Wear 268 (2010) 104–108

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Wear
journal homepage: www.elsevier.com/locate/wear

Assessment of lubricity of compositions of fuel oil with biocomponents derived

from rape-seed
M.W. Sulek, A. Kulczycki, A. Malysa ∗
Techical University of Radom, Department of Chemistry, 26-600 Radom, Chrobrego 27, Poland

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents an assessment of tribological properties of compositions of fuel oil containing fatty
Received 18 December 2007 acid methyl esters derived from rape-seed oil. An HFRR (high-frequency reciprocating rig – ball-on-
Received in revised form 30 April 2009 flat) apparatus was used in this investigation. The studies were carried out for a steel–steel pair in the
Accepted 17 July 2009
concentrated contact.
Available online 24 July 2009
The tribological properties were determined by motion resistances, wear and lubricant film concen-
tration. The surfaces were analysed after tribological tests. The aim of the investigation was an attempt
Keywords:
to obtain a correlation between wear quantities being measured and percentage content of bioadditives
Fuel oil
Friction coefficient
in fuel oil. It was found that at as little as 5% of the additive the coefficient of friction decreases by about
Lubricity 20% while wear decreases twofold relative to fuel oil, which may result from an increase in the stability
Wear of the lubricant film.
Biodiesel © 2009 Elsevier B.V. All rights reserved.
Fatty acid methyl esters

1. Introduction from vegetable oils. On the European and world markets methyl
esters are used as fuel oil additives or in the pure form as the
Fuel oils are a basic energy carrier used to drive a diesel engine. so-called biodiesel (100% methyl esters). Biodiesel has a number
As fuels they must satisfy a number of quality requirements defined of advantages compared to conventional fuel oil, the most impor-
by law. The most important characteristics of fuel oil include tant ones being biodegradability and absence of harmful elements
pumpability, filterability, low corrosivity, chemical stability and and aromatic compounds. The higher cetane number of biodiesel
self-ignition capacity characterized by the cetane number [1,2]. The improves engine performance, while higher ignition temperature
quality of fuels is considerably affected by their lubricity level. The ensures fire safety during storage. It is worth noting that vegetable
fuel oil components that increase lubricity are higher hydrocar- oil esters have less than 20% more oxygen bounded in fatty acids
bons and sulfur compounds. These additive may adversely affect which improves the combustion process of the mixture and reduces
the construction materials of the fuel and lubrication systems. It the emission of carbon black and solid particles to the atmosphere
has been found that sulfur has a deleterious effect on the ther- [4,5,12,14].
mal and thermooxidative stability and a tendency to cause metal Numerous literature data on the application of methyl esters
corrosion. Besides, fuel combustion products containing SO2 and as biocomponents raise doubts and objections mainly among car
SO3 form acids in aqueous environment which cause corrosion of manufacturers and users. Despite the fact that a number of studies
exhaust system elements and pollute the natural environment (acid have been carried out in this field, there is a need to conduct further
rain). However, a reduction in sulfur content in petroleum products systematic research confirming possible application of this kind of
to below 50 mg/kg, due to ecological considerations, resulted in a alternative fuels [6,13].
decrease in lubricating properties of fuel oils [2,3].
The changes described resulted in a necessity to add new
2. Experimental method
non-toxic environment-friendly lubricant additives to conventional
fuels. These criteria can be satisfied by additives based on renewable
2.1. Lubricating substance
resources, particularly by fatty acid methyl esters (FAME) derived

Fatty acid methyl esters prepared by transesterification of rape-

seed oil with methanol in the presence of an alkaline catalyst
∗ Corresponding author. Tel.: +48 0483617080. produced by the “TECHNO-ORG” Wrocław company were used in
E-mail address: [email protected] (A. Malysa). this investigation.

0043-1648/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.wear.2009.07.004
M.W. Sulek et al. / Wear 268 (2010) 104–108 105

Table 1
Basic properties of methyl esters of fatty acids derived from rape-seed oil.

Physicochemical properties Composition of acid

rests in the rape-seed
oil

Density d20 [g/cm3 ] 0.89 C16:0 1–5%

Acid value [mg KOH/g] 0.5–3 C18:0 0–3%
Iodine value [J2 /100 g] 97–120 C18:1 9–25%
Glycerol concentration [%] 0.2 C18:2 11–25%
Water concentration [%] 0.04 C18:3 5–12%
Solid to liquid temperature [◦ C] −20 C20:0 0–2%
Self-ignition temperature [◦ C] >160 C20:1 5–15% Fig. 2. Dependence of friction coefficient on concentration of solutions of fatty acid
C22:0 0–2% methyl esters derived from rape-seed oil in fuel oil. High-frequency reciprocat-
C22:1 30–60% ing rig (HFRR tester). Vibration frequency, 50 Hz; load, 2 N; stroke length, 1 mm;
temperature of liquid, 60 ◦ C; test duration, 75 min.
The following equation represents the transesterification reac-
tion:

The basic physicochemical properties and composition of the prod-

uct have been given by “TECHNO-ORG” in Table 1.
Plain methyl esters and their compositions with fuel oil con-
taining 5, 10, 15, 20, 25 and 30 wt% of the additive were used as
lubricating substances. Fig. 3. Dependence of lubricant film concentration on concentration of solutions
of fatty acid methyl esters derived from rape-seed oil in fuel oil. High-frequency
reciprocating rig (HFRR tester). Vibration frequency, 50 Hz; load, 2 N; stroke length,
2.2. Tribological studies
1 mm; temperature of liquid, 60 ◦ C; test duration, 75 min.

The tests were carried out at the Institute for Fuels and Renew- with the AISE E-52100 standard. Before the measurements all sam-
able Energy (Instytut Paliw i Energii Odnawialnej) in Warsaw, by ples (balls and disks) had been thoroughly chemically cleaned and
means of a tribological tester based on reciprocating motion (HFRR). then dried [8].
The HFRR method makes it possible to observe lubricant film for- The tests were carried out in the presence of fuels or their com-
mation for additives in the boundary lubrication region even with positions with esters. The volume of the solution was 2 cm3 . During
a small volume of the fuel being tested. Besides, it makes it possible the test the plate was fully submerged which ensured friction in the
to assess adhesive and fretting wear also at a low sliding velocity. presence of the liquid being tested. Constant humidity and temper-
At low velocity values the effects of friction-generated heat and vis- ature were maintained taking into account the effect of external
cosity on measurement conditions are reduced [1,8]. A diagram of conditions on the quantities being measured. The measurements
the device can be seen in Fig. 1. were carried out in a chamber ensuring constant humidity and the
The HFRR method is used to assess lubricity of fuel oils and fuels temperature of the liquid was maintained at 60 ◦ C. The test lasted
containing lubricant additives. The concentrated contact is used in for 75 min. On the basis of the measurements conducted it was
the ball-on-flat system. Typical measurement parameters defined possible to determine friction coefficient (), corrected wear scar
in the PN-EN ISO 12156-1 standard were applied. diameter (WS 1.4) and lubricant film concentration.
A test ball (upper sample—Fig. 1) fixed in a grip performed recip- The coefficient of friction between the samples was deter-
rocating motion at the frequency of 50 Hz and with a 1 mm stroke. mined from the following equation:
The diameter of the ball was 6 mm and it was made of steel of Rock-
F
well hardness 58–66 and roughness of RA < 0.05 ␮m. The ball was = ,
P
in frictional contact with a test plate (lower sample—Fig. 1) and the
load applied was 2 N. The steel plate was produced by machining. where F is friction force, and P is load in N.
Its Vickers hardness “HV30” ranged from 190 to 210, whereas its
roughness, whose measure is an arithmetic mean of profile devi-
ation from the mean line RA , was less than 0.05 ␮m in conformity

Fig. 4. Dependence of corrected wear scar diameter (WS 1.4) on concentration of

solutions of methyl esters of fatty acids derived from rape-seed oil in fuel oil. High-
Fig. 1. Diagram of mechanical unit of HFRR, 1: upper sample, 2: heating block, 3: frequency reciprocating rig (HFRR tester). Vibration frequency, 50 Hz; load, 2 N;
lower sample, 4: thermometer, 5: force converter [7]. stroke length, 1 mm; temperature of liquid, 60 ◦ C; test duration, 75 min.
106 M.W. Sulek et al. / Wear 268 (2010) 104–108

The wear scar diameter WS 1.4 was determined on the basis of The contact resistance of friction pair elements is a measure
the measurement of a wear trace generated on the test ball. Then the of lubricant film concentration. High resistance values corre-
value was corrected to the standard water vapour pressure—1.4 kPa spond to the formation of a lubricant film separating rubbing
[8]. elements, whereas for a direct metallic contact the resistance

Fig. 5. Surface roughness: non-mated surface (a), wear scar in the presence of fuel oil (b) and FAME solutions from rape-seed oil of increasing concentrations: 5% (c), 10% (d),
15% (e), 20% (f), 25% (g), 30% (h), 100% (i). Profilometer TOPO L50.
M.W. Sulek et al. / Wear 268 (2010) 104–108 107

equals zero. The number of lubricant film breakages is recorded 3. Test results
electronically during the test and expressed in percentage values
[9,10]. A 75-min test at a constant load (2 N) was performed in the pres-
ence of methyl esters and their solutions in fuel oil. A comparative
2.3. Surface analysis after friction test with fuel oil as a lubricant was also carried out. As a result
arithmetic mean after 3 independent measurements was taken. As
The tests were carried out by means of a profilometer TOPO L50 a measure of mistake a standard deviation of arithmetic mean with
produced at the Institute of Advanced Manufacturing Technology 0.90 confidence level. The dependences obtained have been given
in Kraków (PN-EN ISO 4287 standard). An arithmetic mean of the in Figs. 2 and 3.
profile deviation from the mean line (RA ) and wear profile perpen- The coefficient of friction () decreases with an increase in the
dicular to sliding direction were determined. concentration of the ester reaching the lowest value at 100% con-

Fig. 6. Wear scar profiles in the presence of pure fuel oil (a) and solutions with increasing concentrations of FAME from rape-seed oil: 5% (b), 10% (c), 15% (d), 20% (e), 25% (f),
30% (g), 100% (h). Profilometer TOPO L50.
108 M.W. Sulek et al. / Wear 268 (2010) 104–108

centration. The largest drop in the value (by ca. 20%) can be atively high surface activity of the esters. The experiments have
observed already at 5% concentration of the additive. A further confirmed that surface tension of solutions of the esters in fuel oil
increase in concentration leads to a consistent reduction in whose increases with an increase in their concentration and for 100% solu-
value for “plain” ester is by about 30% lower than that for fuel oil. tions it reaches values that are 1.5-fold lower than those for fuel oil
The lubricant film thickness corresponds well with changes in [6]. A relatively stable lubricant film forms as a result of adsorption
motion resistance (Figs. 2 and 3). An increase in the percentage interactions.
share of a lubricant film is accompanied by a decrease in the coef- It has been found that a percentage share of the lubricant film
ficient of friction. in covering the surface under friction conditions increases with
Antiwear properties of mixtures of methyl esters in fuel oil were an increase in concentration. As a result, motion resistances and
assessed on the basis of the corrected wear scar diameter of the balls roughness decrease as a function of concentration.
(WS 1.4). The results obtained have been presented in Fig. 4. The variations in the corrected wear scar diameter (WS 1.4) and
The changes in the corrected wear scar diameter as a function wear profile as a function of concentration are more complex. A
of concentration of methyl esters in fuel oil are not monotonic. pronounced minimum can be observed in the concentration range
The definitely largest wear scar diameter – 310 ␮m – was found of 10–20%. The minimum value is about twice lower than the one
in the case of pure fuel oil. Wear scar diameters were significantly for fuel oil. An increase in the corrected wear scar diameter at
smaller for compositions of methyl ester solutions. The lowest value higher concentrations may be connected with a decrease in surface
observed for the 15% solution was almost by half smaller (156 ␮m) roughness. The real area of contact of mating friction pair elements
than the one for fuel oil. The wear scar diameter was 217 ␮m for increases, which may lead to increased wear. It should be men-
pure methyl esters derived from rape-seed oil. The results obtained tioned here that the corrected wear scar diameter for fuel oil and
can be related to the latest World Fuel Charter which accepts WS its solutions is considerably smaller than the requirements defined
1.4 = 400 ␮m as the maximum value of the corrected wear scar in the World Fuel Charter (WS 1.4 = 400 ␮m).
diameter for standard HFRR tests. These studies indicate that all
the wear scar diameter values measured are considerably lower. Acknowledgements
The roughness of a mated surface was also studied and the
results were related to a non-mated sample (Fig. 5). The measure- This research was financed by the Ministry of Science and Higher
ments were performed using a profilometer TOPO L50 and the value Education—Research Project No. 3T08A 071 28.
measured was an arithmetic mean of profile deviation from the
mean line (RA ). It appears that under friction conditions the RA
References
value increases as much as fourfold (fuel oil). The addition of the
ester consistently reduces the RA values, even by as much as twofold [1] K. Kardasz, E. Kedzierska, M. Konopka, Cz. Kajdas, Fatty acid methyl esters as
compared to fuel oil (Fig. 5h and i). diesel oil lubricating additive, Exploitation Problems 1 (2003) 191–201.
[2] K. Mitchell, Lubricity of Winter Diesel Fuels, SAE Paper Technical Paper Series
While analysing friction surfaces one can observe an increase in
952370.
the RA values of up to 0.04 ␮m. In the case of ester solutions the RA [3] Essential methods of the quality assessment of industrial lubricants and their
changes as a function of concentration are not significant, although exploitation meaning, Total, part IV, ELF Company Information 2002, 8–26
they tend to decrease. The value of this parameter for pure methyl www.elf.pl.
[4] M.W. Sulek, A. Kulczycki, A. Malysa, Quality assessment of fuels based on bio-
esters is twice lower compared to fuel oil and it equals 0.02 ␮m. components, Polish Journal of Commodity Science 2 (7) (2006) 30–40.
Wear can be characterized by analysing the wear scar profile. [5] M.W. Sulek, A. Kulczycki, A. Malysa, Lubricating properties of fatty acid methyl
The measurements were performed in order to confirm that the esters and fuel oil compositions, Tribology 2 (2006).
[6] M.W. Sulek, A. Kulczycki, A. Malysa, Lubricative Properties of Biodiesel Based
character of wear changes as a function of ester concentration is on Fatty Acid Methyl Esters and Fuel Oil Conference Papers: Tasks of Polish Fuel
not monotonic. Fig. 6 shows wear profiles measured perpendicular Sector in Biodiesel Promotion, Institute of Fuels and Renewable Energy, Warsaw,
to the friction path. It appears that a 5% content of the ester in fuel oil 2006.
[7] J.W. Hadley, G.C. Owen, B. Mills, Evaluation of High Frequency Reciprocated
considerably reduces the depth of a wear scar compared to that oil. Wear Test for Measuring Diesel Fuel Lubricity, SAE Technical Paper Series
An increase in concentration causes an increase in the wear depth. 932692.
The wear profile for 30% solutions is comparable to the one for fuel [8] International Organisation for Standarisation: ISO 12156-1:1997, Diesel Fuel,
Assessment of Lubricity Using the High-Frequency Reciprocating Ring (HFRR).
oil. In the case of 100% solutions the wear depth is lower compared Part 1.Test Method oraz ISO 12156-2:1998 Diesel Fuel.
to 30% solutions and fuel oil. Hence, non-monotonic character of [9] Assessment of Lubricity Using the High-Frequency Reciprocating Rig (HFRR)
wear changes as a function of concentration of solution was con- PN-EN ISO 12156, PKN.
[10] F. Jaroslaw, Assessment of uncertainty of examining of lubricity using the high-
firmed (Fig. 6). It is interesting that in the case of 20%, 25% and 30%
frequency reciprocating rig (HFRR), Masters Thesis in the field of chemical
solutions the wear depths are comparable to or even larger than metrology, Warsaw University, Chemistry Department, Chemical Metrology
those for fuel oil. Center, Warsaw, 2005.
[12] D.P. Geller, J.W. Goodrum, Effects of specific fatty acid methyl esters on diesel
fuel lubricity, Fuel 83 (2004) 2351–2356.
4. Summary and discussion [13] G. Anastopoulos, E. Lois, F. Zannikos, S. Kalligeros, C. Teas, HFRR lubricity
response of an additized aviation kerosene for use, Tribology International 35
The aim of this study was to show that methyl esters of fatty (2002) 599–604.
[14] K.S. Wain, J.M. Perez, E. Chapman, A.L. Boehman, Alternative and low sulfur fuel
acids derived from rape-seed oil and used as fuel oil additives can options: boundary lubrication performance and potential problems, Tribology
favourably modify its lubricating properties. This is due to the rel- International 38 (2005) 313–319.