Materials Science and Engineering A 445–446 (2007) 669–675

Degradation of elastomeric gasket materials in PEM fuel cells

Jinzhu Tan a,b,1 , Y.J. Chao b,∗ , J.W. Van Zee c , W.K. Lee c
a College of Mechanical and Power Engineering, Nanjing University of Technology, Nanjing, Jiangsu 210009, China
b Department of Mechanical Engineering, University of South Carolina, 300 S. Main, Columbia, SC 29208, USA
c Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA

Received 8 August 2006; received in revised form 27 September 2006; accepted 29 September 2006

Abstract
Polymer electrolyte membrane (PEM) fuel cell stack requires gaskets in each cell to keep the reactant gases within their respective regions. Long-
term durability of the fuel cell stacks depends heavily on the functionality of the gaskets. Both the leachants from the seal materials and the cracking
of the seals are of great concern to the overall durability of the fuel cell stacks. The degradation of four commercially available gasket materials
was investigated in a PEM fuel cell environment in this study. Optical microscopy reveals that the degradation starts with surface roughness from
the early stage of exposure and finally results in cracks over time. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy
and X-ray photoelectron spectroscopy (XPS) were employed to study the surface chemistry of the gasket materials before and after exposure to
the PEM fuel cell environment over time. Results from these analyses indicate that the surface chemistry changed initially as a manifestation of
the chemical degradation and proceeded via de-cross-linking and chain scission in the backbone. Atomic adsorption spectrometry analysis was
used to identify the leachants in the soaking solution from the gasket materials. The effect due to applied stress is reported as well.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Gasket material; Fuel cell; Degradation; ATR-FTIR; XPS

1. Introduction ical degradation of fluoroelastomer in an alkaline environment.

Polymer electrolyte membrane (PEM) fuel cell (FC) stacks
requires elastomeric gaskets in each cell to keep the reactant
gases within their respective regions. If any gasket degrades
or fails, the reactant gases (O2 and H2 ) can leak overboard
or mix each other directly during operation or standby, and
affect the overall operation and performance of the FC. The
elastomeric gaskets used as seal in FC are exposed to an acidic
environment, humid air and hydrogen, temperature as high as
80 ◦ C, and aqueous for coolants, and concurrently, is subjected
to mechanical compression between the bi-polar plates form-
ing the cell. Therefore, the long-term stability of the gaskets
in FC assemblies is critical. The performance of elastomeric
materials in various applications was studied extensively, e.g.
see refs. [1–20]. For instance, Gustavsson et al. [14] showed the
aging of Silicone rubber under ac and dc voltages in a coastal
environment. Mitra et al. [17] studied the time-dependent chem-
∗ resistance tests were performed on samples with various bend
Corresponding author. Tel.: +1 803 777 5869; fax: +1 803 777 0106.
E-mail address: chao@sc.edu (Y.J. Chao).
1 Present address: University of South Carolina, Columbia, SC 29208, USA.
Youn and Huh [18] reported the surface degradation of HTV Sili-
cone rubber and EPDM under accelerated ultraviolet weathering
condition. Although there exits a substantial literature regard-
ing degradation of the elastomeric gasket materials, few results
were reported for the degradation and its mechanisms in PEM
FC environment [5].
In this paper, we report the results from investigation on the
degradation of four commercially available gasket materials in a
simulated FC environment. The aim of the study is to determine
the chemical degradation and its mechanisms of the materials in
FC environment. As demonstrated in Fig. 1, the overall scope of
study includes chemical/material degradation and mechanical
property characterization. The chemical and mechanical degra-
dation mechanisms interact each other and lead to the loss of
functionality of the seals. The current paper reports our initial
findings from the chemical degradation.
Two solutions and two temperatures were used in the short-
term, accelerated aging tests of the gasket materials in an effort
towards predicting lifetime. Bend strip environment stress crack
angles. Weight loss was monitored and surface structure changes
were examined using optical microscopy on the samples exposed

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.09.098
670 J. Tan et al. / Materials Science and Engineering A 445–446 (2007) 669–675

Fig. 1. Flow chart for investigating the degradation of gasket materials in fuel cells.

to the simulated FC environment at selected exposure time. The

leachants from the seal materials was analyzed using atomic
adsorption spectrometry. The chemical degradation on the sur-
face of the gasket materials after exposure to the simulated FC
environment over time was elucidated using the attenuated total
reflection Fourier transform infrared (ATR-FTIR) spectroscopy
and X-ray photoelectron spectroscopy (XPS).

2. Experiments

2.1. Materials and simulated fuel cell environment

The materials selected for this study include the elastomeric

sealing materials, Silicone S (SS), Silicone G (SG), ethylene-
propylene-diene-monomer (EPDM or EP) and fluoroelastomer
T (FL) that are commercially available. Silicones are attractive
because of their low cost and easy fabrication. They are widely
used as sealing materials, including in fuel cells [4,20].
Two solutions were used in the simulated FC environment for
our present study, that is, an accelerated durability test (ADT)
solution for short-term accelerated aging tests, and a regular
solution which is similar to that in a real fuel cell. Forty-eight per-
cent HF and 98% H2 SO4 were dissolved in balance reagent grade
water to make both the ADT solution and the regular solution.
The composition of the ADT solution is 1 M H2 SO4 , 10 ppm HF
and reagent grade water having 18 M resistance. The compo-
sition of the regular solution is 12 ppm H2 SO4 , 1.8 ppm HF and
reagent grade water having 18 M resistance.
Test temperatures were selected as 80 and 60 ◦ C which are
close to the operating temperatures of actual PEM fuel cells.
2.2. Aging and characterization methods
Fig. 2. Fixture for tests with 120◦ bend angle.
in weight was monitored on the samples exposed to the ADT
solution every 1 or 2 weeks and in the regular solution every 2 or
4 weeks. The surface conditions of the samples were examined
before and after exposure to the solutions using optical micro-
scope (Leco, OLYMPUS PME-3) at selected time.
In the bend strip test, each gasket sample was submerged in
the solution. The solution exposed to each sample was taken
out at selected time and analyzed for leachants using atomic
adsorption spectrometry (Perkin-Elmer 3300).
Samples were submerged in the ADT solution bottles at 80
and 60 ◦ C for various periods. The aged samples were taken
Table 1
Dimensions of the test samples
Materials Bend angle (◦ ) Length × width × thickness (mm)

Silicone S 0, 90, 120 40 × 10 × 1

Rectangular-shaped specimens from four gasket materials Silicone G 90, 120 40 × 10 × 3.2
were prepared and bent to 90◦ , 120◦ or 180◦ angle using fix- EPDM 90, 120 40 × 10 × 1.6
tures shown in Fig. 2, and then submerged in the two solutions Fluoroelastomer T 90, 120 40 × 10 × 2.0
mentioned in the previous section. Different bend angles were Silicone S 180 60 × 10 × 1
designed to result in different maximum stress level at the apex Silicone G 180 60 × 10 × 3.2
EPDM 180 60 × 10 × 1.6
of the bend specimen. The dimensions of specimens are listed in Fluoroelastomer T 180 60 × 10 × 2.0
Table 1. The tests were performed at 80 and 60 ◦ C. The change
 J. Tan et al. / Materials Science and Engineering A 445–446 (2007) 669–675
Fig. 3. Weight change with exposure time for samples having 120◦ bend angle
in ADT solution.
out of the test bottle at selected times and the weight loss was
measured. In addition, ATR-FTIR spectroscopy was performed
on the surface of the gasket samples using a Nexus Model 670
Instrument (Nicolet Instrument Corporation) and run with 128
scans at a resolution of 4 cm−1 . The infrared radiation (IR) pen-
etrates the surface of the test sample to approximately 1 ␮m.
The surface topography before and after the exposure was also
monitored using the optical microscope.
Samples with 15 mm (length) × 10 mm (width) × (1–
3.2) mm (thickness) were prepared and exposed to ADT solu-
tion at 80 and 60 ◦ C. The aged samples were taken out of the test
bottles at selected times for XPS analysis using a Kratos AXIS
165 spectrometer with monochromatic Al K␣ (1486.71 eV) X-
ray source operated at a take-off angle of 90◦ in a probe depth
of 0.3–5 nm. The pressure used in the XPS chamber was about
2.67 × 10−7 Pa and increased to approximately 2.53 × 10−5 Pa
during ion bombardment. The survey spectra in the range of
0–1200 eV were recorded in 1 eV step for each sample. Atomic
concentrations of each element were calculated by determining
the relevant integral peak intensities. High-resolution analysis
was performed in the carbon 1s (C 1s) and the silicon 2p (Si
2p) regions. The spectra were deconvoluted by curve-fitting.
The high-resolution spectra were recorded in 0.1 eV steps from
which the detailed compositions were calculated. The full width
at half maximum (FWHM) for all peaks were constrained to
1–2.0 eV.
Note that in order to avoid the effect due to the remaining ADT
solution on the sample surface on the ATR-FTIR and the XPS
results, the surface of the sample was cleaned using reagent grade
Fig. 4. A broken sample of Silicone S having 120◦ bend angle after 45 weeks exposure to ADT solution at 60 ◦ C.
671
Fig. 5. Comparison of weight loss: Silicone S samples with 0◦ , 90◦ and 120◦
bend angles in ADT at 80 ◦ C.
water having 18 M resistance and dried at room temperature
before the analyses.
3. Results and discussion
3.1. Bend strip environmental stress crack resistance tests
Fig. 3 shows the change of weight from samples having 120◦
bend angle in the ADT solution at 80 and 60 ◦ C. It is shown from
Fig. 3 that SS samples are the most affected by weight lost and
they completely failed after 6 weeks exposure at 80 ◦ C and 45
weeks exposure at 60 ◦ C (see Fig. 4). SG also degraded as repre-
sented by its weight loss and completely failed after 4 weeks at
80 ◦ C. Unlike Silicones, both EPDM (EP) and fluoroelastomer
(FL) showed a slight increase in weight after 1 week. After that,
they seem to maintain constant weight with time. The change of
weight from the samples with bend angles of 90◦ and 180◦ at
80 and 60 ◦ C in our pervious work [21] is similar to the trends
as those samples having 120◦ bend angle in ADT solution at 80
and 60 ◦ C.
It appears that the temperature has a significant effect on the
degradation of the four materials as seen from Fig. 3, i.e. the
higher the temperature, the more material loss. Among them,
SS is the most affected. Similar trend, but less weight loss, is
observed for SG.
Fig. 5 shows the comparison of weight change for Silicone
S samples with bend angles of 120◦ , 90◦ and no bend in ADT
solution at 80 ◦ C. It is concluded that the applied stress in the
sample accelerated the degradation of the materials with time.
672 J. Tan et al. / Materials Science and Engineering A 445–446 (2007) 669–675

Fig. 6. Optical micrographs for Silicone S and Silicone G samples with bend angle of 120◦ exposed to ADT solution at 60 ◦ C, 500×. (a) Before exposure for SS,
(b) 10 week exposure for SS, (c) 14 week exposure for SS, (d) before exposure for SG, (e) 6 week exposure for SG and (f) 8 week exposure for SG.

3.2. Optical microscopy
Optical microscopy was used to visually observe the degra-
dation of the surface of the materials. Fig. 6 shows the optical
micrographs of SS and SG samples with 120◦ bend angle before
and after exposure to ADT solution at 60 ◦ C at selected times.
All photos were taken at the center of the apex of the sample
where the tensile stress is maximum. The magnification used in
the tests is 500×.
The results clearly show that surface conditions were changed
over time from initially smooth to rough and to cracked surface.
Specifically, after 14 and 6 weeks of exposure to the simulated
fuel cell environment for the SS and SG samples, respectively,
small cracks appeared on the surface (see Fig. 6c and e). The
crack size increased significantly with exposure time after that.
It is believed that stress corrosion had contributed to the gradual
crack propagation afterwards.
3.3. Atomic adsorption spectrometry
In order to identify the foreign materials leached from the
gasket samples into the soaking solution, the atomic adsorption
spectrometry was employed to analyze the solution. Both cal-
cium and magnesium were identified in the solution. Table 2
shows the calcium and magnesium values in ADT and regular
solution from the 180◦ bend samples. Fig. 7 shows the calcium

Table 2
Calcium and magnesium values (mg/l)
Sample materials Exposure time (weeks) ADT solution Regular solution

80 ◦ C 60 ◦ C 80 ◦ C 60 ◦ C

Ca Mg Ca Mg Ca Mg Ca Mg

Silicone S 8 (1–8) 44a 1.70a

19 (1–19) 11a 0.45a
24 (1–24) 18.9 0.14 5.07 0.05
14 (25–38) 7.73 0.09 2.95 0.06
Silicone G 28 (1–28) 0.50 0.13
24 (1–24) 0.40 0.05 0.92 0.03 0.78 0.03
14 (25–38) 0.28 0.04 0.23 0.02 0.13 0.03 0.41 0.02
EPDM 28 (1–28) 0.50 0.05
24 (1–24) 0.30 0.04 0.42 0.02 0.35 0.02
14 (25–38) 0.12 0.03 0.28 0.02 0.36 0.04 0.25 0.02
Fluoroelastomer 28 (1–28) 0.90 1.60
24 (1–24) 0.40 0.64 0.80 1.80 0.50 0.71
14 (25–38) 0.27 0.21 0.42 0.16 0.34 0.11 0.37 0.12
a Failed sample.
 J. Tan et al. / Materials Science and Engineering A 445–446 (2007) 669–675
Fig. 7. Calcium values (mg/l) in ADT solutions with exposure time for 120◦
bend samples.
values in ADT solutions with exposure time from the 120◦ bend
samples. It can be seen from Table 2 and Fig. 7 that the con-
centration of these leaching chemicals increased with exposure
time.
It is well-known that the mechanical properties of elastomeric
gasket material, such as tensile strength, hardness, the resis-
tance to compression set and so on, depend considerably on
the fillers in the compound. When the gasket samples were
submerged into the FC solution in our study, the fillers in the
elastomeric gasket material, such as magnesium oxide, calcium
carbonate, apparently were attacked by the solution. And con-
sequently, the chemicals, such as calcium and magnesium, were
formed and detected in the soaking solution. The identification
of these materials in the soaking solution indicates that these
elastomeric gasket materials were degraded in the simulated FC
environment. Furthermore, these chemicals in the solution could
severely impair the electrochemical process of the FC.
3.4. ATR-FTIR
The aim of the ATR-FTIR analysis is to determine the chem-
istry changes that occurred to the test materials after exposure to
simulated fuel cell environment. The spectra for the SS samples
before and after exposure to the simulated fuel cell environment
at various times are shown in Fig. 8.
The unexposed data in Fig. 8 show that the strongest and
broadest band is between 1020 and 1090 cm−1 which is from the
vibration of ␯(Si O Si) stretching mode [22]. It can also been
seen that long-chain Siloxanes have two broad IR bands near
1020 and 1090 cm−1 . The intensity of these bands decreased
sharply after only 1 week exposure and then almost disappeared
after 5 weeks exposure for SS at 80 ◦ C (see Fig. 8A). Simi-
lar observations in Fig. 8A can be made for the characteristic
band at 866 cm−1 , which is due to the ␳(Si CH3 ) rocking vibra-
tion, and at 1260 cm−1 which is due to the ␦(Si CH3 ) bending
mode. In Fig. 8B, similar observation can also be obtained for
the characteristic band at 2960 cm−1 which is due to the ␯(CH3 )
stretching vibration mode. Simultaneously a group of new band
emerges in the spectra near 1040 cm−1 , which is likely due to
the ␯(Si−O) stretching mode. Similar trends are observed for
673
Fig. 8. Comparison of ATR-FTIR spectra for Silicone S in ADT solution at
80 ◦ C: (a) without exposure and after (b) 1 week, (c) 3 weeks, (d) 5 weeks, (e)
7 weeks and (f) 10 weeks. (A) ATR-FTIR spectra from 800 to 1400 cm−1 and
(B) ATR-FTIR spectra from 2500 to 3500 cm−1 .
SS at 60 ◦ C except for that the intensity at 1020 and 1090 cm−1
which is from ␯(Si−O−Si) vibration, and the intensities at 866,
1260 and 2960 cm−1 , decreased sharply after 3 weeks exposure
to the ADT solution.
It is concluded that there are significant chemistry changes in
the rubber backbone after 1 week at 80 ◦ C and 3 weeks at 60 ◦ C
for SS in the FC environment.
3.5. X-ray photoelectron spectroscopy
XPS is a surface sensitive analysis method to elucidate the
surface chemicals. In our study, XPS was used to obtain qual-
itative and quantitative information on the surface of the four
gasket materials before and after exposure to ADT solution at
80 and 60 ◦ C.
Fig. 9 shows XPS survey spectra for SS samples before and
after 4 weeks exposure to ADT at 80 ◦ C. The spectra revealed
the presence of carbon (C), oxygen (O), silicon (Si) and small
amount of fluorine (F). The atomic concentrations of these ele-
ments are given in Table 3. The presence of F may result from
the environment occurred on the surface of the sample. From
Fig. 9, it can be seen that the carbon peak decreased and the
oxygen peak increased with exposure times. Table 3 also shows
the ratios of concentration (C/Si and O/Si) for SS material before
and after different exposure times. As shown in Table 3, the C/Si
ratio decreased significantly with increasing exposure time. This
674 J. Tan et al. / Materials Science and Engineering A 445–446 (2007) 669–675

trochemical process, and therefore the long-term durability of

PEM FC.

4. Conclusion and future work

The degradation of commercial elastomeric gasket materials

in simulated fuel cell environment was studied. The following
conclusion can be made:

1. Both Silicone S and Silicone G were degraded, judged by

Fig. 9. XPS survey spectra for Silicone S sample before and after exposure to
ADT solution at 80 ◦ C. (A) Before exposure and (B) 4 week exposure.
behavior could be due to that the methyl group on the silicon
atom was attacked and oxidized to form the Si O bonds. The
increase of O/Si ratio with exposure time may indicate that the
chain in the backbone ( Si O Si ) was attacked and broken.
These changes of chemical components reflect the chemical
degradation of the materials exposed to the FC environment. The
degradation proceeded via de-cross-linking and chain scission
in the backbone. The XPS results are in agreement with the FTIR
observations.
In summary, from the ATR-FTIR, XPS and atomic adsorption
spectrometry analyses it appears that the degradation mech-
anism for the gasket materials proceeds via de-cross-linking
and chain scission in the backbone accompanied with the dam-
age of the fillers in the materials. The degradation may affect
the mechanical properties of the gasket materials, the elec-
Table 3
Surface atomic concentration of each element and ratios of atomic concentrations
of O and C to Si for Silicone S sample before and after exposures to ADT solution
at 80 ◦ C
Samples Atomic concentration (at.%)
C O Si F C/Si
mass loss and cracking, in either ADT or regular FC solutions
at 80 and 60 ◦ C, while EPDM and fluoroelastomer showed
little degradation up to 45 weeks exposure to the ADT solu-
tion at bend angle of 120◦ .
2. The degradation of Silicone S and Silicone G is sensitive
to temperature in the ATD solution, i.e. the higher the tem-
perature, the faster material degrades. Silicone S is the most
affected by temperature while the effect of temperature on the
degradation of the EPDM and fluoroelastomer is not remark-
able in the current study.
3. Stress in the sample could accelerate the degradation of the
materials. The material degrades faster with higher applied
stress.
4. Atomic adsorption spectrometry shows the leached materi-
als (calcium and magnesium) from the gasket samples into
the soaking solution, and the concentration of these leaching
chemicals increased with exposure time.
5. Optical microscopy shows that the degradation starts with
surface roughness right from the beginning of the exposure
and finally results in cracks on the surface after exposure over
time. ATR-FTIR spectrometry and XPS analysis reveal that
the surface chemistry changed initially as a manifestation of
the chemical degradation and proceeded via de-cross-linking
and chain scission in the backbone. The degradation may
eventually affect the mechanical and chemical durability of
PEM FC gasket materials.
6. Current work is to reveal the fundamental degradation mech-
anisms on the surface of the gasket materials in PEM FC
environment. Degradation in mechanical properties of the
gasket materials is under investigation and will be reported
later.
Acknowledgements
The work was sponsored by the NSF Industry/University
Cooperative Research Center for Fuel Cells at the University
of South Carolina. Encouragement from the industry partners
and financial support from the center were great appreciated.
The assistance from Dr. C.T. Williams, C.C. Stork and Ivelisse
Ortiz is acknowledged.
Ratios to Si
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