Fatty Acids and Antioxidant Effects On Grease Microstructures
Fatty Acids and Antioxidant Effects On Grease Microstructures
Fatty Acids and Antioxidant Effects On Grease Microstructures
Abstract
The search for biobased material as industrial and automotive lubricants has accelerated in recent years. This trend is primarily
due to the nontoxic and biodegradable characteristics of seed oils that can substitute mineral oil as base fluid in grease making. The
paper discusses the preparation of lithium soap-based soy greases using different fatty acids and the determination of crystallite
structure of soap using transmission electron microscopy (TEM). Lithium soaps with palmitic, stearic, oleic, and linoleic acids
were synthesized and mixed with soybean oil (SBO) and additives to obtain different grease compositions. TEM measurements
have revealed that the soap crystallite structure impact grease consistency. Soap fiber length and their cross-linking mechanism in
the matrix control grease consistency (National Lubricating Grease Institute (NLGI) hardness, ASTM D-217 method). Lithium
stearate-based soy grease has a relatively more compact fiber structure than Li palmitate. Linoleic acid (C18 , = =) with two sites
of C–C unsaturation in the chain has a much thinner and more compact fiber network than oleic acid (C18 , =). The presence of
additive in grease produces a soap with looser network and larger fiber structure than similar grease containing no additive. A
close analysis of grease microstructure will help in the development of better performing grease for industrial applications.
© 2004 Published by Elsevier B.V.
Keywords: Vegetable oils; Li grease; Fatty acids; Transmission electron microscopy; Fiber structure
to various functional properties of grease. Grease determined by gas chromatographic analysis (AACC
consistency (or National Lubricating Grease Institute 58-18, 2000) in percentage: C16:0 = 6; C18:0 = 5.5;
(NLGI) hardness, ASTM D-217 method, 2000) is C18:1 = 22.0; C18:2 = 66.0; and C18:3 = 0.5. This
largely dependent upon the thickener fiber structure oil shows much lower linolenic content (0.5%) than
and its distribution in the grease medium. The perfor- regular soy oil (≈8%). The lower linolenic acid moi-
mance properties of grease are primarily dependent ety in the fatty acid chain results in a significant
on their ability to provide lubrication to mechanically improvement in the thermo-oxidative stability of veg-
operating moving parts by supplying base oil as a thin etable oil structure. Lithium hydroxide monohydrate
film separating the metallic surfaces and also remov- (LiOH·H2 O, 98%), palmitic (90%), stearic (95%),
ing heat and wear debris from the friction zone. The oleic (90%), and linoleic acids (90%) were obtained
physical and chemical degradation of grease during from Aldrich (Milwaukee, WI) and were used without
use (Carré et al., 1983; Araki et al., 1995) and failure any further purification.
of various mechanical parts due to inadequate lubri-
cation (Cann and Lubrecht, 1999) have been reported. 2.2. Additive
Several mechanisms have been proposed on timed
lubricant release and replenishment of starved lubri- Antimony dithiocarbamate used as an antioxidant
cant sites during operation. Laboratory simulations and extreme pressure additive was obtained from
range from simple thermal stability tests to more com- R.T. Vanderbilt Co. Inc. (Norwalk, CT). Additive was
plex lubrication measurements (Aihara and Dowson, added at 0–8% by weight of the total formulation.
1978; Zhu and Neng, 1988; Williamson, 1995). How-
ever, a model of this mechanism resulting in stable 2.3. Grease preparation
lubricant film formation in concentrated metal contact
has not been established and requires more experimen- A mixture of LiOH·H2 O, fatty acid (taken in 1:0.75
tal findings. to 1 equivalent ratio with the Li-based material), and
Unpublished data show that the fatty acid chain SBO (in equivalent weight ratio of the metal–acid
length and C–C unsaturation influence soap fiber struc- mixture) were uniformly mixed with a mechanical
ture and their networking mechanism. Therefore, an stirrer at 90 ◦ C in a 3 l wide-mouth glass reactor. The
understanding of fiber growth and their network struc- temperature was then slowly raised to 190 ± 2 ◦ C
ture in grease matrix is required to relate base oil and maintained for 3 h with stirring. After the cook-
holding capacity and oil release by shear degradation ing period, the mixture was allowed to cool; and at
of soap thickener during operation to additive com- 150 ◦ C, an additional amount of SBO (60–80% of the
patibility, bleed resistance, viscosity, thermal stabil- total reaction mixture) and additive (0–8 wt.% of the
ity, texture, and appearance. Critical physiochemical total reaction mixture) were added. The final mixture
properties are therefore dependent on the consistency was allowed to cool to room temperature to obtain
of grease and their behavior in the mechanical system. the grease. The resulting grease was milled using
Controlling the growth and distribution of soap fiber 3-roll mill equipment. During this process, grease
during grease manufacturing processes can result in was passed through the rollers thrice until it was
products with the desired physical, chemical, and per- thoroughly homogenous and the particle size reached
formance properties. 2–3 m. The final product had a smooth, paste-like
texture. Similar procedure was used to prepare the
other greases made with varying composition of base
2. Materials and methods oil, fatty acid, lithium hydroxide, and additive.
Alkali refined soybean oil (SBO) from Pioneer Hi The grease samples were diluted with water and
Bred Intl. Inc. (Des Moines, IA) was used as the base one drop of grease solution was added with a pipette
fluid. The oil has the following fatty acid composition onto a carbon film of copper grid. Philips EM 400 was
A. Adhvaryu et al. / Industrial Crops and Products 21 (2005) 285–291 287
Fig. 2. Triacylglycerol molecule. Dark circles are oxygen atoms of the ester groups.
288 A. Adhvaryu et al. / Industrial Crops and Products 21 (2005) 285–291
Table 1
Composition and NLGI hardness of lithium-based soy grease
Fatty acid Metala :fatty acid ratio Metal soap:oilb ratio NLGI hardnessc Antioxidant (wt.%)d
chain is oriented away from the metal surface to form the long chain fiber structure, increased interactions
a monomolecular layer with excellent boundary lu- with base oil in the matrix can be achieved. Grease
brication properties. When the molecule is adsorbed developed under such condition shows high consis-
on the metal surface, two types of interactions occur. tency resulting in higher hardness. The composition
The adhesive interaction between the ester group and and NLGI hardness of lithium-based greases prepared
metal is very sensitive to the type and number of with different fatty acids are listed in Table 1.
functional groups. The lateral interaction caused by The TEMs of palmitic [CH3 (CH2 )14 COOH] and
dipole–dipole and dispersive interaction between the stearic [CH3 (CH2 )16 COOH] acids used in the lithium
hydrocarbon chains is sensitive to structural properties soap to develop soybean oil-based grease are shown
including chain length, unsaturation, and stereochem- in Fig. 3a and b, respectively. Under similar magnifi-
istry (Jahanmir and Beltzer, 1986a, 1986b). Similarly, cation (1.81 m), Li stearate-based soy grease shows
the nature of fatty acid in the soap structure of grease a relatively more compact fiber structure than Li
has a significant influence on the physical and chemi- palmitate. This is also evident from the NLGI hard-
cal properties. In the current study using transmission ness of grease presented in Table 2 (more hardness
electron microscopy (TEM), we observed the forma- is represented by higher numerical value). It appears
tion of dispersiod structure with compact network that such compact mesh structure can hold relatively
with an increase in the chain length of the fatty acid in larger amounts of base fluid in the soap matrix due
lithium soap. With more interlocking resulting from to the excellent interaction. This increases the ability
Fig. 3. Effect of fatty acid chain length on the soap fiber structure: (a) Li palmitate soap and (b) Li stearate soap.
A. Adhvaryu et al. / Industrial Crops and Products 21 (2005) 285–291 289
Fig. 4. Effect of C–C unsaturation in the fatty acid chain on the soap fiber structure: (a) Li oleate soap and (b) Li linoleate soap.
290 A. Adhvaryu et al. / Industrial Crops and Products 21 (2005) 285–291
Fig. 5. Effect of additive on the fiber structure of soap: (a) Li stearate soap and (b) 4 wt.% additive doped in Li stearate soap.
influencing its crystallization. Similarly, the optimum The Li stearate-based soy grease has a relatively more
condition for fiber growth through crystallization may compact fiber structure than Li palmitate. The linoleic
vary with different additives. It is believed that the ad- acid (C18 , = =) with two sites of C–C unsaturation in
ditive molecules are first bound to the soap fibers and the chain exhibits a much thinner and more compact
the chains attached to additives hold the oil. The TEMs fiber network than oleic acid (C18 , =). The presence
(Fig. 5a and b) show the effect of antimony dithio- of additive in grease gives a soap with looser net-
carbamate additive on Li stearate soap structure. Un- work and larger fiber structure than similar grease with
der magnification (1.81 m), the additive doped grease no additive. Transmission electron microscopy gives a
has a looser network structure with larger fibers than more defined soap structure with respect to changes in
the non-additive doped grease with similar metal, fatty the fatty acid composition and additive concentration.
acid, and base oil composition (see Table 1). It may Therefore, optimal selection of fatty acids in soap is
be noted, however, that due to the presence of additive required to control the fiber length-to-diameter ratio as
molecules, grease hardness is not altered significantly well as the extent of fiber cross-linking that stabilizes
as a result of changes in the soap fiber length and their the base oil in grease.
distribution in the matrix.
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