Mechanics of Materials 42 (2010) 678–685

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Mechanics of Materials
journal homepage: www.elsevier.com/locate/mechmat

Creep and stress-rupture of NafionÒ membranes under

controlled environment
Roham Solasi a,*, Xinyu Huang b,1, Kenneth Reifsnider c,2
a
Connecticut Global Fuel Cell Center, University of Connecticut, 44 Weaver Rd. Unit 5233, Storrs, CT 06269, United States
b
Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Rd., Cocoa, FL 32922-5703, United States
c
Department of Mechanical Engineering, University of South Carolina, 300 Main Street, Columbia, SC 29208, United States

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

Article history: NafionÒ as a polymer shows time-dependent behavior including creep and relaxation.
Received 2 April 2009 Application of this material in automotive fuel cells and targeted lifetimes require consid-
eration of time-dependent failure of NafionÒ in fuel cell design. In this work, creep tests for
NafionÒ were conducted in a controlled environment at different hydrations and temper-
Keywords: atures. Stress-rupture curves for NafionÒ were obtained for different hydrations (RH = 5%,
NafionÒ 50% and 90%) at room temperature and also for two different temperatures (25 °C & 80 °C)
Creep
at 50% relative humidity. Time-dependent failure was observed for all these conditions
Stress-rupture
Time-dependent failure
regardless of temperature and hydration level (state of water in NafionÒ). Ionic forces cre-
Fuel cell ated by cross linkings (by introducing water to membrane) do not seem to prevent disen-
Time–temperature-hydration parameter tanglements of the chains since there is no change in rate of time-dependent failure results.
A time-hydration/temperature equivalence method (Sherby–Dorn) is suggested as a
method to use short-term test data to estimate rupture times for other conditions.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction low electronic conductivity, good mechanical properties

NafionÒ consists of a hydrophobic polytetrafluoroethyl-
ene (PTFE, Teflon)-like backbone and hydrophilic acidic
sulfonic groups. Water absorption/desorption plays a criti-
cal role in Nafion’sÒ mechanical and electrochemical
behavior. Under humidified conditions, the hydrophilic
end groups segregate into nano-sized clusters, which im-
bibe water and cause swelling of the ionomer. Although
there are a variety of models to describe NafionÒ’s struc-
ture, it is still not very clear how that structure changes
in different environments. The microphase separated mor-
phology between the semi-crystalline hydrophobic matrix
and hydrophilic ionic cluster gives NafionÒ its unique com-
bination of properties such as: high proton conductivity,
* Corresponding author. Tel.: +1 860 748 6188; fax: +1 508 236 2349.
E-mail addresses: roham@engr.uconn.edu (R. Solasi), xhuang@fsec.uc-
f.edu (X. Huang), reifsnider@sc.engr.edu (K. Reifsnider).
1
Tel.: +1 321 638 1706; fax: +1 321 638 1010.
2
Tel.: +1 803 777 0084; fax: +1 803 777 0106.
and low gas permeability (Mauritz and Moore, 2004;
Banerjee and Curtin, 2004). The morphology and the ionic
conducting mechanisms of NafionÒ have been extensively
studied and more research is underway to understand
the micro/nano behavior of perfluorosulphonated
ionomers (Mauritz and Moore, 2004; Gebel, 2000; Gierke
et al., 1981; Rollet et al., 2002; Yeo and Eisenberg, 1977).
Based on the difference in geometry and distribution of
the water clusters in perfluorinated semi-crystalline ma-
trix of NafionÒ, different phenomenological models for its
morphology have been proposed. Existence of a network
of water clusters is consistent in all the suggested models.
These water clusters form interconnected acidic domains,
which are also thought to be the major path for proton
transport. Both the swelling and the proton conductivity
increase with the level of hydration (Zawodzinski et al.,
1991, 1993; Hinatsu et al., 1994; Morris and Sun, 1993;
Bauer et al., 2005). An extensive review about NafionÒ
and its unique properties has been prepared by Mauritz
and Moore (Mauritz and Moore, 2004).

0167-6636/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mechmat.2010.04.005
 R. Solasi et al. / Mechanics of Materials 42 (2010) 678–685
The most frequently cited model is the cluster-channel
model proposed by Hsu and Gierke which suggests an
equal distribution of sulfonate ion clusters in the fluorocar-
bon lattice (Hsu and Gierke, 1982). They further suggest
that short thermodynamically stable channels connect
adjacent water clusters. Phase inversion from the cluster-
channel structure to a connected network of polymer rod
like particles upon hydration is proposed by Gebel (2000)
using small angle scattering techniques. An elongated
polymeric aggregate model is suggested by Rubatat et al.
(2004) which suggests that water is not confined in spher-
ical cavities but between elongated fibrillar objects. Water
in NafionÒ is believed to be in three different states: non-
freezing water which is strongly bound to the polymer
chain, freezable loosely bound water which is weakly
bound to the polymer and free water that is not bound to
polymer and behaves like bulk water (Kim et al., 2003).
Weber and Newman (2003) modified the cluster-network
model and interpreted it as ionic clusters connected by
hydrophobic channels based on surface arguments and
experimental observations including Shroeder’s paradox.
They suggested that percolation of hydrophobic channels
occurs at a water content of k = 2 where water is mostly
bound water. As water content goes up (e.g k = 10), free
water becomes present in the hydrophilic channels (Weber
and Newman, 2003; Liu et al., 2006a).
By studying the tensile behavior and proton conductiv-
ity of NafionÒ, Liu et al. (2006a) proposed a three dimen-
sional bundle-cluster model that takes into account the
concepts of elongated polymer aggregates, nanophase-sep-
arated ionic clusters and also state of water in the polyelec-
trolyte membrane. Ionic water clusters separate the
aggregates which reduce the possibilities of crystallization
and interphase chains connect the bundle of aggregates.
Based on this model they proposed a hypothesis in order
to interpret the stress–strain uniaxial behavior of the
membrane which focuses on the bundle rotation before
yielding and chain disentanglement/reorientation after
yielding. They also interpreted strain rate dependence of
the material behavior and proton conductivity of the mem-
brane at different hydration levels using this model (Liu
et al., 2006a,b).
The mechanical behavior of NafionÒ is also known to be
a strong function of hydration (Liu et al., 2006a; Tang et al.,
2006; Satterfield et al., 2006; Bauer et al., 2005; Solasi
et al., 2007). This class of ionomers also shows time-depen-
dent behavior such as relaxation and creep which is ex-
pected from a polymer. It has been shown that stress-
relaxation of NafionÒ is highly influenced by introducing
water in the structure (Liu et al., 2006b; Kyu and Eisenberg,
1984; Solasi et al., 2008). Creep of the polymers is a time-
dependent increase in deformation under a constant load
which sometimes occurs even at room temperature. This
phenomenon in polyelectrolyte membranes in the fuel cell
can be associated with mechanical failure of the fuel cell
membranes. Stanic and Hoberecht (2004) identified two
different mechanisms of pinhole formation in the fuel cell
membranes by creep. The first mechanism included crack
formation and propagation whereas the second mecha-
nism was reduction of membrane thickness as a result of
creep until the membrane can no longer separate the reac-
679
tant gases. Creep in general brings out two main concerns
in engineering applications. One is excessive deformation
which, in the case of polyelectrolytes, can cause wrinkling
and therefore stress concentration and also thinning in the
membrane electrode assembly structure, and the other is
creep-rupture. For some polymers at certain (mostly high)
temperatures, creep deformation leads to fracture when
the polymer chains can no longer disentangle and accom-
modate the load. This fracture phenomenon because of
long-term creep of the material is referred to as ‘‘creep-
rupture” or ‘‘stress-rupture”. Ultimate failure may be pre-
ceded by shear yielding (necking), cracking, crazing and
in some cases can take place without any signs of warning.
The exact mechanism leading to eventual failure of poly-
mers is typically dependent on the degree of crystallinity
and entanglement of the polymer structure and could be
due to micro-crack and craze formation in the material
(Dowling, 1993).
In general, amorphous glassy polymers under tension
undergo two types of competing deformations: homoge-
neous ductile (non-cavitational) behavior with associated
shear deformation zones (SDZs) and cavitational processes
(resulting in crazing) that results either from chain scission
(CSC) or from chain disentanglement (CDC) Brule et al.,
2003; Zhou et al., 2006. Brule et al. (2003) have found that
entanglement density, molar mass, deformation rate, phys-
ical aging and specimen thickness are major factors govern-
ing competition between SDZs and CSC/CDCs. Transition
temperatures were established for conversion between
the deformation modes but nothing has been reported for
hydration dependence of the transition. Crazing is the fail-
ure mechanism for polymers that have entangled micro/
nanostructures (including NafionÒ), and is a known precur-
sor to crack formation (Rottler and Robbins, 2003). We have
observed in our previous investigations that crazing in Naf-
ionÒ can be introduced by cyclic hydration where creep
deformation could be a contributor to the so-called craze
formation (Huang et al., 2006). High entanglement density
polymers are resistant to craze formation and deform by
shear deformation. Crosslinking (physical or chemical)
has almost the same effect as increasing entanglement den-
sity. Therefore crazing can possibly be suppressed by cross-
linking or increasing the entanglement density (Zhou et al.,
2006; Kuo et al., 1985). Satterfield et al. (2006) conducted
creep tests on extruded NafionÒ (115) and NafionÒ/Tita-
nia(TiO2) composite membranes at room temperature. Naf-
ionÒ 115 crept approximately 40% more than the composite
membrane over a certain period of time under the same
stress. We suspect that this reported enhancement in creep
deformation of NafionÒ composite is due to introduction of
chemical crosslinkings (Titania particles) and as a result of
that, more difficult molecular disentanglement (and there-
fore crazing) in the polymer network.
The reduction of the crystallinity of NafionÒ compared
to its fully crystalline Teflon backbone is approximately
88–97% (Liu et al., 2006a). So far there is no evidence in
the literature that shows time-dependent failure of Naf-
ionÒ membrane as a semi-crystalline material. In this pa-
per creep and creep rupture behavior of membrane will
be characterized as a function of temperature and hydra-
tion; to date this dataset is not available in literature. These
680 R. Solasi et al. / Mechanics of Materials 42 (2010) 678–685
data can be used in a strength model for time-dependent
deformation and failure of the membrane under fuel cell
operating conditions. Currently, it is not clear whether in-
crease in water content which is believed to lead to fewer
but larger water clusters stops time-dependent failure
(crazing disentanglement) due to ionic forces and cross-
linking of the polymer chains or this second phase of soft
material makes the chain disentanglement and failure eas-
ier. Influence of water content and state of water on the
time-dependent failure of NafionÒ will be briefly discussed
in this work.
2. Experiment
Creep experiments have been conducted on dispersion-
cast NafionÒ NR111 (1 mil thickness) in the acid form (the
new generation of NR111 manufactured by DuPont is now
called NRE-211). Sharp scalpels and roller blades were
used to cut sample strips from sheet stocks. An environ-
ment chamber with independent relative humidity and
temperature control was used to reach different condi-
tions. Details of the environmental chamber have been
presented in our previous publications (Huang et al.,
2006; Yue, 2007). Sample gauge lengths were approxi-
mately 30 mm and the width of the samples was a quarter
of an inch. Constant load was applied by applying a dead
weight to one side of the specimen with a nylon fishing
string while the other side was connected to a load cell
by a rod. The nylon string was passed through pulleys
and a plastic container was attached to it. Different loads
are applied by adding steel shot to the plastic container.
In order to keep the grips aligned frictionless Teflon block
was used to elevate the side that was connected to the
string and make it align with the grip connected to the load
cell. The friction caused by the Teflon block and two pul-
leys did not show any significant effect on the value of
the load applied to the specimen.
Displacement (creep) of the specimen was measured by
attaching an LVDT to the bottom of the plastic container
and the data were recorded with a computer using Lab-
View software. Whenever the sample broke during a creep
test, the plastic bottle was detached from the sample and
the LDVT recorded a jump in the displacement (voltage).
Fig. 1. (a) Picture of the creep setup along with the environment chamber and (b) schematics of the creep testing setup.
The recorded time corresponding to this jump in recorded
voltage data marked the time-to-failure (time-to-rupture)
of the specimen. After the required condition was reached
in the environment chamber, the sample was mounted in a
stress-free fashion for half an hour before starting the
creep test to make sure it was in equilibrium with the envi-
ronment. Creep displacement and time were recorded after
the specified load was applied quasi-statically and the
sample was in tension because of the initial load. Fig. 1
shows the different parts of the creep testing equipment
along with the environmental chamber.
3. Creep and creep rupture results
Creep tests on NafionÒ111 were done at room temper-
ature (T = 25 °C) for three different relative humidity levels
(RH = 5%, 50% and 90%). They were also conducted at two
different temperatures (T = 25 °C and 80 °C) at a constant
relative humidity (RH = 50%). Fig. 2 shows the creep curves
at room condition for different stress levels (loads). Fig. 3
demonstrates the typical creep behavior of NafionÒ at
room temperature for three different relative humidities.
Stress-rupture (creep-rupture) data for NafionÒ111 at
room temperature for different relative humidities (hydra-
tions) are shown in Fig. 4. Stress-rupture data for a con-
stant hydration (RH = 50%) at temperatures of T = 25 °C
1.6
σ=11.4 MPa
1.4
σ=9.7 MPa
1.2 σ=7.85 MPa
σ=8.2 MPa
1 σ=6.7 MPa
Strain
0.8
0.6
0.4
0.2
0
0 10000 20000 30000 40000 50000
Time (s)
Fig. 2. Creep curves for NafionÒ111 at room condition (T = 25 °C and
RH = 50%).
 R. Solasi et al. / Mechanics of Materials 42 (2010) 678–685 681

1.6 and 80 °C were obtained for a different batch of Naf-

1.4 RH=5% (σ=15.7 MPa)
ionÒ111 and are shown in Fig. 5. In general, the mechanical
properties of NafionÒ are slightly different from batch to
1.2 RH=90% (σ=6.8 MPa)
batch. Therefore, it is better to compare results from the
1
Strain

RH=50% (σ=6.7 MPa) same batch of material. Unfortunately data reported in

0.8 Figs. 4 and 5 are from different batches of NafionÒ; there-
0.6 fore the room temperature results are not identical.
0.4 Creep in polymers is generally in the form of viscous
creep (Dowling, 1993). When stress is applied to an amor-
0.2
phous solid, polymer chains slide relative to one another in
0
a time-dependent manner resulting in creep deformation.
0 10000 20000 30000 40000 50000 60000 70000
Such molecular motion which is a form of diffusional flow
Time (s)
is enhanced when temperature rises. Hence, creep be-
Fig. 3. Example of creep curves at room temperature for different comes more significant in temperatures higher than the
hydrations. glass transition temperature (Tg) of the polymer where

30

25
y = -1.2385Ln(x) + 26.622
R2 = 0.9355
20 RH=50%
RH=5%
Stress (MPa)

RH=90%
15
Log. (RH=50%)
y = -1.4871Ln(x) + 22.392 Log. (RH=5%)
10 R2 = 0.9682 Log. (RH=90%)

5 y = -1.4648Ln(x) + 21.4
R2 = 0.9491

0
1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05
Time (s)
Ò
Fig. 4. Stress-rupture of Nafion 111 at room temperature for various relative humidity (water content: k): RH = 5% (k = 0.8), RH = 50% (k = 3.5) and
RH = 90% (k = 10).

25

20

y = -1.0566Ln(x) + 19.161
Stress (Mpa)

15 R2 = 0.8033 T=25 C
T=80 C
Log. (T=25 C)
10 Log. (T=80 C)

y = -1.1022Ln(x) + 12.985
5 R2 = 0.9082

0
1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05
Time (s)

Fig. 5. Stress-rupture of NafionÒ111 at 50% relative humidity for 25 °C and 80 °C temperatures.

682 R. Solasi et al. / Mechanics of Materials 42 (2010) 678–685
the material behavior becomes more rubbery. Chemical
bonding in the direction of chains or networks is strong,
but adjacent chains are bonded sideways only by weak
secondary Van der Waal or hydrogen bonding. Creep
mechanisms are due to various complex motions and
interactions of the long chain-like molecules in the struc-
ture of the polymer. However, sliding of the molecular
chains gets more difficult when they are easily entangled.
Entanglements in the chain-like structure of polymers
causes creep resistance or even recovery. Any obstacle in
the micro-structure has the same effect as entanglements
and limits creep. These obstacles could be bulky side
groups or cross-linking.
From Fig. 4 it can be seen that creep-rupture curves at dif-
ferent hydrations are roughly parallel to each other. It can be
concluded that time-dependent failure in NafionÒ is due to
the same creep mechanism that does not change by changes
in the moisture level of the membrane. Hydration level just
changes the time-to-rupture at different stress levels. This
observation can suggest a consistent disentanglement
mechanism for different hydrations. Therefore, ionic forces
created by cross linkings (e.g., by introducing water to the
membrane) do not seem to prevent disentanglements of
the chains since there is no change in the rate of time-depen-
dent failure results. The same behavior is also observed for
failure of NafionÒ at different service temperatures as two
stress-rupture curves at constant relative humidity of 50%
shown in Fig. 5 are parallel to each other as well.
The creep phenomenon in polymers is a thermally acti-
vated mechanism (Dowling, 1993). The rate of a thermally
activated process is governed by an Arrhenius equation,
Eq. (1):
Q
e_ ¼ AðrÞe RT ð1Þ
where dote is strain rate, T is temperature, Q is activation
energy, and A is a material constant that depends on the le-
vel of stress applied to the material. The proportionality of
strain rate and stress is known to be a key feature of creep
due to viscous flow. Activation energy, Q, is a measure of
the energy barrier that must be overcome for relative mo-
tion of the chains to occur. This quantity is ideally constant
unless the mechanism of creep changes due to changes in
temperature or changes in the molecular structure of the
material. For Q in units of calories/mole and temperature
T in Kelvin, the quantity R  2 is the universal gas constant
in units of cal/(K mole). In the reminder of this paper, the
quantity R will be included in the activation energy and
we rewrite Eq. (1) in the following form:
Q
e_ ¼ AðrÞe T ð2Þ
Ò
In the case of the Nafion membrane, besides the temper-
ature, hydration also serves as an independent field vari-
able. Such a situation is a case of hygro-thermal
activation instead of solely thermal activation. One can
attribute two different activation energies to creep behav-
ior of the material: thermal and hydration (humidity/mois-
ture) activation energies. Then we can rewrite Eq. (2)
which is the rate of a thermally activated process in the fol-
lowing form as rate of a hygro-thermally activated process:
Q T Q k
e_ ¼ AðrÞe T e k ð3Þ
QT and Qk are activation energies associated with creep dri-
ven by temperature and hydration of NafionÒ, respectively.
It must be noted that even though we used the same nota-
tion for these two physical constants they obviously do not
have the same units. But since they are from the same gen-
eral nature and indicate a measure of energy barrier
against molecular motion in the polymer we are referring
to them as activation energies. k is water content of Naf-
ionÒ (the number of water molecules per sulfonic acid site)
which was used as a field variable instead of water activity
(relative humidity). RH (relative humidity or water activ-
ity, a) is a parameter determined by the environment,
whereas k is a direct measurement of the material water
content; in addition, k has a linear and one-to-one correla-
tion with the membrane expansion or shrinkage, including
the range where k is between 14 and 22 (Morris and Sun,
1993). In reality, the membrane loses water gradually
when changing from a liquid hydrated state to a saturated
vapor state. The k parameter captures the absolute amount
of water in the membrane during such changes, but the RH
parameter cannot capture those changes, partly because of
Schroeder’s paradox, the difference in water uptake due to
the type of reservoir in contact with the membrane (Za-
wodzinski et al., 1993; Weber and Newman, 2003; Choi
and Datta, 2003). According to this phenomenon water up-
take into the polymer membrane from saturated vapor
phase (14 at room temperature) is lower than the water
uptake from the liquid phase (22 at room temperature)
even though water activity in either case is the same
(100% relative humidity, water activity = 1). Eqs. (4) and
(5) can be used to relate k (water content) to relative
humidity (water activity, a) when water uptake is from
the saturated vapor phase (Hinatsu et al., 1994; Springer
et al., 1991).
@ T ¼ 25  C : k ¼ 0:043 þ 17:81a  39:85a2 þ 36:0a3 ð4Þ
@ T ¼ 80  C : k ¼ 0:300 þ 10:8a  16:0a2 þ 14:1a3 ð5Þ
p
a¼
po
where k is water content, a is water activity (relative
humidity), p is water vapor pressure and po is saturation
water-vapor pressure at the temperature of the experi-
ment. In order to get stress-rupture results for the liquid
phase, creep tests must be done with the membrane spec-
imen submerged in water. This can be done by designing a
temperature controlled water bath for the specimen. Such
tests were not conducted as part of this work.
4. Time–temperature-hydration equivalence for stress-
rupture
In engineering design of fuel cells, membrane failure
can be linked to a combination of different phenomena
including chemical degradation as a result of peroxide rad-
ical attacks, mechanical fatigue due to cyclic hydration and
stress-rupture (Huang et al., 2006). Currently, service life
targets for automotive fuel cells are 5000 h over a wide
range of temperatures (Uni, 2006). Creep and creep-rup-
 R. Solasi et al. / Mechanics of Materials 42 (2010) 678–685 683

ture effects in the membranes during service life of the fuel
cells must be taken into account for various temperature
and hydration conditions. The use of time–temperature
8 y = 2.4406x + 4.5105
R2 = 0.9937
7 σ=5 MPa
6 y = 2.1826x + 3.0858

log tr, log (s)

parameters has been widely used to estimate the long- σ=10 MPa
R2 = 0.9961

term behavior of the material based on the data from rela- 5

tively short time tests but at higher service temperatures 4 y = 1.9246x + 1.6612
σ=15 MPa R2 = 0.9983
(Dowling, 1993). Based on Eq. (3) for creep of NafionÒ, 3
the Sherby–Dorn (S–D) approach was used for this type 2 y = 1.6666x + 0.2366
σ=20 MPa R2 = 0.9998
of membrane. A key assumption is that the activation en-
1
ergy for creep is constant at different conditions. This
means that there is no change in the creep-mechanism 0
0 0.5 1 1.5
when the environment (temperature or hydration) 1/λ
changes.
First we consider the case with constant room temper- Fig. 6. Graphical interpretation for the Sherby–Dorn parameter at
ature and various hydrations shown in Fig. 4. Eq. (3) can be constant temperature (T = 25 °C). Slope of the parallel lines is hydration
activation parameter, Qk.
reformulated in the following form:
Q k
e_ ¼ A0 ðr; TÞek ð6Þ
25
0
The coefficient (A ) is a function of stress and temperature. 20

Stress, MPa
By integrating Eq. (6) we arrive at:
15
Q k
e ¼ A0 ðr; TÞte k ¼ A0 # k ð7Þ 10

#k is hydration-compensated time. Eq. (7) suggests that for 5

a constant stress and temperature, creep strains form a un-
0
ique curve if plotted versus #k. Therefore strain-to-break 0 1 2 3 4 5
(rupture strain) is constant for a given value of hydra- PSD, Sherby-Dorn Parameter, log (s)
tion-compensated time to break (#k;r ). The Sherby–Dorn
parameter is defined by taking the logarithm of #k;r where Fig. 7. Hydration Sherby–Dorn parameter at different stress levels for
time is t = tr: creep-rupture of NafionÒ111 at room-temperature.
 
1
P SD ¼ log #k;r ¼ log t r  Q k ð8Þ
k 9
y = 100.34x + 3.8622
Values for hydration activation energy Qk can be obtained 7 σ=0 MPa
y = 97.248x + 1.9307
log tr , log (s)

by plotting creep-rupture data shown in Fig. 4 as a loga-

5 σ=5 MPa
rithm of time-to-rupture (log tr) versus inverse of water y = 94.156x - 0.0008
content (1/k) which are illustrated in Fig. 6 as parallel lines 3 σ=10 MPa
for different stress values. The Sherby–Dorn parameter for y = 91.064x - 1.9323
1 σ=15 MPa
each stress is the intercept with the y-axis and Qk is the
slope of the constant-stress lines. Calculated hydration -1
Sherby–Dorn parameters (PSD) at room temperature for
-3
different stress levels are demonstrated in Fig. 7 where 0 0.01 0.02 0.03 0.04 0.05
data for all stresses and hydrations fall together along a 1/T, (1/C)
single curve. Having values for activation energy, the Sher-
by–Dorn parameter as a function of stress, and using Eq. Fig. 8. Graphical interpretation for the Sherby–Dorn parameter at
(8) we can estimate the long-term creep behavior and rup- constant relative humidity (50%). Slope of the parallel lines is tempera-
ture activation parameter, QT.
ture of the dry membrane by running a relatively shorter
time creep test for a more hydrated condition.
The same concept can be applied to changes in temper- 20
ature instead of hydration by reformulating Eq. (3) in order
Stress, MPa

to find temperature compensated time (#T ) as follows: 15

Q T
e ¼ A00 ðr; TÞte T ¼ A00 #T ð9Þ 10
 
1 5
P SD ¼ log #T;r ¼ log tr  Q T ð10Þ
T
0
#T;r is temperature-compensated time when time is t = tr. -3 -1 1 3 5
Figs. 8 and 9 illustrate the Sherby–Dorn parameter defini- PSD, Sherby-Dorn Parameter, log(s)
tion at 50% relative humidity for two different tempera-
tures. The slope of the log tr versus inverse of hydration Fig. 9. Hydration Sherby–Dorn parameter at different stress levels for
and temperature curves which denotes activation energy creep-rupture of NafionÒ111 at 50% relative humidity.
684 R. Solasi et al. / Mechanics of Materials 42 (2010) 678–685
in Figs. 4 and 6 is constant. The constant activation energy
is the basic assumption in order to use the Sherby–Dorn
time-hydration-temperature equivalence method. Other-
wise, other methods such as Larson–Miller (L–M) and
Manson–Haferd (M–H) approaches must be used (Dow-
ling, 1993).
A more general definition of temperature-hydration-
compensated time #kT is also possible by integrating Eq.
(3):
Q k Q T
e ¼ AðrÞte k e T ¼ A#kT ð11Þ
   
1 1
PSD ¼ log #kT;r ¼ log t r  Q k  QT ð12Þ
k T
By introducing Eq. (12) a 3-D representation of log tr versus
inverse of T and k can be plotted. In this way the Sherby–
Dorn parameter for any given stress, hydration and tem-
perature can be obtained. Since experimental data re-
ported in Figs. 4 and 5 are from different batches of
NafionÒ, this more general form of temperature-hydration
equivalence will not be reported here.
5. Discussion and conclusion
Time-dependent failure for NafionÒ has been observed
under different hydration and temperature environments.
For a range of hydrations (vapor-phase) and temperatures,
when subjected to a constant load, NafionÒ deformed to
the point of rupture. There was no evidence of visible neck-
ing at the fracture region in any of the conditions tested. It
appears that the movement of chains and therefore their
disentanglement, results in the rupture of the material
after a certain time. The stress-rupture data of NafionÒ
suggest that there is no change in the creep mechanism
(crazing and micro-void formation in this case) of the
membrane over a wide range of hydrations (from close to
zero to a water content of 10 at room temperature).
As stated earlier, it is not clear whether the existence of
water clusters in the hydrated NafionÒ (which are softer
compared to the polymer backbone) makes disentangle-
ment creep of the molecular chains easier or if these water
molecules work as barriers against chain slippage and inhi-
bit disentanglement and the eventual rupture. As it turns
out from this work, for the range of hydrations for which
our creep-rupture tests were conducted, the water content
does not change the time-dependent nature of the failure.
However it seems that dependence of creep deformation
on hydration is stronger when the membrane is in a nearly
dry state. From Fig. 4 as hydration goes up and water clus-
ters form in the membrane (between k = 3 and k = 10)
stress-rupture curves get closer and creep behavior is al-
most the same with change in hydration. As mentioned be-
fore, the state of water in the membrane changes from
bound water to bulk-like free water as it gets humidified
from a dry state. This could explain the vertical shift in
stress-rupture curves from a dry state (k = 0.8) to the
humidified phase (k = 3.5–10) shown in Fig. 4. Bulk free
water seems to accelerate the rupture behavior compared
to loosely and tightly bound water but even at those dry
states, where there is no free water; the membrane still
shows time-dependent rupture with the same trend but
with some greater delay. More (underwater) creep experi-
ments at higher water contents (k > 14) could possibly por-
tray a better picture to relate state of water to time-
dependent failure of NafionÒ.
Consistency of the rupture mechanisms has also been
observed at different temperatures for a constant hydra-
tion which implies that temperature shift also does not
change the rupture behavior. The creep behavior of poly-
mers is known to be complicated at intermediate temper-
atures where the behavior is rubbery (slightly above Tg).
For a crystalline thermoplastic polymer at temperatures
above Tg, secondary bonds between carbon-based molecu-
lar chains are weak and chain sliding and disentanglement
which can eventually lead to rupture are expected. For the
case of NafionÒ membranes, which are semi-crystalline
polymers, one would also expect to see the time-depen-
dent failure at higher temperatures (above Tg). But it was
observed as part of this work that time-dependent failure
happens at even room temperature. It should be noted that
the glass transition temperature of NafionÒ in the litera-
ture has been reported to be around 100 °C (Mauritz and
Moore, 2004; Physical Properties for Nafion, 2003). Assum-
ing this Tg of approximately 100 °C stress-rupture is unli-
kely to happen. Recently it was suggested that on-set of
thermally activated main chain motion should be assigned
to the beta-relaxation (Tb  20 °C) as supported by DMA
and SAXS evidence. This beta relaxation is assigned to
the Tg of NafionÒ (Page et al., 2005). Our stress-rupture
data appear to support the new Tg assignment.
From our observations, even at stress levels consider-
ably lower than the yield stress (15–50% ry), creep defor-
mation will continuously progress with a constant rate
after its initial (primary creep) phase till final rupture.
These stress-rupture phenomena occur regardless of the
temperature and hydration in the range we experimented.
At lower temperature and drier conditions, the stress-rup-
ture process proceeds more slowly. Stress-rupture can be
an engineering concern especially when the constrained
fuel cell membrane stays in an overly dry (tensile stress)
state for a long period of time. Therefore, excessive defor-
mation and possible long-term rupture have to be ac-
counted for in engineering design of automotive fuel cell
membranes even at dry conditions; even though the mem-
brane in an operating fuel cell is always hydrated. In order
to get around test-time limitations, a time-equivalence
method is required to estimate the long time creep behav-
ior. Based on the stress-rupture results for different hydra-
tions and temperatures in this work, Sherby–Dorn time-
hydration/temperature parameters have been successfully
obtained for this purpose. This equivalence method can be
used to estimate the creep behavior at other conditions
based on the short-time creep data at higher temperatures
and hydrations.
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