Polymer Degradation and Stability 109 (2014) 122e128

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Degradation of silicone rubbers with different hardness in various

aqueous solutions
Jun Feng a, Qinglian Zhang a, Zhengkai Tu a, b, *, Wenmao Tu b, Zhongmin Wan c,
Mu Pan a, b, Haining Zhang a, b, *
a
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of Technology, Wuhan 430070, PR China
b
Hubei Key Laboratory of Fuel Cells, Wuhan University of Technology, Wuhan 430070, PR China
c
School of Physics, Hunan Institute of Science and Technology, Yueyang 414006, PR China

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

Article history: Durability is one of the remaining challenges for practical application of proton exchange membrane fuel
Received 22 February 2014 cells. Seals or gaskets around perimeters of each cell in a fuel cell stack are important to prevent leakage
Received in revised form of reactant gases, avoiding the decay in utilization of gases and in overall cell performance. In this study,
30 April 2014
degradation of silicone rubbers, often used as sealing material in fuel cells, with different hardness in
Accepted 8 July 2014
Available online 16 July 2014
various aqueous solutions is investigated. Although the weight loss increases with the increase in
hardness, the durability seems enhanced with the increase in hardness, as revealed by the variation of
surface morphology and mechanical properties of silicone rubbers before and after exposure to acidic
Keywords:
Proton exchange membrane fuel cell
aqueous solutions. It also turns out that the degradation of silicone rubbers can be catalyzed by protons,
Silicone rubbers leading to severe corrosion of materials in strong acidic environment. The results described in this study
Gaskets may provide guidance to evaluation or selection of silicone rubbers as seals for PEMFC applications.
Degradation © 2014 Elsevier Ltd. All rights reserved.
Chemical decomposition

1. Introduction several hundreds of single cells, depending on the designed power

As concerns mount on limited energy sources and ecological
challenges, it is essential to develop alternative, renewable, and
environmentally friendly sources of energy to meet the changing
and growing global energy demands. Fuel cell, particularly proton
exchange membrane fuel cell (PEMFC) that is an electrochemical
device directly converting the chemical energy of a fuel into elec-
tricity, emerges as a promising alternative to the depleting fossil
energy sources due to its green nature, high energy density, and
wide range of applicability including automotive and stationary
application [1,2]. Nonetheless, the durability of PEMFC remains a
major challenge towards its commercial viability and has attracted
great attention from researchers worldwide [3,4].
PEMFC stack is assembled by connecting each single cell in se-
ries, which consists of membrane electrode assembly, gas diffusion
layer, gaskets, and bipolar plates with flow channels for reactant
gases. In general, one PEMFC stack contains several tens to even
* Corresponding authors. State Key Laboratory of Advanced Technology for Ma-
terials Synthesis and Processing Wuhan University of Technology, Wuhan, 430070,
PR China. Tel.: þ86 27 87651839; fax: þ86 27 87879468.
E-mail addresses: tzklq@whut.edu.cn (Z. Tu), haining.zhang@whut.edu.cn
(H. Zhang).
of the stack. For each cell, gaskets or seals have to be used around
the perimeters to prevent the leakage of reactant gases from the
active area. If any seal or sealing material degrades during fuel cell
operation, a leakage leading to mixture of reactant gases can occur.
This will not only affect the performance of fuel cells and the uti-
lization of fuel gases, but may also bring the danger of burning from
the mixture of hydrogen and oxygen (air). Thus, the stability and
durability of sealing materials are of great importance for fuel cell
applications.
Considering the operation conditions and key materials of a
typical PEMFC, the seals are often exposed to acidic aqueous solu-
tion, humid air, mechanical stress, and elevated temperatures
(65e80
C) as well. In addition, if small ions leach out of the sealing
materials, they can migrate to the surface of polymer electrolyte
membrane or catalyst and affect the proton conductivity or cata-
lytic activity respectively. Therefore, sealing materials for PEMFC
applications should be stable and durable during the operation of
fuel cells throughout the entire life of designed fuel cells [5e7].
Although the suitable sealing materials in PEMFC strongly
depend on the conditions for stack assembly and operation con-
ditions of the stack, It is generally realized that the hardness (Shore
A) of sealing materials in the range of 20e60 is suitable for PEMFC
application [8]. Silicone rubbers have attracted much attention as

http://dx.doi.org/10.1016/j.polymdegradstab.2014.07.011
0141-3910/© 2014 Elsevier Ltd. All rights reserved.
 J. Feng et al. / Polymer Degradation and Stability 109 (2014) 122e128
sealing materials in PEMFCs because of their low cost, good me-
chanical properties, wide temperature ranges for application as
well as easy manufacturing process [9e14]. Extensive studies have
been conducted on the variation of chemical and mechanical
properties of silicone rubbers while exposed to different environ-
ments [15e25]. As sealing material for PEMFC applications, Chao
and co-workers have systematically studied the degradation
behavior of silicone rubbers exposed to solutions simulating fuel
cell environment and accelerated durability test solutions [26e32].
They found that silicone rubbers corrode severely with the increase
in acidity of exposed solutions and the degradation of silicone
rubbers was attributed to both chemical decomposition of silicon
based backbone and leaching of fillers. Schulze et al. observed that
small particles were released from silicone rubbers after operation
of an assembled fuel cell [33]. The released small particles could
further migrate to the surface of membrane at anode side and
migrate to interface of gas diffusion layer and catalyst layer, leading
to the decay of the overall fuel cell performance. Generally, most of
the works reported in literature are focused on the degradation
mechanism of silicone rubbers under different conditions or the
comparison of silicone rubbers with other elastic materials. How-
ever, the degradation of silicone rubbers with different hardness
has not been reported.
In this study, degradation of silicone rubbers with different
hardness exposed to various aqueous solutions was investigated.
Considering the elastic properties required for practical fuel cell
applications [8], three silicone rubbers with Shore hardness of 30,
40, and 50 were selected. It turned out that the degradation of
silicone rubbers could result in weight loss and voids or cracks on
the surface of tested materials because of the chemical decompo-
sition of silicon based backbone and leaching of fillers. With the
increase in hardness, silicone rubbers became more durable in
tested aqueous solutions. The results described here may provide
guidance for evaluation or selection of silicone rubbers as seals for
PEMFC applications.
2. Experimental
Methylvinyl silicone rubbers with hardness of 30, 40, 50 (Shore
A) used in this study have thickness of 0.5 mm and were purchased
from For long Silicone Rubber Products Co. Ltd (China). Reagent
grade acetic acid, sulfuric acid (98%), and hydrofluoric acid (48%)
were received from Sinopharm Chemical Reagent Co. Ltd (China).
Water was de-ionized through a Milli-Q system (Barnsted Nano-
pore, resistivity ¼ 18.0 MU cm1). Prior to degradation tests, sili-
cone rubbers were flushed with de-ionized water to clean the
surface.
Aqueous solution to simulate the operation environment of
proton exchange membrane fuel cells (denoted as simulated solu-
tion) consists of 98% H2SO4 and 48% HF diluted in de-ionized water.
The final composition was 12 ppm H2SO4, 1.8 ppm HF, and de-
ionized water. The pH value of this simulated solution was 3.35,
that is close to the fuel cell environment [34]. The strong acid so-
lution used in this study also consists of 98% H2SO4 and 48% HF
diluted in de-ionized water. The final composition is 1.0 M H2SO4,
1.8 ppm HF, and de-ionized water. An acetic acid solution with pH
of 5.0 was employed as weak acid.
All the tested specimens have square-shape with dimensions of
7.0 cm in both length and width. The samples were submerged into
solutions in different containers placed in an oven for degradation
test. Since the typical PEMFC is operated at temperature range of
65e80
C, degradation tests of silicone rubbers were carried out at
80
C. The degraded samples were taken out after a specific time
period and thoroughly rinsed with de-ionized water and dried in
air for further analysis. The overall exposure time was 15 days for
123
samples exposed to strong acid solution and 30 days for other
aqueous solutions.
The weight of samples was measured using electronic balance
(Mark MW3, Boyue Instrument Co.) with resolution of 1.0 mg. The
contents of silicon and calcium in aged solution were determined
on Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-
AES, Optima 5300DV, PekineElmer). The wavelength is in the range
of 165e782 nm with a resolution of 0.006 nm. Mechanical property
of silicone rubbers were tested at room temperature using an
Electromechanical Universal Testing Machine (WDW-1C, Shanghai
Hualong Co., China). Samples were measured at a strain rate of
50 mm per minute. Fourier transform infrared spectra (FTIR, Bio-
Rad FTS 300) were recorded with a resolution of 4 cm1 to inves-
tigate the chemical degradation of silicone rubbers. Surface
morphology of silicone rubbers before and after degradation in
desired solutions was examined using scanning electron micro-
scopy (SEM, JEOL JSM-5610LV).
3. Results and discussion
After exposure to desired solutions, the percentage of weight
loss of the tested sample, defined as the ratio of weight change
before and after degradation test to the initial weight of the tested
samples, was first investigated. Fig. 1a displays the percentage of
weight loss of silicone rubbers with different hardness as a function
of exposure time in simulated solution. It can be clearly seen that all
the tested samples gradually lost weight with the increase in
exposure time in simulated solution. Furthermore, with the in-
crease in the hardness of silicone rubbers, the weight loss becomes
more significant. As can be seen from Fig 1a, after exposure to
simulated solution for 30 days, the weight loss for materials with
hardness of 30 is about 0.98% whereas it is about 1.8% for materials
with hardness of 50. Since the environment during PEMFC opera-
tion is acidic, the weight loss of silicone rubber with hardness of 40
was also investigated in different acidic conditions, as shown in Fig
1b. It is apparent that the weight loss of the tested material
increased with the increase in acidity of the exposed solution,
reaching 2.1% in strong acid solution even within 15 days. However,
even when exposed in de-ionized water, the tested material also
lost weight after a certain period of time. Typically, fillers including
silicon dioxide and calcium carbonate are often impregnated into
silicone rubbers to improve their mechanical properties. While
exposed to aqueous solution, the polysiloxane backbone of silicon
rubbers swells up and causes the fillers to leach out, leading to the
weight loss of the tested materials. In addition, the existence of F
in both simulated and strong acid solutions could also result in the
chemical decomposition of silicone rubbers under acidic environ-
ment. Thus, the weight loss in strong acid aqueous solution is more
pronounced.
As the leaching of fillers from silicone rubber is closely related to
the swelling of the silicone rubber, the volume expansion proper-
ties of silicone rubbers in different aqueous solutions were further
investigated. Fig 2a displays the volume expansion ratio, defined as
the ratio of volume change before and after exposure in solution to
the initial dry volume of tested samples, as a function of exposure
time in simulated solutions. Clearly, after 30 days of exposure to
simulated solution, all the tested silicone rubbers swelled, reaching
the volume expansion percentages of 18.3%, 17.7%, and 16.0% for
silicone rubbers with hardness of 30, 40, and 50, respectively. The
swelling of silicone rubbers indicates that the fillers in silicone
rubbers can leach out from the bulk materials, resulting in the
weight loss of tested materials. Although the swelling degree of
silicone rubber with hardness of 50 is the lowest one due to the
high density of cross-linking, the highest weight loss value for the
sample with hardness of 50, as described in the above paragraph,
124 J. Feng et al. / Polymer Degradation and Stability 109 (2014) 122e128

Fig. 1. Weight loss of silicone rubbers with different hardness after exposure to simulated solution (a) and of silicone rubber with hardness of 40 exposure to different aqueous
solutions (b). Solid lines are guide to eyes.

Fig. 2. Volume change of silicone rubbers with different hardness after exposure to simulated solutions (a) and of silicone rubber with hardness of 40 after exposure to different
aqueous solutions (b). Solid lines are guide to eyes.

was probably attributed to the largest amount of fillers impreg-
nated among the tested samples. Fig 2b showed the swelling of
silicone rubber with hardness of 40 in different aqueous solutions.
Since silicone rubbers can be dissolved in strong acid, the volume of
sample shrinks after exposure to strong acid aqueous solution. It is
also evident, that silicone rubber exhibits larger volume expansion
ratio in acetic acid solution than that in simulated solution
although the pH value of the used acetic acid solution (pH ~5.0) is
higher than that of simulated solution (pH ~3.35). This can be
attributed to the existence of HF molecules in simulated solution,
which can accelerate decomposition of SieO bonds in silicone
rubbers.
As it is hypothesized that the weight loss of silicone rubbers
mainly results from the leaching of fillers, the leachants were
identified by determining the concentration of silicon and calcium
atoms in the solutions after exposure of silicone rubbers using
inductively coupled plasma atomic emission spectroscopy (ICP-
AES). Fig 3a displays the detected silicon in solutions after expo-
sure of different silicone rubbers as a function of exposure time. It
is shown that all the three tested silicone rubbers had consider-
able silicon leachant and the amount of tested silicon in solutions
increased with the increase in exposure time. In addition, the
silicon leaching from tested materials became more severe with
the increase in hardness of silicone rubbers, possibly attributed to
the increased amount of silicon dioxide fillers. This result is
consistent with the weight loss data shown in Fig 1a. Similar to
the weight loss results, exposure in strong acid solution leads to
significant fast leaching of silicon. As displayed in Fig 3b, even
within 15 days of exposure to strong acid solution, the silicon
concentration in solution was detected to be 55.4 mgL1, which is
much higher than that in simulated solution (~47.5 mgL1) for 30
days.

Fig. 3. Concentration of leached silicon from simulated solutions for silicone rubbers with different hardness (a) and from different aqueous solutions for silicone rubber with
hardness of 40 (b). Solid lines are guide to eyes.
 J. Feng et al. / Polymer Degradation and Stability 109 (2014) 122e128
Fig. 4. Concentration of leached calcium from simulated solutions for silicone rubbers with different hardness (a) and from different aqueous solutions for silicone rubber with
hardness of 40 (b). Solid lines are guide to eyes.
Fig 4 shows the detected calcium ions concentration from
simulated solutions for silicone rubbers with different hardness (a)
and from different solutions for silicone rubber with hardness of 40
(b). Despite that the leaching trend of calcium is very similar to that
of silicon, the calcium concentrations in all tested solutions are less
than 1.0 mgL1. The results suggest that the major weight loss of
silicone rubbers in simulated solution is attributed to the leaching
of silicon based materials as also reported in literature where sili-
cone resins were soaked in regular and accelerated durability test
solutions [13,26]. The effect of cation contaminant on the proton
conductivity of polymer electrolyte membranes has been analyzed
both theoretically [35] and experimentally [36]. It was found that
contaminant tolerance limit for divalent cation is about 380 ppm
[35]. Since leached calcium ions were clearly detected, the degra-
dation of silicon rubbers would affect the proton conduction of
membranes. In addition, the leached silicon based materials can
also affect the properties of gas diffusion media as described in
literature [33].
To determine whether the chemical degradation occurred after
exposure of silicone rubbers to aqueous solutions, FTIR spectra
were recorded in Fig 5. In general, the absorption peak at
2960 cm1 is assigned to stretching vibration of CH3. The absorp-
tion peak at 1410 cm1 is assigned to the rocking vibration of
eCH2e. The absorption peaks at 1260 cm1 and 864 cm1 are
assigned to bending vibration and rocking vibration of SieCH3. The
absorption peaks at 1080 cm1 and 1010 cm1 are assigned to the
stretching vibration of SieOeSi on backbone of silicone rubbers.
The absorption peak at 793 cm1 is assigned to the coupling of
stretching vibration of SieC and rocking vibration of eCH3. Fig 5a
shows the FTIR spectra of silicone rubbers with different hardness
before and after exposure to the simulated solutions for 30 days. It
is evident, that the intensity of absorption peaks at 1080 cm1 and
Fig. 5. FTIR spectra of silicone rubbers with different hardness before (dash lines) and after (solid lines) exposure to simulated solutions (a) and of silicone rubber with hardness of
40 after exposure to different aqueous solutions (b).
125
1010 cm1 decreased significantly after exposure in simulated so-
lutions for all the tested samples, indicating that some of SieOeSi
bonds were broken under the attack of protons [23]. The decrease
in intensity of absorption peaks at 2920 cm1, 1410 cm1,
1260 cm1, 864 cm1, and 793 cm1 suggested the decomposition
of methyl groups attached to silicon atoms. Fig 5b displays the FTIR
spectra of silicone rubber with hardness of 40 after exposed to
different aqueous solutions. For comparison, the spectrum of un-
treated silicone rubber was plotted in the same figure. It can be
clearly seen that the chemical degradation of silicone rubber
became more severe with the increase in acidity of the exposed
solutions, indicating that protons can accelerate the chemical
degradation of silicone rubbers. Hydrothermal decomposition
induced the decrease in FTIR absorption intensity was also
observed in a cross-linked liquid silicone rubber system [37].
Based on the degradation mechanism of silicone rubbers
[37e39], the decomposition of methyl groups attached to silicon
atoms leads to generation of silanol groups, which can be further
cross-linked by the formation of new SieOeSi bonds through
condensation reaction. Accordingly, the increased degree of cross-
linking can result in the increase in elastic modulus. Fig 6a dis-
plays the variation of elastic modulus of silicone rubbers with
different hardness after exposed to simulated solutions for a period
of times. As expected, all the samples exhibited slight increase in
elastic modulus with the increase in exposure time. While the
hardness of silicone rubbers increased, the increase in elastic
modulus under the same conditions became less pronounced. For
example, after exposure to simulated solution for 30 days, the
elastic modulus for silicone rubber with hardness of 30 increased
by 45.9% whereas only 8.5% increase was observed for silicone
rubber with hardness of 50, indicating that silicone rubbers became
more durable in simulated solutions with the increase in hardness.
126 J. Feng et al. / Polymer Degradation and Stability 109 (2014) 122e128

Fig. 6. Variation of elastic modulus of silicone rubbers with different hardness after exposure to simulated solutions (a) and of silicone rubber with hardness of 40 after exposure to
different aqueous solutions (b). Solid lines are guide to eyes.

This phenomenon could be attributed to the increased degree of
cross-linking with the increase in hardness of silicone rubbers. Fig
6b shows the variation of elastic modulus of silicone rubber with
hardness of 40 in different solutions. It can be seen that the change
of elastic modulus of the tested material exposed to simulated so-
lution is slightly smaller than that exposed to acetic solution and is
much smaller than that exposed to strong acid solution. This could
be attributed to the possible dissolution of silicone rubbers in high
acidic solutions, particularly with the presence of Fþ in solutions.
Scanning electron microscopy (SEM) was applied to investigate
the surface morphology after degradation of silicone rubbers in
different solutions. Fig 7 displays the SEM images of silicone rub-
bers with different hardness before and after exposure to simulated
solution for 30 days. All initial samples have rather smooth surface
and no voids or cracks were observed. After degradation in simu-
lated solutions, voids appeared on surfaces of all the tested sam-
ples. Furthermore, both the size and number of voids increased
with the decrease in hardness, indicating that stability of silicone
rubbers increased with the increase in hardness. This agrees with
the above discussed variation of elastic modulus for silicone rub-
bers exposed to simulated solutions.
Fig 8 shows the surface morphology of silicone rubbers with
hardness of 40 exposed to different solutions. It can be clearly seen
that the corrosion of silicone rubbers became more severe with the
increase of acidity of exposed solutions. Even within 15 days, the
sample exposed to strong acid solution exhibits large voids with
diameter of about 10 mm and even cracks with length of about
several tens micrometers.
4. Conclusion
Degradation of silicone rubbers with different hardness in
various aqueous solutions at 80
C was studied. The solutions used
include de-ionized water, acetic acid, fuel cell environment simu-
lated solution, and strong acid. When exposed to acidic aqueous
solutions, silicone rubbers degrade through chemical decomposi-
tion of silicon based materials as well as leaching of fillers. With the
increase in exposure time in aqueous solutions, the degradation of
silicone rubbers becomes more severe. Since silicone rubber with
hardness of 50 has larger amount of fillers than those with hardness
of 30 and 40, it losses more weight than the other two samples
under the same conditions. However, both mechanical properties
and surface morphology results indicate that the silicone rubber
with hardness of 50 is more durable than silicone rubbers with
hardness of 30 and 40 in acidic aqueous solutions, suggesting that
the degradation of silicone rubbers should not be characterized
simply using weight loss measurements. As protons can catalyze
the decomposition of SieC and SieOeSi bonds, silicone rubbers
degraded severely in strong acid solutions, even leading to rela-
tively large cracks and voids on the surface.

Fig. 7. SEM images of silicone rubbers with hardness of 30 (a, b), 40 (c, d), and 50 (e, f) before (a, c, d) and after (b, d, f) exposed to simulated solutions.
 J. Feng et al. / Polymer Degradation and Stability 109 (2014) 122e128
Fig. 8. SEM images of silicone rubber with hardness of 40 after exposed to de-ionized water (a), acetic acid (b), simulated solution (c), and strong acid aqueous solution (d).
Acknowledgments
This work was supported by the Major State Basic Research
Development Program of China “973 Project” (Grant No.:
2012CB215504), the National Natural Science Foundation of China
(No. 51372192), the National Hi-Tech R&D Program of China
(2014AA052501), and Hubei Provincial Natural Science Foundation
of China (2013CFB339).
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