Fig. 5).
A part of wear scar is covered by remained wear protection layer.
Such picture correlates to the torque results - lower friction
correspond to small and even wear surface.
[FIGURE 5 OMITTED]
Surfaces have much more scratches if they operate at higher
loading. Operation with FA modified rapeseed oil caused much more
scratches (Fig. 5, d). Higher friction reflects in this picture even if
the wear value was lower.
It confirms that the modification of rapeseed oil with FA additives
is not efficient at the lubrication of friction pairs which operate on
higher contact loads.
5. Conclusions
The modification of rapeseed oil with free fatty acid is effective
regarding the reduction of friction and wear. The investigated mixtures
are more efficient at the lower load compared to the reference oil.
However the wear decreasing at higher loads is not sufficient. The use
of rapeseed oil, modified with free fatty acid, can ensure wear
protection of machine elements and reduces the friction losses at low
load conditions.
Acknowledgement
The authors thank LUBRIZOL Company for the research materials.
Received September 30, 2010
Accepted March 15, 2011
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J. Padgurskas, Lithuanian University of Agriculture, Studentu 15,
53362 Akademija, Kauno r., Lithuania, E-mail: juozas.padgurskas@lzuu.lt
R. Kreivaitis, Lithuanian University of Agriculture, Studentu 15,
53362 Akademija, Kauno r., Lithuania, E-mail:
raimondaskreivaitis@gmail.com
A. Kupcinskas, Lithuanian University of Agriculture, Studentu 15,
53362 Akademija, Kauno r., Lithuania, E-mail: arturas.kupcinskas@lzuu.lt
A. Zunda, Lithuanian University of Agriculture, Studentu 15, 53362
Akademija, Kauno r., Lithuania, E-mail: audrius.zunda@lzuu.lt
Table
Physicochemical properties of tested oils
Material
Rapeseed Rapeseed
Property Oil Oil + 1% FA Reference
Viscosity, cSt: 34.7 35.1 63.2
at 40[degrees]C at 8.0 8.1 13.9
100[degrees]C
Viscosity index 213 217 231
Acidity, mg KOH/g 0.07 0.75 n.d.
Copper corrosion A1 A1 n.d.