Modification of rapeseed oil and lard by monoglycerides and free fatty acids/Rapsu aliejaus ir kauliu tauku modifikavimas monogliceridais ir laisvosiomis riebalu rugstimis.
Kupcinskas, A. ; Kreivaitis, R. ; Padgurskas, J. 等
1. Introduction
Biological plastic lubricants (greases) are lubricating materials
based on vegetable (rapeseed, sunflower, soy, flax and other oils) or
animal (lard, beef, co-liver oil or other fat) origin. Such lubricants
are environmentally friendly taking into account that in the environment
no less than 80% of them disintegrate during 21 days while only 15-20%
of mineral lubricants do it in the same period [1].
Plastic lubricants are produced of basic materials (oil or fat),
thickeners and multipurpose functional additives which strengthen their
adequate operating properties.
Thickener is one of the key components as plastic lubricants
rendering them the form. Its main prerequisite is that they constitute
small-sized particles which are uniformly distributed and are capable to
form a sufficiently stable gel structure with the basic lubricant. Its
structure may be filamentary (metal soaps), laminar or spherical
(non-saponifiable thickeners). Basic lubricant contains about 70-90% of
lubricant material and 10-20% of thickener [2-4].
Lately scientists have started emphasizing more and more that oil
resources are abating, oil products are polluting the environment,
"a greenhouse effect" on the nature and human health is
increasing--all this result in the need to expand the use of biological
lubricants and fuels. For this reason greater attention is diverted to
alternative sorts of biological materials from renewable sources [4-6].
Vegetable oils consist of triglycerides which determine physical
and chemical properties of the oil. Triglycerides consist of glycerol with three fat acids. Triglyceride scheme is given in Fig. 1. Fat acids
contained in triglyceride may be saturated and unsaturated. In this case
(Fig. 1) triglyceride consists of saturated acids: saturated stearic,
monounsaturated oleic and polyunsaturated linoleic. Exactly these fatty
acids determine lubricating, oxidizing and temperature properties
[7-10]. Fatty acids contained in the oils may be saturated, mono- and
polyunsaturated.
Saturated fat acids in hydrocarbon chains do not have any double
links (Fig. 1) therefore they are resistant to oxidation. They are
desirable in lubricating materials for improving their oxidative
stability However, when hydrocarbon links stretch; the fatty acids
increase the temperature of mixture freezing. Compare: C12:0 (Lauric)
fat acid whose freezing temperature is about 44[degrees]C and C20:0
(Arachidic) who's freezing temperature is 76[degrees]C. It is
stated that high freezing temperatures are influenced by long, straight
hydrocarbon links capable of occupying very close interposition. In the
light of it, fatty acids in lubricating materials operating at low
temperatures are unwanted [7, 10].
[FIGURE 1 OMITTED]
In addition to oxidative stability saturated fat acids have one
more positive property ensuring the limiting lubrication of friction
surfaces. Stearic fatty acid contained in palm oil methyl ester is known
to constitute on the friction surface the adsorption layer of polar
molecules which reliably separates the interactive surfaces [7]. In
estimating temperature stability, greater unsaturation always reduces
the freezing temperature, and it is due to the geometric structure of
unsaturated fat acids.
CIS double link makes fatty acids molecules coil. The greater is
the number of CIS double links, the greater deformation of a fatty acid
molecule appears. Deformation minimizes the potential of the atoms to
distribute closely i.e. to crystallize. Thus, molecules occupying larger
volume remain in the liquid form up to the comparatively low
temperatures. Compare: the freezing point of oleic C18:1 acid is about
4[degrees]C while that of linoleic C18:3 is -11[degrees]C, and the
freezing point of arachidonic C20:4 is only -50[degrees]C [7].
An important property of plastic lubricants is their ability to
remain in a friction couple during its operation. It is greatly
influenced by both lubricating material and thickener. External
mechanical (load, movement speed) and thermal effects have an impact on
changes in the lubricant structure and its destruction which determine
substantially its mechanical as well as tribological properties. Owing
to these factors the thickener texture may be decomposed, the lubricant
colloidal structure disrupted and friction surfaces will not be
separated from each other, thus friction losses and wear will increase
[4, 11].
Friction and wear in the machine elements consume a great part of
the energy required. It depends on the properties of the lubricant and
acting surfaces as well. Various surface treatment techniques and
specific lubricants are suggested [12, 13].
The objective of this work is to investigate the impact of
monoglycerols, stearic and oleic acids on tribological and plastic
properties of the greases of rapeseed oil (RO) and lard (L).
2. Tested materials
Refined rapeseed oil (RO) and lard (L) and mixtures obtained by
modifying with monoglycerols (MG), stearin (SA) and olein acids (OA)
were tested. The amount of MG in rapeseed oil and lard was 10 and 20%,
respectively, while o SA and OA--2% (according to mass).
Monoglycerides are glycerides containing one sort of fat. They are
usually used as emulsifiers and stabilizers and as thickeners for
increasing consistence [9, 13, 14]. Mixtures were stirred with magnetic
blender TK 22. The obtained results were compared to commercial plastic
lubricant (reference). High quality universal plastic lubricant with
molybdenum disulfide additives for lubrication of various automobile
units was taken as reference.
3. Experimental procedures
Penetration was determined according to ASTM D 217-97. A 102.5 g
weight penetration cone was used.
A four-ball type tribotester was used to perform tribological
tests. The balls of 12.7 mm diameter were made of 100Cr6 bearing steel
(E = 21.98 [10.sup.4] MPa; v = 0.3; 63-66 HRC). The testing procedure
was adapted from the standard DIN 51 350, Part 3 [15].
A test oil sample of 22 [cm.sup.3] was poured into the sample
compartment fully submerging stationary balls. Under the applied load of
150 N and 300 N and the rotation speed of 1420 rpm, the machine was run
for 1 hour. Prior to each experiment, all the appropriate parts of the
machine, i.e. bottom and upper ball holders, oil vessel and test balls
were washed in an ultrasonic bath with hydrocarbon solvents, and then
dried.
The wear scar diameter on three stationary balls was measured with
an optical microscope. The results were recorded and reported in
millimeters as an average of the wear scar diameter (WSD) of three
balls. During the test the friction moment between the balls and the
temperature change of the oil sample were recorded.
4. Results and discussion
Results of penetration measurements are given in Table. By
modifying rapeseed oil with monoglycerides its consistence was increased
up to 00 NLGI class. Having additionally poured stearic or oleic acid,
the lubricant consistence increased up to 0 NLGI class. 00 and 0 classes
correspond to the consistence of lubricants used for lubricating
gearwheels in central lubricating systems.
Results of wear analysis are given in Figs. 2 and 3 when
lubricating with rapeseed oil and lard and after modifying them with
stearic and oleic acids and monoglycerides. The diagrams show that
modification with stearic and oleic acids and monoglycerides improved
the antiwear properties of the lubricants. Modification of rapeseed oil
and lard only with monoglycerides had no significant effect on anti-wear
characteristics. Only rapeseed oil modified with 10% monoglycerides
stands out when the wear trace diameter increased 1.1 times comparing to
that of pure rapeseed oil. The biggest antiwear efficiency was reached
by modifying rapeseed oil and lard with monoglycerides (20%) and stearic
acid (2%). Comparing the ball wear of pure lard and rapeseed oil to the
modified lubricants the difference is evident--after modification the
wear decreased 1.4 times. The modified lard and rapeseed oil have shown
similar results as the reference oil. The reason may lie in stearic and
oleic fat acids. They are attributed to polar molecules which make up an
absorption layer. Oleic acid is known as an additive for improving
lubricating properties of rapeseed oil, this acid making favorable
conditions to formation of the limiting oil layer. During the
experimental work under larger load (300 N, contact load 1325 MPa) and
lubricating with rapeseed oil modified with monoglycerides (20%) and
stearic acid (2%), the ball wear was 1.3 times greater than that when it
was lubricated with modified lard. Wear resistance of modified lard was
close to that of the reference oil. It testifies good antiwear
characteristics of modified lard.
Different images of traces have been observed when analyzing the
worn surfaces with an optical microscope. On the picture of the wear
trace surface when pure lard was used (Fig. 4, a) many small scars are
seen. The situation changes when monoglycerides (20%) (Fig. 4, b) are
added--the number of scars substantially decrease and distinct relieves
appear on the trace surface. With another addition of 2 of oleic acid
there are less scars and trace relief becomes more distinct. These
changes may occur when the microhardness of the deforming surface
decreases because of impact of fat acids. The microhardness in wear
trace is 8.25 GPa (at 5.1 mN loading) when using the lard. The
modification of the lard with 20% monoglycerides and 2% oleic acid
reduces the microhardness up to 5.76 GPa.
[FIGURE 2 OMITTED]
[FIGURE 3 OMITTED]
It is likely to be Rebinder's effect (decrease in strength of
the absorption surface layer). Compared to the reference oil (Fig. 4, e)
the wear traces at modified lard (Fig. 4, b, c, d) are significantly
smaller.
In Fig. 5 the images of wear traces which appear when lubricating
with modified lard and rapeseed oil are presented. They are obtained
with SEM microscope. The boundaries of wear traces indicate that the
wear was so negligible that the traces of the ball surface treatment
remained in the wear zone. It testifies about especially good wear
resistance characteristics of these materials.
Diagrams of variation of the friction moments during
experimentation are given in Fig. 6. They demonstrate that modification
of rapeseed oil and lard with monoglycerides (MG) and stearic acid (SA)
considerably (1.5 times) reduces the average friction moment. It should
be noted that modification with MG and SA, besides the reduction in
friction losses, substantially changes the friction moments variation
during the experiments. When testing pure RO under 150 N load, the
friction moment increases insignificantly and after three quarters of
the testing time the friction moment suddenly increases 1.5 times.
[FIGURE 4 OMITTED]
[FIGURE 5 OMITTED]
When testing pure lard, the increase in friction moment begins
sooner, namely, in the first third of the testing time. Having increased
by 40%, it remains stable. While testing RO at 300 N load, the increase
in friction moment begins earlier and later it stabilizes. The stable
friction moment during the whole testing period is typical for the lard,
but it is greater than testing RO. Having modified RO and L with
monoglycerides and stearic acid, the friction moment is decreasing
during the whole testing period. When testing the modified RO and L
under bigger (i.e. 300 N load), the variation of the friction moment is
analogous to the lower load, whereas a greater initial (static) friction
moment is typical for modified rapeseed oil and not for modified lard
(100 mNm and 75 mNm, respectively). The decrease in friction moment and
its greater instability during testing is typical for the reference oil
and the average friction moment is greater than testing both modified RO
and modified lard.
[FIGURE 6 OMITTED]
5. Conclusions
1. Concentration of monoglycerides has a direct impact on the
consistence of both rapeseed oil and lard. Additional modification with
stearic and oleic acid (2%) increases the rapeseed oil consistency, but
decreases that of lard. It testifies to different interaction of these
acids with the basic lubricating material.
2. When testing at 150 N loads, 10% monoglyceride additive has no
impact on wear resistance characteristics of lard but increase the wear
at rapeseed lubricants. Under this load the best characteristics are
demonstrated by the compositions consisting of basic lubricating
material (RO or L) with 20% monoglycerides and 2% stearic acid.
3. When testing at 300 N loads, the best antiwear characteristics
are demonstrated by the lard modified with 20% monoglycerides and 2%
stearic acid. Wear resistance characteristics of this lubricating
material are close to those of the reference plastic lubricant.
4. Modification of rapeseed oil and lard with monoglycerides and
stearic acid decreases the average friction moment (about 1.5 times) and
also changes the friction moment variation--it tended to decrease during
testing. The average friction moment of modified rapeseed oil and lard
is significantly lower than lubricating with reference oil.
5. Decrease in friction losses and wear of lubricating compositions
of basic material (RO or L), monoglycerides (20%) and stearic acid (2%)
may be explained by strength decrease in the adsorption layer
(Rebinder's effect).
http://dx.doi.org/ 10.5755/j01.mech.18.1.1292
References
[1.] CEC L-33-A-93 (U) 1995. Biodegradadility of Two-Stroke Cycle
Outboard Engine Oils in Water, The Coordinating European Council for the
Development of Performance Tests for Transportation Fuels, Lubricants
and Other Fluids, Brussels.
[2.] Jucas, P. 1992. Fuels and Lubricants, Mokslas 255 p. (in
Lithuanian).
[3.] Baltenas, R.; Sologubas, L.; Sologubas, R. 1998. Fuels and
Lubricants of Automobile, TEV, 415 p. (in Lithuanian).
[4.] Sukirno, Fajar, R.; Bismo, S.; Nasikin, M. 2009. Biogrease
based on palm oil and lithium soap thickener: evaluation of antiwear
property, World Applied Sciences Journal 6(3): 401-407.
[5.] Kadarohman, A.; Hernani Khoerunisa, F.; Astuti, R.M. 2010. A
potential study on clove oil, eugenol and eugenyl acetate as diesel fuel
bio-additives and their performance on one cylinder engine, Transport
25(1): 66-76. http://dx.doi.org/10.3846/transport.2010.09
[6.] Lebedevas, S.; Lebedeva, G.; Makarevicien?, V.; Kazanceva, I.;
Kazancev, K. 2010. Analysis on the ecological parameters of the diesel
engine powered with biodiesel fuel containing methyl esters from
camelina sativa oil, Transport 25(1): 22-28.
http://dx.doi.org/10.3846/transport.2010.04
[7.] Erhan, S. Z.; Perz, J. M. 2002. Biobased Industrial Fluids and
Lubricants, AOCS Press, Champaign, Illinois, 135 p.
[8.] Lamsa, M.; Kosonen, K. 2008. Third generation biohydraulics,
16th International Colloquium Tribology-Lubricants, Materials and
Lubrication Engineering, Ostfildern/Germany.
[9.] Murrenhoff, H. 2004. Environmentally friendly fluids--Chemical
modifications, characteristics and condition monitoring, O+P Olhydraulic
und Pneumatik 3: 48.
[10.] Kab, H. 2001. Market analysis: High oleic vegetable oils
possibilities to use in industry, Gulzower Fachgesprache: Band 19 (in
Germany).
[11.] Matveevskij, P.M.; Lashxi, V.L.; Bujanovskij, I.A. a.o. 1988.
Lubricants: Antifriction and antiwear properties. Test Methods:
Handbook, Moscow, Maschinostroenije, 220 p. (in Russian).
[12.] Jankauskas, V.; Belyaev, S. 2010. Influence of conterbody
surface hardness of a friction part "steel-steel" on
tribological behaviour of zinc nanopewder in oil, Mechanika 3(83):
45-50.
[13.] Gumbyte, M.; Makareviciene, V. 2007. Selectivity of Lipases
as Biocatalyst in the Glycerolysis of Oleic Acid and Glycerol, Vagos
77(30): 90-95 (in Lithuanian).
[14.] Zdravecka, E.; Suchanek, J.; Tacova, J.; Trpcevska, J.;
Brinkiene, K. 2010. Investigation of wear resistance of high velocity
oxy-fuel sprayed WC-Co and Cr3C2-NiCr coatings, Mechanika 4(84): 75-79.
[15.] DIN 51350-3. Testing of lubricants--Testing in the four-ball
tester--Part 3: Determination of wearing characteristics of liquid
lubricants, 1977 (in Germany).
A. Kupcinskas, Lithuanian University of Agriculture, Studentu 15,
LT-53362 Akademija, Kauno r., Lithuania, E-mail:
arturas.kupcinskas@lzuu.lt
R. Kreivaitis, Lithuanian University of Agriculture, Studentu 15,
LT-53362 Akademija, Kauno r., Lithuania, E-mail:
raimondaskreivaitis@gmail.com
J. Padgurskas, Lithuanian University of Agriculture, Studentu 15,
LT-53362 Akademija, Kauno r., Lithuania, E-mail:
juozas.padgurskas@lzuu.lt
V. Makareviciene, Lithuanian University of Agriculture,
Universiteto 10, LT-53361 Akademija, Kauno r., Lithuania, E-mail:
violeta.makareviciene@lzuu.lt
M. Gumbyte, Lithuanian University of Agriculture, Universiteto 10,
LT-53361 Akademija, Kauno r., Lithuania, E-mail: milda.gumbyte@lzuu.lt
Received February 11, 2011
Accepted February 02, 2012
Table
The penetration number of tested materials (according to ASTM D 217-97)
Tested materials RO + MG RO + MG 20% RO + MG 20%
20% + OA2% + SA 2%
NLGI class 00 0 0
Penetration at 400-430 355-385 355-385
25[degrees]C
Tested materials L L + MG 10% L + MG 20%
NLGI class 1 2 4
Penetration at 310-340 265-295 175-205
25[degrees]C
Tested materials L + MG 20% L + MG 20% Reference
+ OA 2% + SA 2%
NLGI class 2 2 3
Penetration at 265-295 265-295 220-250
25[degrees]C