2007-01-4061
Fluoroelastomer Compatibility with Biodiesel Fuels
Eric W. Thomas, Robert E. Fuller and Kenji Terauchi
Copyright © 2007 SAE International
This paper is reprinted with permission © 2007 SAE International.
ABSTRACT
Global acceptance and use of biofuels is growing rapidly
in the transportation sector. Diminishing reserves of
fossil fuels will continue to drive investment in
sustainable biofuels. Market drivers for biofuels include a
renewable supply, reduced greenhouse gas emissions
and airborne pollutants, and reducing dependence on
energy imports. One such fuel is biodiesel, an alternative
diesel fuel produced by transesterification of vegetable
oils or animal fats with alcohol, usually methanol.
The use of biodiesel fuels is rapidly growing in North
America, not only for the environmental and economic
reasons mentioned above, but because of its inherent
lubricity. EPA emission regulations now require the use
of ultra-low sulfur diesel (ULSD) fuels in all highway
diesel engines. ULSD has inherently poor lubricity and
biodiesel’s superior lubricating properties can reduce
wear in diesel engines fueled with blends of ULSD,
thereby extending engine life and warranty.
The compatibility of seal and hose materials commonly
used in automotive fuel systems using conventional
hydrocarbon fuels has long been established. However,
there is much less information available on the
compatibility of fuel system elastomers with biodiesel
fuels.
In this presentation the compatibility of several
fluoroelastomers with biodiesel and biodiesel blend fuels
will be reviewed. Conventionally formulated
fluoroelastomers that have historically been used for
petrodiesel and biodiesel service will be compared to
optimized formulations that display improved
compatibility with biodiesel fuels. The significance of
rubber formulation will be discussed. Accelerated testing
will characterize physical properties and property
retention in biodiesel through 3024 hours at 125°C.
Properties relevant to sealing applications and hose will
also be discussed and best in class will be highlighted,
so that, in gaining a better understanding of the
respective capabilities of high performance
fluorohydrocarbon elastomers, the engineer may design
more robust sealing systems for biodiesel service.
DuPont Performance Elastomers L.L.C.
INTRODUCTION
Market forces are driving diesel developments to lower
vehicle emissions, improve fuel efficiency and reduce
“greenhouse gases”, predominately carbon dioxide
(CO2). Trends in diesel engine technology include the
drive towards more powerful, higher torque, lighter
weight, more fuel-efficient engines, with accompanying
reductions in noise and emissions, as well as better
reliability, improved operating safety and reduced cost.
As a result, engine producers are driven towards
biodiesel fuels in order to achieve optimum engine
performance with a net lower CO2 global footprint and
longer engine life. High pressure common rail (HPCR)
diesel fuel injection systems have established a new
benchmark in performance and reliability and are the
preferred technology for the heavy-duty market and will
continue to gain acceptance in the light-duty direct
injection automotive engine market, particularly in North
America [1].
Biodiesel is defined as the monoalkyl esters of long
chain fatty acids derived from vegetable oils, waste
cooking oils, or animal fats [2]. Fatty acid oil methyl
esters (FAMEs) are made from vegetable oil or animal
fat by transesterification in the presence of a catalyst
(usually a base) with alcohol (usually methanol) to form
methyl esters and glycerine as a byproduct. Biodiesel
contains practically no sulfur and no aromatics and has
a much narrower compound distribution.
Biodiesel is a somewhat unfortunate name as it implies
chemical similarity with petroleum diesel. Petrodiesel is
a mixture of hydrocarbons, while biodiesel is a mixture of
unsaturated fatty acid esters. Concern arises from the
fact that petrodiesel and biodiesel have such different
chemical structures and consequent different effects on
elastomers.
Pure biodiesel is a biodegradable, non-toxic, clean-
burning, renewable fuel that can be used in
compression-ignition (diesel) engines with few or no
engine modifications. Biodiesel can also be blended with
petroleum diesel to produce biodiesel blend fuels
denoted as Bxx, where the xx represents the volume
percent of biodiesel in the blend. European norm EN
14214 [3] is the common international standard for
biodiesel. ASTM Standard D 6751 [4] covers pure
biodiesel (referred to as “B100”), for blending with site monomers and unique polymer end group chemistry
petrodiesel in levels up to 20% by volume, e.g. up to B20 that were applied to the manufacture of these polymers.
blends.
While the basic building blocks (monomers) are the
Biodiesel fuel burns much cleaner than petroleum-based same, polymer architecture has advanced considerably.
diesel, creating about 60% less net carbon dioxide The APA polymers have superior properties and
emissions. In addition, because it is produced processing characteristics when compared to their
domestically from renewable resources such as predecessors. These advances in polymer design have
soybeans or rapeseed, its use decreases dependence been necessary to keep pace with the automotive seal
on foreign oil. fabricators quest to optimize part quality and
manufacturing yields, in order to maintain competitive
Most diesel engine producers warranty their engines for position, without sacrificing end-use properties.
biodiesel blends up to B5 (5% biodiesel mixed with
regular petrodiesel by volume) provided the unblended Table 1 lists those fluoroelastomers evaluated in this
biodiesel or B100 meets ASTM D 6751 or EN 14214 study and describes some of their attributes.
specification. Blends of 20% biodiesel with 80%
petroleum diesel (referred to as "B20") can generally be Table 1 - Fluoroelastomers Evaluated
used in unmodified diesel engines found in many trucks
and some cars. Biodiesel can also be used in its pure Product General Description
form (B100), however its use may require certain engine FKM-A401C Viton® A-401C, VF2/HFP, 66.0%
alterations to avoid maintenance and performance fluorine, bisphenol cure
problems. FKM-F605C Viton® F-605C, VF2/HFP/TFE,
70.0% fluorine, bisphenol cure
EPA emission regulations, effective June 2006, require
FKM-GBL-S Viton® GBL-600S,
the use of ultra-low sulfur diesel (ULSD) fuels in all
VF2/HFP/TFE/CSM, 68.0%
highway diesel engines. ULSD has inherently poor
fluorine, peroxide cure
lubricity and biodiesel’s superior lubricating properties
can reduce wear in diesel engines fueled with blends of FKM-GF-S Viton®GF-600S,
ULSD, thereby extending engine life and warranty [5,6]. VF2/HFP/TFE/CSM, 70.2%
fluorine, peroxide cure
EXPERIMENTAL FKM-GLT-S Viton® GLT-600S,
VF2/TFE/PMVE/CSM, 64.0%
The materials evaluated in this study were prepared fluorine, peroxide cure
using commercial grades of fluoroelastomers. ASTM FKM-GFLT-S Viton® GFLT-600S,
D1418 designations will be used to describe each VF2/TFE/PMVE/CSM, 66.5%
material. fluorine, peroxide cure
Monomer Description
FLUOROLEASTOMERS EVALUATED VF2 = vinylidene fluoride
HFP = hexafluoropropylene
TFE = tetrafluoroethylene
Typically, fluoroelastomers are differentiated by their PMVE = perfluoromethylvinylether
monomer composition and the cure system employed. CSM = proprietary cure-site monomer
Traditional copolymer and terpolymer compositions, New APA grades are designated with an “S” suffix
based on vinylidene fluoride (VF2), hexafluoropropylene Viton® fluoroelastomer is a registered trademark of DuPont
(HFP) and tetrafluoroethylene (TFE), are considered Performance Elastomers
“standard” products within the rubber industry. Other
products offering some special aspect of functionality not
provided for by the standard products are considered As we will illustrate later in this paper, the resistance of
“specialty” types. For example, FKM- GLT-S and FKM- FKM compounds to biodiesel is dependent upon the
GFLT-S contain the monomer perfluoromethylvinylether incorporation of metal oxides or hydroxides in the
(PMVE) to provide enhanced low temperature flexibility. formulation. The type and level of metal oxide/hydroxide
used in the formulations are listed in parentheses after
Recently, advanced polymerization and curing the FKM designation as shown below.
technology designed to manufacture specialty (Ca(OH)2 or (Ca(OH)2-3.0) = 3 parts calcium hydroxide
fluoroelastomers with end use properties that meet
evolving market needs was developed and (Ca(OH)2-1.5) = 1.5 parts of calcium hydroxide
commercialized [7,8]. These polymers, called Viton® (NMO) = no metal oxide used
fluoroelastomer made with Advanced Polymer
Architecture (APA Polymers), were designed to provide Metal oxides are an integral part of the bisphenol cure
an excellent balance of processing and physical system, and the bisphenol cured compounds, FKM-
properties [9,10]. These improvements are due to the A401C and FKM-F605C, that are referred to in this
modified molecular weight distributions, improved cure paper contained 3 parts of magnesium oxide and 6 parts
of calcium hydroxide.
FUELS EVALUATED
A series of extended agings were conducted in the
following fuels (reference Appendix):
• Rapeseed Methyl Ester (RME) – B100 RME,
meeting the requirements of SAE J1681, Appendix
C - Table C4
• Certification No. 2 Diesel Fuel (low sulfur), meeting
the requirements of SAE J1681, Appendix B - Table
B6 blended with B100 RME to make B20 (20% RME
/ 80% Diesel) and B5 (5% RME / 95% Diesel)
• Rapeseed Methyl Ester (RME) – B100 RME blended
with 0.5 % distilled water
• Certification No. 2 Diesel Fuel blended with B100
RME to make B20 (20% RME / 80% Diesel) and B5
(5% RME / 95% Diesel), each blended with 0.5%
distilled water respectively
Test Protocols - Standard Property and Aging Tests
Sample Preparation: Compounding of the
fluoroelastomers was carried out using standard rubber
lab equipment (internal mixer and two-roll mill.) Standard
processing techniques commonly practiced in the
industry were employed in preparation of test
specimens. Compound formulations were typical of
those recommended for sealing service. All
fluoroelastomers contained 30 pph MT carbon black (N-
990) to produce a nominal 70-80 durometer hardness.
Standard ASTM slabs were prepared by compression
molding for five (5) minutes at 177°C and then post-
curing in a 232°C oven for 16 hours. Following post
cure, the FKM test specimens for physical property and
aging tests were die-cut from the molded slabs and
tested per ASTM methods.
Test Methods: The fluoroelastomers were characterized
using the test methods described below:
• Stress-strain according to ASTM D 412-98a, Die C
• Hardness according to ASTM D 2240-02
• Fluid immersion according to ASTM D 471-98 – all
fuel testing was conducted in sealed 1 liter 316
stainless steel Parr pressure vessels
Vulcanizates of the FKM materials were subjected to
immersion in the various biodiesel fuels at elevated
temperature. The testing employed methods typically
used to characterize elastomeric sealing performance:
hardness changes, retention of stress-strain properties
(tensile strength and elongation) and volume swell.
Historically, volume swell, as performed in the laboratory
under accelerated conditions, has been used as an
indicator of an elastomers' chemical resistance to a
specific fluid. Although it should not be used as the sole
criterion for material selection, it is of value in predicting
seal compatibility. The amount of volume swell in a
given fluid (fuel, oil, grease) can affect sealing
performance, as it relates to available O-ring groove
volume for example, or the abrasion and wear of
dynamic sealing devices like radial lip seals [11,12].
Volume swell can also be an indication of chemical
attack when the volume swell for a fluid with a minor
amount of additive is significantly different than it is for
the unmodified fluid.
RESULTS AND DISCUSSION
Compatibility of elastomeric components with service
fluids is typically ascertained by accelerated aging under
laboratory conditions evaluating volume swell and
physical property retention after exposure. Accelerated
aging can provide an approximation of potential
problems in service, however it can miss important
second order effects. For example, nitrile butadiene
rubber (NBR) exhibits good resistance to both standard
diesel fuel and ULSD; however field problems have
been reported when rubber parts conditioned to
standard diesel were exposed to ULSD. Seal shrinkage
due to the different degree of swelling of NBR in the two
fluids led to leaks. Another example of second order
effects is the increased aggressiveness of modern
engine oils toward FKM caused not by the base oils but
by the corrosion inhibitor additive packages used with
them.
Historically, elastomer compatibility testing has shown
that FKM has generally been judged to be resistant to
biodiesel based on accelerated fluid aging [13].
However, we are seeing an indication that this testing is
missing an important second order effect.
In one experiment, compounds of bisphenol cured FKM-
A401C, bisphenol cured FKM-F605C and conventionally
formulated peroxide cured FKM-GBL-S exhibited low
swell and good retention of physical properties when
aged in fresh RME. Volume swells were less than 6%
and hardness changes were less than 5 Shore A
durometer points when aged 3024 hrs at 125°C in fresh
RME that was changed weekly during the testing.
However, in an essentially identical experiment using
“old” RME that had been stored in our laboratory for
several months, the FKM-A401C and FKM-GBL-S
compounds gave volume swells of 115% and 31% after
only two weeks at 125°C. These compounds lost about
70% of their original tensile strength and 15 to 20 points
of hardness after 1008 hours in this “old” RME.
The storage conditions of the “old” RME were not ideal,
but they were not what one would consider severe. The
RME was stored in our lab at room temperature in a
partially filled steel drum. The drum had not been
blanketed with an inert gas and thus the RME was
exposed to oxygen (and some water vapor) during
several months of storage.
Comparisons of volume swell and hardness changes in
“old” vs. “fresh” RME aged for equal periods at 125°C
are shown in Figures 1 and 2 below.
 Figure 1 A number of other internal studies have shown similar
results where formulations that appeared acceptable
Volume Change under one set of conditions gave poor performance
FKM Compounds Aged in "Old" RME vs "Fresh" RME@ 125°C
under conditions believed to be similar. Long term
140
testing has also shown problems where formulations
120
that looked good in the early part of the testing exhibited
Volume Change (%)

100 high swell after longer times. In one test with a

80 conventionally formulated peroxide cured FKM-GLT
60
compound tested in a B25 biodiesel blend at room
temperature, the volume swell increased from about 5%
40
at 2000 hours to over 15% after 4000 hours.
20

0 Biodiesel aging results appear to be highly variable and

GBL-S Ca(OH)2 A401C
non-reproducible. This is an indication that these studies
"Old" RME 336 Hrs "Old" RME 1008 Hrs
"Fresh" RME 336 Hrs "Fresh" RME 1008 Hrs
are missing an important second order effect. We
initiated work to identify this second order effect so that
a solution could be defined.
Figure 2
Review of the data and the results of an initial scouting
Hardness Change experiment reported in Table 2 indicate that water and/or
FKM Compounds Aged in "Old" RME vs "Fresh" RME@ 125°C carboxylic acid play a role in this effect.
0
-2 GBL-S Ca(OH)2 A401C

-4
Table 2
Hardness Change (pts)

-6 Effect of Acid and Water on FKM-GBL-S

-8 Volume Swell after 2 Weeks at 125°C (%)
-10
FKM GBL-S
-12
-14 RME (0.05% Water) 4
-16
RME (0.5% Water) 21
-18
-20 RME (0.05% Water + 20% Carboxylic 14
"Old" RME 336 Hrs "Old" RME 1008 Hrs Acid)
"Fresh" RME 336 Hrs "Fresh" RME 1008 Hrs
Carboxylic Acid (100%) 16
Carboxylic Acid: 50/50 blend of oleinic acid and linoleic acid
Figure 3 below compares the retained tensile strength
measured on the compound aged in “old” RME after Note: FKM-GBL-S formulation contained 3 pph Ca(OH)2
only 336 hours at 125°C to the retained tensile strength
after 3024 hours in “fresh” RME at the same Both water and carboxylic acid are likely components of
temperature. The compound made with FKM-GBL-S and commercially dispensed biodiesel. Water is a common
containing Ca(OH)2 lost 74% of its tensile strength after contaminant in diesel and often exists as a separate
only 336 hours exposure in “old” RME vs. a 27% loss phase in the bottom of storage takes. Biodiesel absorbs
after 3024 hours with “fresh” RME. FKM-A401C showed several times more water than conventional petroleum
a 66% loss after 336 hours in “old” RME vs. 31% loss diesel with the room temperature saturation level being
after 3024 hours exposure in “fresh” RME. about 1200 ppm (as compared to ~30 ppm for
Figure 3 unsaturated hydrocarbon). Water that would be in a
separate phase in conventional diesel fuel will be
Tensile Change dissolved in biodiesel. Some OEMs have reported that
FKM Compounds Aged in "Old" RME vs "Fresh" RME@ 125°C water levels in conventional diesel have increased in
0 North America due to slower removal of water from
GBL-S Ca(OH)2 A401C
-10 underground storage tanks.
Tensile Strength Change (%)

-20
-30
Carboxylic acids are oxidative degradation products of
-40
biodiesel [14]. Biodiesel is susceptible to oxidation upon
-50 `

-60
exposure to air with oxidation proceeding in as little as a
-70
few hours depending on storage conditions and the
-80 amount of unsaturation of the fatty acids. The acid
-90 number of biodiesel tends to increase over time in
-100 storage. Oxidation initially produces hydroperoxides at
"Old" RME 336 Hrs "Old" RME 1008 Hrs "Fresh" RME 3024 Hrs
the unsaturation points of the fatty acids. These
decompose to aldehydes, ketones and shorter chain
carboxylic acids [15].
Fang and McCormick [16] presented spectroscopic work
examining potential biodiesel degradation mechanisms,
oxidation under accelerated conditions (elevated
temperature), peroxide formation and decomposition
products (i.e., aldehydes, ketones, organic acids),
oligimer formation, antagonistic effects, and the
decomposition of methyl esters by hydrolysis and other
related mechanisms. In their work the impact of
hydrolysis on oxidation of B20 in off-highway diesel at
120°C with aeration clearly shows that hydrolysis is
enhancing the rate of oxidation.
Esters, such as those found in biodiesel, are easily
hydrolyzed in the presence of water to form carboxylic
acids. This hydrolysis reaction is catalyzed by either acid
or base so that the acid formed is a catalyst for further
hydrolysis. If basic metal oxides or hydroxides are
present, such as those found in excess in conventionally
formulated FKM, these acids can coordinate to the metal
oxide surface and form carboxylate salts. These
carboxylate salts can effectively act as phase transfer
agents and serve to dehydrofluorinate the polymer,
changing its chemical properties and swelling
characteristics.
Metal oxides and/or metal hydroxides such as
magnesium oxide and calcium hydroxide are required to
facilitate the curing chemistry of bisphenol cured FKM.
Metal oxides are also used in conventionally formulated
peroxide cured FKM to help scavenge the minor
amounts of halides formed during cure and improve the
efficiency of the peroxide curing reactions. The resultant
metal halides formed during these reactions are
hygroscopic and will help draw water needed for further
hydrolysis into the polymer. Lewis acid metal halides
such as magnesium fluoride can themselves function as
catalysts for hydrolysis.
The general hypothesis that metal oxides and metal
hydroxides are deleterious for volume swell is postulated
and the following mechanism of FKM attack is proposed
below.
Proposed Mechanism of FKM Attack
1 RME + H2O RCOOH + CH3OH [H+ or OH- Catalyzed]
2 2 RCOOH + MO [M+2][RCOO-]2 FKM MF2 + 2 RCOOH + dehydrofluorinated FKM
containing formulations. This enables us to test the
hypothesis that metal oxides are deleterious to biodiesel
resistance and to formulate practical compounds without
metal oxides. Two such metal oxide free compounds
were formulated from FKM-GBL-S and FKM-GF-S.
These compounds were tested in biodiesel and
biodiesel-diesel blends to which an excess of water was
added and compared to conventionally formulated FKM
compounds.
These “wet” biodiesel fuels were formulated with 0.5%
added water and the testing was conducted in sealed
Parr pressure vessels to assure that the water remained
available throughout the testing at 125°C. This “wet”
biodiesel is admittedly very aggressive and contains
more water than likely to be seen in practice, particularly
in view of the fuel filter and water separator/trap
technology routinely employed with advanced HPCR
diesel engines. These traps remove water that is present
in a separate phase, however are less efficient at
removing the water dissolved in the biodiesel.
Testing with this “wet” biodiesel indicates that it is not
significantly more aggressive than the “old” biodiesel
reported above. The same FKM-A401C compound that
gave 115% volume swell after 2 weeks (336 hours) in
the “old” biodiesel, gave a swell of 48% in the “wet”
biodiesel after the same exposure time and temperature.
AGING IN “FRESH” BIODIESEL
Volume Swell
Figure 4 shows the swell values for several FKM
compounds when immersed in fresh B100 RME for up to
3024 hours (18 weeks) at 125°C. Fuels were changed at
each measurement interval of 2, 4, 6, 9, 12, and 18
weeks. Here we see that the degree of swell is very
similar for all the polymers tested (3-6%), with the lowest
swell observed with those polymers containing the
highest weight percent fluorine (FKM-F605C, FKM-GF-
S). All displayed good resistance to B100 RME. Based
on this testing one may conclude that rapeseed methyl
ester by itself is not aggressive to FKM as all the
fluoroelastomers evaluated here display good
compatibility with RME.
Figure 4

3 2 RCOOH + M(OH)2 [M+2][RCOO-]2 + H2O FKM MF2 + 2 RCOOH + dehydrofluorinated FKM

Volume Change
Aged in B100 RME at 125°C
7

6
Following the above reactions, double-bonds are
Volume Change (%)

generated which are the sites of backbone cleavage. 5

4
The above analysis suggests that the best biodiesel 3
resistance will be obtained if the FKM compound is 2
formulated without metal oxide. One of the advantages
1
of the peroxide cured APA polymers is that they cure
0
efficiently in the absence of metal oxide acid
GLT-S A401C GFLT-S GBL-S F605C GF-S
scavengers. Metal oxide free compounds, or no metal Low Fluorine (wt %) High
oxide (NMO) compounds, cure fast and efficiently, and 336 hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours
give physical properties comparable to metal oxide
AGING IN “WET” BIODIESEL occurs in practice, it could lead to seal leakage similar to
the problems mentioned above where NBR was
As mentioned earlier, when fatty acid oil methyl esters exposed to ULSD after equilibrating with standard
hydrolyze, chemical reactions affect the observed diesel. The NMO compounds do not show this
swelling behavior and the swelling characteristics decreasing swell phenomenon.
become dependent not only on the composition of the
polymer but also on the formulation of the compound. The same trends were seen with “wet” B20, however, in
this case, higher swell was observed with FKM-F605C
“Wet” RME biodiesel fuels were prepared by adding 5 ml (75%) than with the lower fluorine containing FKM-401C
distilled water to 1000 ml fuel, either B100 RME, B20 (39%). Figure 6 provides the details.
RME, or B5 RME. Properties were evaluated after
testing 336, 672, 1008, 1512, 2016 and 3024 hours Figure 6
immersion at 125°C. Fuels were changed at the time of
interval testing. Volume Change
Aged in "wet" B20 RME at 125°C
80
Volume Swell in “Wet” Biodiesel
70

60

Volume Change (%)

Figure 5 shows the volume swell values for each FKM
compound when immersed in “wet” B100 RME through 50

3024 hours (18 weeks) at 125°C. Here we see a very 40

different picture versus the “fresh” B100 RME swell 30

values shown in Figure 4. All the conventionally 20
formulated FKM elastomers containing metal oxides 10
exhibit significantly higher swell values, with FKM-401C
0
and FKM-F605C showing alarmingly high values, GBL-S (NMO) GF-S (NMO) GBL-S Ca(OH)2 A401C F605C

peaking at 101% and 55% after 672 hours immersion 336 hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours
and gradually decreasing to 64% and 43% respectively
over the remaining 3024 hour immersion period. The
conventionally formulated FKM-GBL-S Ca(OH)2 Figure 7 shows the volume change values in “wet” B5
containing 3 pph of calcium hydroxide had a maximum after 3032 hours immersion. The swell values are not as
swell of 33% decreasing to 20% at the end of the large as those seen in B20 or B100, presumably due to
exposure period. The fluoroelastomers formulated the lower level of RME in the fuel blend. However, the
without metal oxides, FKM-GBL-S (NMO) and FKM-GF- FKM compounds formulated for acid resistance are
S (NMO), showed excellent compatibility with “wet” RME clearly superior to the conventionally formulated
with volume swell values in the 4-6% range throughout compounds, even with this low level of RME content.
the 3024 hours exposure period.
Figure 7
Figure 5
Volume Change
Volume Change Aged in "wet" B5 RME at 125°C
Aged in "wet" B100 RME at 125°C 25
120

20
100
Volume Change (%)
Volume Change (%)

80 15

60 10

40
5

20
0
0 GBL-S (NMO) GF-S (NMO) GBL-S Ca(OH)2 A401C F605C
GBL-S (NMO) GF-S (NMO) GBL-S Ca(OH)2 A401C F605C
336 hours 672 hours 1008 hours 2016 hours 3024 hours
336 hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours

The decrease in volume swell with exposure time

exhibited by the conventionally formulated FKM is
unusual and an indication that the swell is the result of
chemical changes occurring, rather than just a physical
swell. The reason for this decrease in swell is not yet
understood but we have seen this behavior in more than
one series of tests. If this type of swelling behavior
The Significance of Compounding Figure 9

When designing for long-term compatibility with “wet” Volume Change

Comparison of FKM-GBL-S (NMO) vs FKM-GF-S (NMO)
acidic biodiesel, compound ingredient selection and aged in "wet" Biodiesel Fuels for 3032 hours at 125°C
dosing is significant with FKM formulations. As 8
previously noted, basic metal oxides are components of 7
conventionally formulated FKM compounds. These

Volume Change (%)

6
metal oxides contribute to the curing reaction of 5
bisphenol cure compounds and are added to 4
conventional peroxide cured FKM to facilitate cure
3
efficiency and promote thermal stability. In both cases,
2
they are added in stoichiometric excess and are thus
1
available to promote ester hydrolysis in cured FKM
0
compounds exposed to biodiesel. B5 RME B20 RME B100 RME

GBL-S (NMO) GF-S (NMO)

The effect of Ca(OH)2 level on volume swell for
compounds made with FKM-GBL-S is shown below.
Note that swell increases significantly as a function of Hardness Change in “Wet” Biodiesel
metal oxide, from 5% for the compound with no metal
oxide, to 19% with a formulation containing 1.5 pph and
All of the fluorelastomers evaluated exhibit greater
increasing further to 33% with 3.0 pph. In all of these
softening in the “wet” vs. ‘fresh” RME fuels evaluated in
tests with wet RME, the compound formulated with 1.5
this study. The hardness loss can be appreciable. For
parts was less affected than the similar compound
example, FKM-A401C and FKM-605C softened 24-27
formulated with 3 parts. This metal oxide level effect is
points respectively during the first 1008 hours (6 weeks)
shown clearly in the B100 swell data in Figure 8.
immersion in B100 RME at 125°C. The best retention of
hardness was observed with FKM-GBL-S (NMO) and
Figure 8 FKM-GF-S (NMO) containing no metal oxide. Even after
3032 hours exposure, both were within 9 points of their
Volume Change
Aged in "wet" B100 RME at 125°C
original hardness as is shown in Figure 10.
35

30
Figure 10
Volume Change (%)

25
Hardness Change
20
Aged in "wet" B100 RME at 125°C
0
15 GBL-S (NMO) GF-S (NMO) GBL-S A401C F605C
-5 Ca(OH)2
10
Hardness Change (pts)

5 -10

0
-15
GBL-S NMO GBL-S (CaOH2-1.5) GBL-S (CaOH2-3.0)

336 hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours -20

-25

This level effect of metal oxide lends support the -30

hypothesis that the metal oxide is participating in the
336 hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours
reactions leading to high swell of these compounds.

Figure 9 provides an overall view of volume swell with

acid resistant formulations of FKM-GBL-S and FKM-GF-
S containing no metal oxide when tested in “wet” B100,
“wet” B20 and “wet” B5 biodiesel blends, tested out to
3024 hours at 125°C. All swell values were within the 4-
7% range, which is indicative of excellent compatibility
with these acidic fuels.
Figure 11 shows the significant effect on hardness by Figure 13 illustrates the hardness change values in “wet”
the concentration of Ca(OH)2 when formulated with B5 after 3024 hours immersion. The hardness changes
FKM-GBL-S. Here we observed 9 points of softening are not as large as those seen in B20 or B100, again
after 3024 hours in B100 with FKM-GBL-S (NMO) presumably due to the lower concentration of RME in
containing no metal oxide versus 17-20 points of the fuel blend.
softening with formulations containing 1.5 and 3.0 pph of
Ca(OH)2 respectively. This response fits well with the Figure 13
volume change response shown in Figure 5 previously.
Hardness Change
Figure 11 Aged in "wet" B5 RME at 125°C
6
Hardness Change
Effect of Metal Oxide in FKM-GBL-S 4
Aged in "wet" B100 RME at 125°C

Hardness Change (pts)

0 2
GBL-S NMO GBL-S (CaOH2-1.5) GBL-S (CaOH2-3.0)
0
-5 GBL-S (NMO) GF-S (NMO) GBL-S A401C F605C
Hardness Change (pts)

-2 Ca(OH)2

-10
-4

-15 -6

-8
-20
336 hours 1008 hours 1512 hours 2016 hours 3024 hours

-25
336 hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours

Stress-Strain Property Retention in “wet” Biodiesel

Figure 12 illustrates the hardness changes in “wet” B20 Figure 14 illustrates the loss of tensile strength and
RME after 3024 hours immersion. The hardness loss is elongation with the fluoroelastomers after 3032 hours
not as large as those seen in B100, presumably due to immersion in “wet” B100 RME at 125°C. Fuels were
the lower concentration of RME in the fuel blend, with changed at the time of interval testing. FKM-A401C
the exception of the softening observed with FKM-605C. shows the greatest loss of tensile strength and
FKM-605C exhibited the greatest softening (31 points) elongation after 3032 hours exposure. FKM-401C lost
after 1008 hours, followed by FKM-A401C showing an 72% tensile strength and 43% elongation, while FKM-
18 points loss after 1008 hours. The best retention of F605C lost 55% tensile strength and gained 4%
hardness was observed with FKM-GBL-S (NMO) and elongation.
FKM-GF-S (NMO) containing no metal oxide.
Figure 14
Figure 12
Stress-Strain Change
Hardness Change Aged in "wet" B100 RME after 3024 hours at 125°C
Aged in "wet" B20 RME at 125°C
0
GBL-S (NMO) GF-S (NMO) GBL-S A401C F605C 20
-5 Ca(OH)2
Stress-Strain Change (%)

0
Hardness Change (pts)

-10
GBL-S GF-S (NMO) GBL-S A401C F605C
-20 (NMO) Ca(OH)2
-15

-20 -40

-25
-60
-30
-80
-35
Tensile Strength Elongation at Break
336 hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours
CONCLUSION
Chemical compatibility testing in biodiesel must take into
account the fact that these fuels are more hygroscopic
than conventional diesel and much more prone to
oxidation. We recommend that water and carboxylic acid
be added to the test fuels to better simulate field
conditions and avoid missing important second order
effects associated with them.
Understanding the chemistry can lead to formulations
with significantly improved resistance to biodiesel. The
incorporation of metal oxides has been shown to be
deleterious to the performance of fluoroelastomers
vulcanizates immersed in biodiesel fuels containing
water or acid. Formulations without metal oxides are
practical with the APA polymers and provide compounds
that offer robust long-term protection against these
second order effects.
Two such formulations were developed based on FKM-
GBL-S and FKM-GF-S and these NMO compounds
without added metal oxide show excellent resistance to
“wet” biodiesel under conditions that lead to high swell of
conventionally formulated, metal oxide containing FKM.
A variety of fluoroelastomers have been reviewed in this
paper to evaluate their compatibility with biodiesel fuels.
The following is a summary of our conclusions:
• It was found that fresh, presumably pure, RME is not
aggressive toward FKM compounds and does not
swell FKM, even conventionally formulated FKM
containing metal oxide.
• Commercial biodiesel is not stored under conditions
conducive for long term stability, either in the
production facility or in the fuel tank of the user.
Biodiesel fuels are easily oxidized and contain acids
and water.
• Biodiesel fuels containing water, acid or both can be
very aggressive toward conventionally formulated
FKM, causing metal oxide-containing FKM to swell,
in some cases severely.
• Peroxide cured FKMs, such as the APA polymers,
when formulated without any metal oxide are
resistant to the aggressive wet, acidified biodiesel
fuels.
• These “no metal oxide” (NMO) formulations
performed well under all test conditions.
• Biodiesel-petroleum diesel blend fuels containing
acid or water are also aggressive toward metal
oxide containing FKM. “Wet” B20 was about as
aggressive as “wet” B100.
• ”Wet” B5 was not as aggressive as B20, swells were
typically less than 10%, however B5 was still more
aggressive toward conventionally formulated FKM
than toward the NMO formulations.
• Bisphenol cured formulations containing the high
level of metal oxide required by the cure system
performed poorly in the B100 and B20 fuels and
exhibited higher swells in B5.
• Hardness changes and tensile/elongation changes
correlate with the volume swell data.
• Care should be taken when drawing conclusions
about chemical compatibility from short term testing
in pure biodiesel.
• The “wet” biodiesel, as used in this study, is
aggressive toward FKM containing metal oxides.
However, it was not more aggressive than RME
stored for several months at room temperature
under an air atmosphere.
• Conclusions about FKM compatibility with the “wet”
acidified biodiesel blends when tested under the
accelerated aging conditions presented in this study
should be continued in order to correlate bench and
field experience.
Although conventional VF2/HFP fluoroelastomers
continue to be used extensively in automotive engines,
the specialty types of fluoroelastomers capable of being
formulated for optimum acid resistance and crosslinked
with peroxides offer superior compatibility with RME
biodiesel and the byproducts of its oxidation. For this
reason, materials like the advanced polymer architecture
grades, FKM-GBL-S and FKM-GF-S, as well as the
PMVE-containing types, FKM-GLT-S and FKM-GFLT-S,
will find increasing adoption, since they display the best
property retention in biodiesel fuels.
ACKNOWLEDGMENTS
The authors would like to thank John Leonhard and
Russ Morrison, Laboratory Technologists, DuPont
Performance Elastomers - Akron Lab, for their dedicated
work in generating the data presented in this paper. The
authors are also appreciative for the valued consultation
regarding the chemistry of biodiesel and fluoroelastomer
attack provided by Dr. Walter Schmiegel, Senior
Scientist, and Dr. Peter Fox, Sr. Technology Chemist,
DuPont Performance Elastomers, Wilmington,
Delaware.
REFERENCES
1. Dingle, Phillip J. G. and Ming-Chia D. Lai, “Diesel
Common Rail and Advanced Fuel Injection
Systems”, Publication T-117, p. 9-13, SAE
International, Warrendale, PA, 2005.
2. Knothe, Gerhard, Jon Van Gerpen, and Jurgen
Krahl, “The Biodiesel Handbook”, AOCS Press,
Urbana, IL, p. 1-3, 2005.
3. EN 14214 (Europe): “Automotive Fuels: FAME for
Diesel Engines. Requirements for Test Methods”,
2003.
4. D 6751, “Standard Specification for Biodiesel Fuel
Blend Stock (B100) for Middle Distillate Fuels”,
ASTM International, West Conshohocken, PA, 2006.
5. Schumacher, Leon, Biodiesel Lubricity. In: “The
Biodiesel Handbook”, ed. By Knothe, Gerhard, Jon
Van Gerpen, and Jurgen Krahl, AOCS Press,
Urbana, IL, p. 137-144, 2005.
6. Knothe, Gerhard, “The Lubricity of Biodiesel”, SAE
Paper # 2005-01-3672, October 24-27, 2005.
7. Stevens, Ronald D. & Donald F. Lyons, Paper #29,
“New, Improved Processing HFP-Peroxide Cured
Types of Viton®”, 160th meeting of the Rubber
Div./ACS, Cleveland, OH, October 2001.
8. Lyons, Donald F. & Ronald D. Stevens, Paper #30,
“New, Improved Processing PMVE-Peroxide Cured
Types of Viton®”, 160th meeting of the Rubber
Div./ACS, Cleveland, OH, October 2001.
9. Bowers, Steven, “New Specialty Viton® Products for
Automotive Sealing Applications”, 17th International
Conference on Fluid Sealing, York, United Kingdom,
April 8-10, 2003.
10. Thomas, Eric, “New Fluoroelastomer Developments
for Aerospace Sealing Applications”, 163rd meeting
of the Rubber Division, American Chemical Society,
San Francisco, CA, April 28-30, 2003.
11. Dobel, Theresa M. and John G. Bauerle, “New FKM
Developments for Automotive Powertrain
Applications”, SAE Paper # 2000-01-0745, March 6-
9, 2000.
12. Thomas, Eric W., “Fluoroelastomer and
Perfluoroelastomer Compatibility with Advanced Gas
Turbine Lubricants”, SAE Paper # 2003-01-3029,
September 8-12, 2003.
13. Frame, E. and R.L. McCormick, “Elastomer
Compatibility Testing of Renewable Diesel Fuels”,
NREL/TP-540-38834, November 2005.
14. Waynick, J. Andrew, “Characterization of Biodiesel
Oxidation and Oxidation Products”, Southwest
Research Institute, Project No. 08-10721, August
2005.
15. Knothe, Gerhard, Jon Van Gerpen, and Jurgen
Krahl, “The Biodiesel Handbook”, AOCS Press,
Urbana, IL, p. 122-124, 2005.
16. Fang, Howard L. and Robert L. McCormick,
“Spectroscopic Study of Biodiesel Degradation
Pathways”, SAE Paper 2006-01-3300, October 16-
19, 2006.
CONTACT
Eric Thomas is a Senior Technology Engineer with
DuPont Performance Elastomers located in Stow, Ohio.
He may be reached at 330-929-6914 or email at
eric.w.thomas@dupontelastomers.com.
Robert Fuller is a Technology Associate with DuPont
Performance Elastomers located in Wilmington,
Delaware. He may be reached at 302-792-4321 or email
at robert.e.fuller @dupontelastomers.com.
Kenji Terauchi is a Technical Service Representative
with DuPont Performance Elastomers located in
Yokohama, Japan. He may be reached at +81-45-938-
8101 or email at kenji.terauchi@dupontelastomers.com.
APPENDIX
RME 100 and Certification No. 2 Diesel Fuel available
from:
Specified Fuels & Chemicals
1201 South Sheldon Road
Channelview, TX 77530-0429
Phone: 281-457-2768
SPECIAL NOTE:
The information set forth herein is furnished free of charge and
is based on technical data that DuPont Performance
Elastomers believes to be reliable. It is intended for use by
persons having technical skill, at their own discretion and risk.
Handling precaution information is given with the
understanding that those using it will satisfy themselves that
their particular conditions of use present no health or safety
hazards. Since conditions of product use and disposal are
outside our control, we make no warranties, express or implied,
and assume no liability in connection with any use of this
information. As with any material, evaluation of any compound
under end-use conditions prior to specification is essential.
Nothing herein is to be taken as a license to operate or a
recommendation to infringe on patents.
Caution: Do not use in medical applications involving
permanent implantation in the human body. For other medical
applications, discuss with your DuPont Performance
Elastomers customer service representative and read Medical
Caution Statement H-69237