Energy 36 (2011) 1814e1819

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Energy
journal homepage: www.elsevier.com/locate/energy

Degradation of physical properties of different elastomers upon exposure

to palm biodiesel
A.S.M.A. Haseeb*, T.S. Jun, M.A. Fazal, H.H. Masjuki
Department of Mechanical Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

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

Article history: Biodiesel, as an alternative fuel, is gradually receiving more popularity for use in internal combustion
Received 11 March 2010 engines. However questions continue to arise with regard to its compatibility with elastomeric materials.
Received in revised form The present work aims to investigate the comparative degradation of physical properties for different
9 December 2010
elastomers [e.g. ethylene propylene diene monomer (EPDM), silicone rubber (SR), polychloroprene (CR),
Accepted 12 December 2010
polytetrafluroethylene (PTFE) and nitrile rubber (NBR)] upon exposure to diesel and palm biodiesel.
Available online 26 January 2011
Static immersion tests in B0(diesel), B10 (10% biodiesel in diesel), B20, B50 and B100(biodiesel) were
carried out at room temperature (25
C) for 1000 h. Different physical properties like, changes in weight
Keywords:
Elastomers
and volume, hardness and tensile strength were measured at every 250 h of immersion time. Compo-
Degradation sitional changes in biodiesel due to exposure of different elastomers were investigated by Gas chro-
Diesel matography mass spectroscopy (GCMS). The overall sequence of compatible elastomers in palm biodiesel
Biodiesel is found to be PTFE > SR > NBR > EPDM > CR.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Since past few decades, biodiesel, as a renewable alternative
fuel is receiving much attention to substitute diesel partially or
completely. It is composed of fatty acid alkyl esters derived from
vegetable oils or animal fats [1,2]. Biodiesel having very close
property to that of diesel fuel provides some technical advan-
tages over traditional diesel. These include reduced exhaust
emission, higher cetane number, higher flash point, better
lubricity etc. [3e5]. However, compatibility of biodiesel with
automotive materials is being considered as a rising concern
[6e8]. Elastomers as one of the most important groups of
materials, used in fuel system are of particular concern [9]. This is
because the elastomers are vulnerable attack by various chem-
icals and can undergo degradation of their physical properties
and stability [10].
Bessee and Fey [11] investigated the effect of different blends of
methyl soyester and diesel on hardness, tensile strength, elonga-
tion and swelling of several common elastomers. They observed
that nitrile rubber, nylon 6/6, and high-density polypropylene
exhibited change in physical properties while TeflonÒ, VitonÒ 401-C
* Corresponding author. Tel.: þ60 3 79674492; fax: þ60 3 79675317.
E-mail addresses: haseeb@um.edu.my (A.S.M.A. Haseeb), sjten@yahoo.com
(T.S. Jun), jewel_mme.buet@yahoo.com (M.A. Fazal), masjuki@um.edu.my
(H.H. Masjuki).
and VitonÒ GFLT were unaffected. In another study, methyl esters
have been found to cause swelling of trilobutyl-dilene and nitrile
rubber [12]. Such effects were found even for lower biodiesel blend
(e.g. B10) on acrylic rubber and hydrogenated nitrile rubber (HNBR)
[13]. The later researchers, Trakarnpruk et al. [13], found a decrease
in volume of NBR/PVC (Nitrile rubber/Polyvinylchloride) and NBR
with immersion time in B10 (palm biodiesel). On the other hand,
Frame and McCormick [14] reported that NBR swelled by 14e18%
volume when immersed in B20 soy-biodiesel blend. The interaction
of biodiesel with elastomers is complicated. Sometime apparently
contradictory results are found for the same polymer e.g. NBR in the
literature [13,14].
Under the circumstances of exposure of elastomers in biodiesel,
the extent of fuel absorption as well as the extraction of soluble
components such as plasticizers is different for different types of
elastomer [13]. A full clarification of observed phenomena will
require in-depth investigations in this area. Currently, the most
common elastomer materials that are used in gasket, fuel hose,
o-ring etc. are nitrile rubber (NBR), polychloroprene (CR), ethylene
propylene diene monomer (EPDM), silicone rubber (SR), poly-
tetrafluroethylene (PTFE) etc. These are rival materials for their uses
in diesel engine fuel systems because of their flexibility, excellent
barrier, physical properties and ease of fabrication. Fundamental
studies on the compatibility of these elastomers in palm biodiesel
are scarce. The present study aims to characterize the comparative
degradation of physical properties for different elastomers in palm
biodiesel and its different blends.

0360-5442/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2010.12.023
 A.S.M.A. Haseeb et al. / Energy 36 (2011) 1814e1819 1815

2. Experimental in weight, volume, hardness and tensile strength. Samples for

The palm biodiesel used in this study was supplied by Wesh-
chem Technology Sdn Bhd, Malaysia. The analysis report provided
by the supplier is summarized elsewhere [15]. The compatibility of
five different elastomer materials viz, EPDM, NBR, CR, SR and PTFE
with palm biodiesel was assessed by conducting static immersion
tests in B0 (diesel), B10 (10% biodiesel in diesel), B20, B50 and B100
(100% biodiesel). The investigated elastomers were supplied by
Malaysian Rubber Board.
For each elastomer, test was carried out at room temperature
(25
C) for 1000 h. At the end of immersion, degradation behavior
of different elastomers was characterized by measuring changes
tensile tests were prepared in the form of dumbbell shape with
gauge length of 30 mm. Changes in weight were measured by
balance with 4 decimal accuracy. Volume was calculated by
measuring the height, width and length of the sample. Upon
immersion, before measuring weight and volume, samples were
dried by blotting with lint-free cloth followed by air drying by
keeping on clean places at room temperature for 30e40 min. The
value of tensile strength was measured according to ASTM D412
(strain rate of 500 mm/min) by using Instron Tensile Tester (5 kN).
The hardness value of the sample was determined using Cogenix
Dead Load Hardness Tester Model H-14. A 2.5 mm ball indenter was
pressed on the sample and the hardness value was automatically

Fig. 1. Changes of volume for different elastomers after immersion at room temperature.
1816 A.S.M.A. Haseeb et al. / Energy 36 (2011) 1814e1819

(computerized) recorded. Compositional changes in biodiesel were
determined by conducting Gas chromatography mass spectroscopy
(GCMS).
3. Results
Fig. 1 shows the changes in volume of different elastomers upon
exposure into different fuels. It is seen that biodiesel and its blends
cause a grater swelling of CR and NBR compared with that caused
by diesel. On the other hand, EPDM and SR swelled to a greater
extent in diesel compared with that in biodiesel and its blends. It is
also seen in Fig. 1 that PTFE showed a reduction in volume with an
increase in the concentration of biodiesel. Like changes in volume,
similar trends were found for the changes of weight for respective
elastomers (Fig. 2). PTFE showed a slight weight loss, while all other
materials show considerable weight gain.
Fig. 3 shows a comparison of different elastomers in terms of
their respective volume and weight changes. It is seen that the
compatibility, in terms of changes in weight and volumes, for both
EPDM and SR are higher in biodiesel as compared to that in diesel.
On the other hand, CR and NBR are less compatible with biodiesel.
This can be attributed to the higher polarity of ester components in
biodiesel which allows the more polar elastomers to dissolve to
a greater extent.
Fig. 4 shows that upon exposure to biodiesel, tensile strength
values are decreased to a greater extent for EPDM, CR, NBR than SR

Fig. 2. Changes of weight for different elastomers after immersion at room temperature.
 A.S.M.A. Haseeb et al. / Energy 36 (2011) 1814e1819
Fig. 3. Changes of (a) volume and (b) weight for different elastomers after immersion at room temperature for 1000 h.
and PTFE elastomers. Almost similar trends were also found for
respective elastomers for the change of hardness (Fig. 5).
Table 1 shows the compositional changes of EPDM and CR
exposed biodiesel as compared to as-received biodiesel. It is seen
that concentration of palmitate ester is higher in as-received bio-
diesel than that in EPDM and CR exposed biodiesel. On the other
hand, percentage of Methyl Oleate is increased considerably upon
exposure to both EPDM and CR. Elastomer or its constituents may
play an important role to influence the change in composition of
biodiesel.
4. Discussions
Elastomers are basically complex mixture of polar and non-
polar substances including polymers, fillers, oil, plasticizer, stabi-
lizers, curing agents, antioxidants, antizonants and processing aids
[16,17]. When it is immersed in a solvent, the elastomer matrix has
a tendency to swell. Swelling of EPDM, SR, CR and NBR upon
exposure to fuel can be attributed to the absorption of solvent as
well as relaxation of polymer chains. It is seen that the increasing
trends of swelling in biodiesel blends and diesel for EPDM and SR
are higher in the time range of 500e700 h. But in pure biodiesel, the
increased volume remains almost constant for the time range
250e750 h. This demonstrates that EPDM and SR are more resistant
to swelling in biodiesel than in diesel. On the other hand, swelling
rates for CR and NBR are higher in biodiesel as compared to that in
diesel. This indicates that CR and NBR are less compatible in bio-
diesel than that in diesel. Compositionally, NBR is a complex family
of unsaturated copolymers of acrylonitrile (ACN) and butadiene,
while CR refers to polymers of 2-chloro-1,3-butadiene or copoly-
mers of 2-chloro-1,3-butadiene with one or more polymerizable
monomers. For NBR, the greater the acrylonitrile content, the less
Fig. 4. Tensile strength (TS) for as-received elastomers and elastomers exposed to
diesel (B0) and biodiesel (B100) at room temperature for 1000 h.
1817
the swell in fuels as it ensures increased crosslinks in the polymer
backbone [18]. Similarly, glycol dimethacrylates is the crosslinking
agent for polychloroprene which resists swelling. Impact of diesel
and biodiesel on these different ingredients of elastomers bears
different characteristics based on their dissolution capabilities as
well as their molecular polarities.
There is a general rule describing the fact that polar substances
are more likely to dissolve in polar solvents and non-polar
substances are more likely to dissolve in non-polar solvents [19]. It
is noted that the degree of polarity for EPDM and SR is less than that
of CR and NBR [20], while PTFE shows no polarity [21]. For polar
solvent, the positive ends of the molecules will attract the negative
ends of the solute molecules thereby creating an intermolecular
force known as dipoleedipole interaction. The degree of dipo-
leedipole interaction in biodiesel for polar solute seems to be
higher as compared to that in diesel. This is because biodiesel has
additional unique chemical difference arising from the increased
polarity of esters as compared to diesel [22]. Therefore, swelling of
highly polar elastomer material (e.g. CR, NBR) is comparatively
larger in biodiesel than that in diesel fuel. Elastomers seem to swell/
degrade in biodiesel through reactions with the polymer backbone
and crosslinking system or by reactions with the filler system [23].
In practical cases, upon exposure to different metals, biodiesel
becomes oxidized and thereby it can increase its polarity [24]
which may cause further degradation of elastomers. Generally,
the influence of ester base fluids on deterioration of elastomer is
more significant in comparison to that of mineral oils [25]. If the
solventepolymer interactions are more dominant than polymere
polymer interactions, maximum swelling can be obtained [26].
Beside this, even a non-polar solvent has the ability to solvate
the solute molecules. In fact, each molecule has a weak intermo-
lecular force called London Dispersion force by which positive
nuclei of the solute molecule atoms will attract the negative
Fig. 5. Hardness (IRHD) for as-received elastomers and elastomers exposed to diesel
(B0) and biodiesel (B100) at room temperature for 1000 h.
1818 A.S.M.A. Haseeb et al. / Energy 36 (2011) 1814e1819
Table 1
Compositional differences of biodiesel before and after exposure to different elastomers.
Commercial name Chemical formula
Caprylic acid CH3(CH2)6COOH
Methyl Laurate CH3(CH2)10COOCH3
Methyl Myristate CH3(CH2)12COOCH3
Methyl Palmitate CH3(CH2)14COOCH3
Methyl Palmitoleate CH3(CH2)5CH]CH(CH2)7COOCH3
Methyl Stearate CH3(CH2)16COOCH3
Methyl Oleate CH3(CH2)7CH]CH(CH2)7COOCH3
Methyl Linoleate CH3(CH2)4CH]CHCH2CH]CH(CH2)7COOCH3
Methyl Arachisate CH3(CH2)l8COOCH3
electrons of the solvent molecule atoms [19]. The increase in
volume (swelling) and weight may result from the absorption of
higher amount of liquid as compared to the extraction of soluble
components from elastomer. On the other hand, the causes of slight
reduction in mass and volume for PTFE can be discussed in terms of
the absorption of lighter element like diesel or biodiesel vis-a-vis
the dissolution of soluble components such as plasticizers, stabi-
lizers or additives from the elastomers. Decreasing of volume as
a result of reduction in pore size distribution indicates the densi-
fication of network by providing further crosslinks [27]. In other
words, increase of crosslinks can limit the degree of polymer
swelling by providing tie-points (constrains) that limit the amount
of solvent to be absorbed into the elastomer.
Crosslinking agents in elastomers are mostly peroxide based
[28]. During crosslinking, peroxides typically react with the elas-
tomer chains by removing hydrogen atoms from the carbon back-
bone of the polymer. Thus, it creates highly active radicals on the
chain, which attach to a similar site on another chain. This forms
a carbon to carbon crosslink. Upon exposure of different elastomers
in biodiesel, crosslinking agent and/or filler can react with different
components of biodiesel and thereby deteriorate the physical and
mechanical properties. In addition, biodiesel exposed elastomer
may lose its crosslink if hydrogen peroxide is formed by abstracting
hydrogen from the components of biodiesel. Observations of
compositional change of CR exposed biodiesel seem to indicate that
hydrogen abstraction by CR from palmitate has converted a small
amount of palmitate (16:0) into palmitoleate (16:1). This may
partly cause for the reduction of palmitate from 44.272% to 40.79%
and the increase of palmitoleate from 0.497% to 3.215%. Such type
of change was not found for less polar EPDM exposed biodiesel.
Concentration of different components in biodiesel such as methyl
oleate, methyl linoleate, methyl linolenate etc. may also be change
due to presence of catalyst [29]. In present study, environmental
factors (e.g. light, air) or certain constituents of elastomer may act
as catalyst to increase the concentration of methyl oleate after
exposure to elastomers. In fact, the entanglements of the long
elastomer chains act as obstructions to the movement of the
polymer chains. These obstructions enable the elastomer to sustain
stable property. But, as a result of reaction between fillers and fuel,
different mechanical properties can be influenced [30]. Results
from change in hardness and tensile strength show that biodiesel is
more aggressive than diesel. This can be attributed to the ester
components of biodiesel. In addition, hygroscopic nature of bio-
diesel may introduce water into polymer matrix. Diffusion of water
into polymer matrix can also deteriorate the mechanical properties
[31]. Upon exposure to biodiesel, both tensile strength and hard-
ness were reduced as compared to that of as-received samples.
Decrease of tensile strength and hardness for EPDM and CR are
comparatively higher than that for SR, NBR, PTFE. This suggests that
after immersion into biodiesel higher degradation occurs for CR
and EPDM. Change in volume of CR (80.48%) is comparatively
higher than that of EPDM (49.48%). However, the sequence of
As-received B100 B100 exposed to EPDM B100 exposed to CR
0 0 0.12
1.066 0.671 1.11
3.700 3.7 3.21
44.272 41.079 40.79
0.497 0.307 3.215
4.128 4.13 3.96
35.934 41.28 39.486
0 0 0.163
0.236 0.148 0.24
biodiesel exposed elastomers that show more close hardness value
to that of their respective as-receive states is PTFE > SR > NBR.
Similar sequence is also found for the tensile strength.
5. Conclusions
This study suggests the following conclusions:
1. Biodiesel and its blends swelled polychloroprene (CR) and
nitrile rubber (NBR) to a greater extent than did diesel. On the
other hand, ethylene propylene diene monomer (EPDM) and
silicone rubber (SR) swelled to a greater extent in diesel
compared with that in biodiesel and its blends. Polytetra-
fluroethylene (PTFE) showed a slight reduction in weight and
volume with an increase in the concentration of biodiesel.
2. Upon exposure into biodiesel, both tensile strength and hard-
ness were greatly reduced for EPDM and CR as compared to
that in as-received condition. But changes of these properties
were not so significant for SR, PTFE and NBR.
3. The overall sequence of compatible elastomers in palm bio-
diesel is found to be: PTFE > silicone rubber (SR) > NBR >
EPDM > polychloroprene (CR).
4. Although PTFE seems to be the most compatible materials
among those tested, it undergoes a slight reduction of main
constituents. The effects of such dissolution on fuel properties
require further investigation.
Acknowledgments
The authors would like to acknowledge the financial support
provided by the Ministry of Science, Technology & Innovation
(MOSTI) under the science Fund by Grant No: 03-02-03-SF3073 and
by the Institute of Research Management and Consultancy, Univer-
sity of Malaya (UM) under the IPPP Fund Project No.: PS110/2010A
and PS093/2008B. Special appreciation is also expressed to Mr. Md.
Aris bin Ahmad from Malaysia Rubber Board for his valuable
suggestion and help to conduct this research work.
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