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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

Connecticut Global Fuel Cell Center, University of Connecticut, 44 Weaver Rd. Unit 5233, Storrs, CT 06269, United States 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
NafionÒ as a polymer shows time-dependent behavior including creep and relaxation. Application of this material in automotive fuel cells and targeted lifetimes require consideration 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 temperatures. Stress-rupture curves for NafionÒ were obtained for different hydrations (RH = 5%, 50% and 90%) at room temperature and also for two different temperatures (25 °C & 80 °C) at 50% relative humidity. Time-dependent failure was observed for all these conditions regardless of temperature and hydration level (state of water in NafionÒ). Ionic forces created by cross linkings (by introducing water to membrane) do not seem to prevent disentanglements 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.

Article history: Received 2 April 2009

Keywords: NafionÒ Creep Stress-rupture Time-dependent failure Fuel cell Time–temperature-hydration parameter

1. Introduction NafionÒ consists of a hydrophobic polytetrafluoroethylene (PTFE, Teflon)-like backbone and hydrophilic acidic sulfonic groups. Water absorption/desorption plays a critical role in Nafion’sÒ mechanical and electrochemical behavior. Under humidified conditions, the hydrophilic end groups segregate into nano-sized clusters, which imbibe water and cause swelling of the ionomer. Although there are a variety of models to describe NafionÒ’s structure, it is still not very clear how that structure changes in different environments. The microphase separated morphology between the semi-crystalline hydrophobic matrix and hydrophilic ionic cluster gives NafionÒ its unique combination 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.ucf.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. 0167-6636/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.mechmat.2010.04.005

low electronic conductivity, good mechanical properties 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 matrix 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).

2006b. NafionÒ 115 crept approximately 40% more than the composite membrane over a certain period of time under the same stress. Ionic water clusters separate the aggregates which reduce the possibilities of crystallization and interphase chains connect the bundle of aggregates.. This phenomenon in polyelectrolyte membranes in the fuel cell can be associated with mechanical failure of the fuel cell membranes. 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..R. High entanglement density polymers are resistant to craze formation and deform by shear deformation. (2006) conducted creep tests on extruded NafionÒ (115) and NafionÒ/Titania(TiO2) composite membranes at room temperature. Liu et al. These . An elongated polymeric aggregate model is suggested by Rubatat et al. 2008). can cause wrinkling and therefore stress concentration and also thinning in the membrane electrode assembly structure.. Bauer et al. Tang et al. molar mass. This fracture phenomenon because of long-term creep of the material is referred to as ‘‘creeprupture” or ‘‘stress-rupture”. 2006.. Creep of the polymers is a timedependent increase in deformation under a constant load which sometimes occurs even at room temperature.. Kuo et al.. (2006a) proposed a three dimensional bundle-cluster model that takes into account the concepts of elongated polymer aggregates. / Mechanics of Materials 42 (2010) 678–685 679 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 fluorocarbon lattice (Hsu and Gierke. 2006. They also interpreted strain rate dependence of the material behavior and proton conductivity of the membrane at different hydration levels using this model (Liu et al. Water in NafionÒ is believed to be in three different states: nonfreezing water which is strongly bound to the polymer chain... deformation rate.. crazing and in some cases can take place without any signs of warning. 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. 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. and is a known precursor to crack formation (Rottler and Robbins. They further suggest that short thermodynamically stable channels connect adjacent water clusters.. in the case of polyelectrolytes. cracking.g k = 10). 2003). Kyu and Eisenberg. to date this dataset is not available in literature. The reduction of the crystallinity of NafionÒ compared to its fully crystalline Teflon backbone is approximately 88–97% (Liu et al. We have observed in our previous investigations that crazing in NafionÒ can be introduced by cyclic hydration where creep deformation could be a contributor to the so-called craze formation (Huang et al. So far there is no evidence in the literature that shows time-dependent failure of NafionÒ membrane as a semi-crystalline material. Brule et al. By studying the tensile behavior and proton conductivity of NafionÒ. 2006a. physical aging and specimen thickness are major factors governing competition between SDZs and CSC/CDCs. more difficult molecular disentanglement (and therefore crazing) in the polymer network. In general. This class of ionomers also shows time-dependent behavior such as relaxation and creep which is expected from a polymer. Transition temperatures were established for conversion between the deformation modes but nothing has been reported for hydration dependence of the transition.b). Liu et al. They suggested that percolation of hydrophobic channels occurs at a water content of k = 2 where water is mostly bound water. free water becomes present in the hydrophilic channels (Weber and Newman. 2006. 2006a. As water content goes up (e.. 2003. 2007). Phase inversion from the clusterchannel structure to a connected network of polymer rod like particles upon hydration is proposed by Gebel (2000) using small angle scattering techniques. One is excessive deformation which. It has been shown that stressrelaxation of NafionÒ is highly influenced by introducing water in the structure (Liu et al. Therefore crazing can possibly be suppressed by crosslinking or increasing the entanglement density (Zhou et al. creep deformation leads to fracture when the polymer chains can no longer disentangle and accommodate the load. For some polymers at certain (mostly high) temperatures.. Satterfield et al. Crosslinking (physical or chemical) has almost the same effect as increasing entanglement density. 2005. 1984.. amorphous glassy polymers under tension undergo two types of competing deformations: homogeneous 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) have found that entanglement density. Solasi et al.. The exact mechanism leading to eventual failure of polymers 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. 2006a). In this paper creep and creep rupture behavior of membrane will be characterized as a function of temperature and hydration. Zhou et al. and the other is creep-rupture. 2006a). (2004) which suggests that water is not confined in spherical cavities but between elongated fibrillar objects.. Ultimate failure may be preceded by shear yielding (necking).. The first mechanism included crack formation and propagation whereas the second mechanism was reduction of membrane thickness as a result of creep until the membrane can no longer separate the reac- tant gases. Solasi et al. 2003. 2006. Satterfield et al. 1993). 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. nanophase-separated ionic clusters and also state of water in the polyelectrolyte membrane. The mechanical behavior of NafionÒ is also known to be a strong function of hydration (Liu et al. Creep in general brings out two main concerns in engineering applications. Solasi et al. 2006). 1982). 1985). Crazing is the failure mechanism for polymers that have entangled micro/ nanostructures (including NafionÒ). Stanic and Hoberecht (2004) identified two different mechanisms of pinhole formation in the fuel cell membranes by creep.

6 1..680 R.8 0. . Solasi et al. The nylon string was passed through pulleys and a plastic container was attached to it. 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 LabView software. 3. 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 recorded time corresponding to this jump in recorded voltage data marked the time-to-failure (time-to-rupture) of the specimen. Influence of water content and state of water on the time-dependent failure of NafionÒ will be briefly discussed in this work. 1.7 MPa σ=8.4 MPa σ=9. 50% and 90%). 3 demonstrates the typical creep behavior of NafionÒ at room temperature for three different relative humidities. Different loads are applied by adding steel shot to the plastic container. 2 shows the creep curves at room condition for different stress levels (loads). An environment chamber with independent relative humidity and temperature control was used to reach different conditions. / 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. 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 environment. Fig. 2006. 1. Fig. the plastic bottle was detached from the sample and the LDVT recorded a jump in the displacement (voltage). Creep and creep rupture results Creep tests on NafionÒ111 were done at room temperature (T = 25 °C) for three different relative humidity levels (RH = 5%. Sample gauge lengths were approximately 30 mm and the width of the samples was a quarter of an inch. Creep curves for NafionÒ111 at room condition (T = 25 °C and RH = 50%).2 0 0 10000 20000 30000 40000 50000 Time (s) Fig. Stress-rupture data for a constant hydration (RH = 50%) at temperatures of T = 25 °C 2. 4.4 1. Fig.2 σ=11. 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.4 0. 1 shows the different parts of the creep testing equipment along with the environmental chamber.85 MPa σ=6. The friction caused by the Teflon block and two pulleys did not show any significant effect on the value of the load applied to the specimen. 2. (a) Picture of the creep setup along with the environment chamber and (b) schematics of the creep testing setup. Currently. After the required condition was reached in the environment chamber. 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. They were also conducted at two different temperatures (T = 25 °C and 80 °C) at a constant relative humidity (RH = 50%). it is not clear whether increase 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 crosslinking of the polymer chains or this second phase of soft material makes the chain disentanglement and failure easier. 2007).6 0. Experiment Creep experiments have been conducted on dispersioncast NafionÒ NR111 (1 mil thickness) in the acid form (the new generation of NR111 manufactured by DuPont is now called NRE-211). Fig. Whenever the sample broke during a creep test.2 MPa σ=7. Yue.7 MPa Strain 1 0. Stress-rupture (creep-rupture) data for NafionÒ111 at room temperature for different relative humidities (hydrations) are shown in Fig. Sharp scalpels and roller blades were used to cut sample strips from sheet stocks. Details of the environmental chamber have been presented in our previous publications (Huang et al.

(RH=90%) Stress (MPa) 5 y = -1.E+00 1.E+05 Time (s) Fig.4648Ln(x) + 21. . Solasi et al. therefore the room temperature results are not identical.E+03 1.8033 Stress (Mpa) 15 10 y = -1. 4 and 5 are from different batches of NafionÒ.8 0.9355 20 15 y = -1. Ò 25 20 y = -1. the mechanical properties of NafionÒ are slightly different from batch to batch. When stress is applied to an amorphous solid.9491 0 1.2 1 0.2 0 0 10000 20000 30000 40000 50000 60000 70000 RH=5% (σ=15.E+00 1. 5.E+05 Time (s) Fig.8).2385Ln(x) + 26.E+01 1.E+02 1.E+01 1.9682 10 RH=50% RH=5% RH=90% Log. (RH=5%) Log.7 MPa) RH=90% (σ=6.5) and RH = 90% (k = 10). 4.E+03 1.E+04 1.9082 T=25 C T=80 C Log.8 MPa) RH=50% (σ=6. it is better to compare results from the same batch of material.622 R2 = 0. (T=25 C) Log. Hence.6 0. (RH=50%) Log. Therefore. Unfortunately data reported in Figs.4 R2 = 0.0566Ln(x) + 19. Creep in polymers is generally in the form of viscous creep (Dowling. 1993). (T=80 C) 5 0 1. Example of creep curves at room temperature for different hydrations. creep becomes more significant in temperatures higher than the glass transition temperature (Tg) of the polymer where Strain 30 25 y = -1.7 MPa) Time (s) Fig.R.1022Ln(x) + 12.E+04 1. polymer chains slide relative to one another in a time-dependent manner resulting in creep deformation.4871Ln(x) + 22.392 R2 = 0. RH = 50% (k = 3. / Mechanics of Materials 42 (2010) 678–685 681 1. Stress-rupture of NafionÒ111 at 50% relative humidity for 25 °C and 80 °C temperatures. Such molecular motion which is a form of diffusional flow is enhanced when temperature rises.E+02 1. In general.6 1. and 80 °C were obtained for a different batch of NafionÒ111 and are shown in Fig.985 R2 = 0. 5. 3.161 R2 = 0.4 0.4 1. Stress-rupture of Nafion 111 at room temperature for various relative humidity (water content: k): RH = 5% (k = 0.

but adjacent chains are bonded sideways only by weak secondary Van der Waal or hydrogen bonding. and A is a material constant that depends on the level of stress applied to the material. 4 it can be seen that creep-rupture curves at different hydrations are roughly parallel to each other. 1993. Eqs. a is water activity (relative humidity). but the RH parameter cannot capture those changes. (1): _ e ¼ AðrÞe T e ÀQ T ÀQ k k ð3Þ _ e ¼ AðrÞe RT ÀQ ð1Þ where dote is strain rate. ionic forces created by cross linkings (e. a) when water uptake is from the saturated vapor phase (Hinatsu et al. Any obstacle in the micro-structure has the same effect as entanglements and limits creep. It must be noted that even though we used the same notation for these two physical constants they obviously do not have the same units. 2006). Entanglements in the chain-like structure of polymers causes creep resistance or even recovery. RH (relative humidity or water activity. the difference in water uptake due to the type of reservoir in contact with the membrane (Zawodzinski et al. water activity = 1). Such a situation is a case of hygro-thermal activation instead of solely thermal activation. k is water content of NafionÒ (the number of water molecules per sulfonic acid site) which was used as a field variable instead of water activity (relative humidity). Q is activation energy. The rate of a thermally activated process is governed by an Arrhenius equation. Springer et al. Such tests were not conducted as part of this work. membrane failure can be linked to a combination of different phenomena including chemical degradation as a result of peroxide radical attacks. in addition. 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. 4. Creep and creep-rup- In the case of the Nafion membrane.g. Therefore. 2003). whereas k is a direct measurement of the material water content. 1994. hydration also serves as an independent field variable. Currently. the membrane loses water gradually when changing from a liquid hydrated state to a saturated vapor state. k has a linear and one-to-one correlation with the membrane expansion or shrinkage. is a measure of the energy barrier that must be overcome for relative motion of the chains to occur. service life targets for automotive fuel cells are 5000 h over a wide range of temperatures (Uni. According to this phenomenon water uptake 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. Creep mechanisms are due to various complex motions and interactions of the long chain-like molecules in the structure of the polymer. the quantity R $ 2 is the universal gas constant in units of cal/(K mole).. But since they are from the same general nature and indicate a measure of energy barrier against molecular motion in the polymer we are referring to them as activation energies. Solasi et al. 2006). mechanical fatigue due to cyclic hydration and stress-rupture (Huang et al. @ T ¼ 25  C : k ¼ 0:043 þ 17:81a À 39:85a2 þ 36:0a3 ð4Þ @ T ¼ 80  C : k ¼ 0:300 þ 10:8a À 16:0a2 þ 14:1a3 p a¼ po ð5Þ _ e ¼ AðrÞe T ÀQ ð2Þ Ò where k is water content. a) is a parameter determined by the environment.682 R.. In order to get stress-rupture results for the liquid phase. 5 are parallel to each other as well. including the range where k is between 14 and 22 (Morris and Sun. This can be done by designing a temperature controlled water bath for the specimen. besides the temperature. For Q in units of calories/mole and temperature T in Kelvin. In reality. / Mechanics of Materials 42 (2010) 678–685 the material behavior becomes more rubbery. Chemical bonding in the direction of chains or networks is strong. (1) in the following form: QT and Qk are activation energies associated with creep driven by temperature and hydration of NafionÒ. (4) and (5) can be used to relate k (water content) to relative humidity (water activity. 1993). Hydration level just changes the time-to-rupture at different stress levels. Time–temperature-hydration equivalence for stressrupture In engineering design of fuel cells. Then we can rewrite Eq. Weber and Newman. partly because of Schroeder’s paradox. In the reminder of this paper. One can attribute two different activation energies to creep behavior of the material: thermal and hydration (humidity/moisture) activation energies. However. The proportionality of strain rate and stress is known to be a key feature of creep due to viscous flow. This observation can suggest a consistent disentanglement mechanism for different hydrations. These obstacles could be bulky side groups or cross-linking. creep tests must be done with the membrane specimen submerged in water. 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. 1993). The k parameter captures the absolute amount of water in the membrane during such changes. The creep phenomenon in polymers is a thermally activated mechanism (Dowling.. sliding of the molecular chains gets more difficult when they are easily entangled. Q. T is temperature. 1991). 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... Eq. 2003. the quantity R will be included in the activation energy and we rewrite Eq. p is water vapor pressure and po is saturation water-vapor pressure at the temperature of the experiment. Activation energy. Choi and Datta. (2) which is the rate of a thermally activated process in the following form as rate of a hygro-thermally activated process: . respectively. 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-dependent failure results. From Fig.

r ).r where time is t = tr: PSD.1826x + 3.r ¼ log t r À Q k   1 k ð8Þ 9 7 σ=0 MPa σ=5 MPa σ=10 MPa σ=15 MPa y = 100. Hydration Sherby–Dorn parameter at different stress levels for creep-rupture of NafionÒ111 at 50% relative humidity.9998 σ=20 MPa 1. The slope of the log tr versus inverse of hydration and temperature curves which denotes activation energy PSD.8622 y = 97.04 0.0008 y = 91. (3) can be reformulated in the following form: 8 7 σ=5 MPa log tr. 8 and 9 illustrate the Sherby–Dorn parameter definition at 50% relative humidity for two different temperatures. and using Eq. / Mechanics of Materials 42 (2010) 678–685 683 y = 2.34x + 3. TÞte ÀQ k k ¼ A0 # k ð7Þ #k is hydration-compensated time. 4 as a logarithm of time-to-rupture (log tr) versus inverse of water content (1/k) which are illustrated in Fig. log (s) 6 5 4 3 2 1 0 0 0.2366 R2 = 0.4406x + 4. log(s) Fig. (7) suggests that for a constant stress and temperature. Solasi et al.01 0.064x . This means that there is no change in the creep-mechanism when the environment (temperature or hydration) changes.9961 y = 1.9246x + 1. TÞe ÀQ k k 0 ð6Þ Stress. _ e ¼ A0 ðr. Slope of the parallel lines is hydration activation parameter. Slope of the parallel lines is temperature activation parameter. Graphical interpretation for the Sherby–Dorn parameter at constant relative humidity (50%). the Sherby–Dorn parameter as a function of stress. 8. log (s) 5 3 1 -1 -3 0 0. (8) we can estimate the long-term creep behavior and rupture of the dry membrane by running a relatively shorter time creep test for a more hydrated condition. Qk. Having values for activation energy.1.03 0. 6 as parallel lines for different stress values. A key assumption is that the activation energy for creep is constant at different conditions. 6. MPa 25 20 15 10 5 0 0 1 2 3 4 5 The coefficient (A ) is a function of stress and temperature. MPa Values for hydration activation energy Qk can be obtained by plotting creep-rupture data shown in Fig. (1/C) Fig. log (s) Fig. 7. Sherby-Dorn Parameter. (3) for creep of NafionÒ.5105 R2 = 0. TÞte P SD ¼ log #T. The Sherby–Dorn parameter for each stress is the intercept with the y-axis and Qk is the slope of the constant-stress lines.R. 20 15 10 5 0 -3 -1 1 3 5 e ¼ A00 ðr. First we consider the case with constant room temperature and various hydrations shown in Fig.9983 y = 1. P SD ¼ log #k. the Sherby–Dorn (S–D) approach was used for this type of membrane. Eq.248x + 1.r is temperature-compensated time when time is t = tr. Graphical interpretation for the Sherby–Dorn parameter at constant temperature (T = 25 °C).9323 Stress. The same concept can be applied to changes in temperature instead of hydration by reformulating Eq. The use of time–temperature parameters has been widely used to estimate the longterm behavior of the material based on the data from relatively short time tests but at higher service temperatures (Dowling. .5 1/λ Fig.156x . creep strains form a unique curve if plotted versus #k. The Sherby–Dorn parameter is defined by taking the logarithm of #k. By integrating Eq. Based on Eq. (3) in order to find temperature compensated time (#T ) as follows: log tr . Eq. 4.r ÀQ T T   1 ¼ log tr À Q T T ¼ A00 #T ð9Þ ð10Þ #T.6612 R2 = 0. Figs.9307 y = 94. 1993).02 0. Therefore strain-to-break (rupture strain) is constant for a given value of hydration-compensated time to break (#k. Sherby-Dorn Parameter. 7 where data for all stresses and hydrations fall together along a single curve.5 1 σ=15 MPa σ=10 MPa y = 2.0858 R2 = 0.6666x + 0. 9. Calculated hydration Sherby–Dorn parameters (PSD) at room temperature for different stress levels are demonstrated in Fig. Hydration Sherby–Dorn parameter at different stress levels for creep-rupture of NafionÒ111 at room-temperature. QT.9937 ture effects in the membranes during service life of the fuel cells must be taken into account for various temperature and hydration conditions.05 1/T.0. (6) we arrive at: e ¼ A0 ðr.

. For the case of NafionÒ membranes.. This could explain the vertical shift in stress-rupture curves from a dry state (k = 0.8) to the humidified phase (k = 3. one would also expect to see the time-dependent failure at higher temperatures (above Tg). The constant activation energy is the basic assumption in order to use the Sherby–Dorn time-hydration-temperature equivalence method. As it turns out from this work. hydration and temperature can be obtained. A more general definition of temperature-hydrationcompensated time #kT is also possible by integrating Eq. Since experimental data reported in Figs. Based on the stress-rupture results for different hydrations and temperatures in this work. 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. This beta relaxation is assigned to the Tg of NafionÒ (Page et al. As stated earlier. Discussion and conclusion Time-dependent failure for NafionÒ has been observed under different hydration and temperature environments.r ÀQ k ÀQ T T     1 1 À QT ¼ log t r À Q k k T ¼ A#kT ð11Þ ð12Þ By introducing Eq. From our observations. 1211–1216. R. K. 4 as hydration goes up and water clusters form in the membrane (between k = 3 and k = 10) stress-rupture curves get closer and creep behavior is almost the same with change in hydration. 5. (12) a 3-D representation of log tr versus inverse of T and k can be plotted. Solasi et al. S. a time-equivalence method is required to estimate the long time creep behavior. In order to get around test-time limitations. Recently it was suggested that on-set of thermally activated main chain motion should be assigned to the beta-relaxation (Tb $ À20 °C) as supported by DMA and SAXS evidence. 2004. creep deformation will continuously progress with a constant rate after its initial (primary creep) phase till final rupture. (3): e ¼ AðrÞte k e PSD ¼ log #kT. 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. 2005).. . for the range of hydrations for which our creep-rupture tests were conducted. These stress-rupture phenomena occur regardless of the temperature and hydration in the range we experimented. Otherwise. even though the membrane in an operating fuel cell is always hydrated. Consistency of the rupture mechanisms has also been observed at different temperatures for a constant hydration which implies that temperature shift also does not change the rupture behavior. where there is no free water. the water content does not change the time-dependent nature of the failure. NafionÒ deformed to the point of rupture. Moore. other methods such as Larson–Miller (L–M) and Manson–Haferd (M–H) approaches must be used (Dowling. Therefore. Curtin. Our stress-rupture data appear to support the new Tg assignment. Journal of Fluorine Chemistry: Fluorine in Alternative Energy Sources 125 (8). 4 and 6 is constant. For a crystalline thermoplastic polymer at temperatures above Tg. For a range of hydrations (vapor-phase) and temperatures. More (underwater) creep experiments at higher water contents (k > 14) could possibly portray a better picture to relate state of water to timedependent failure of NafionÒ. It appears that the movement of chains and therefore their disentanglement. State of understanding of Nafion. 4 and 5 are from different batches of NafionÒ.684 R. There was no evidence of visible necking at the fracture region in any of the conditions tested. However it seems that dependence of creep deformation on hydration is stronger when the membrane is in a nearly dry state. the membrane still shows time-dependent rupture with the same trend but with some greater delay. 2003). secondary bonds between carbon-based molecular chains are weak and chain sliding and disentanglement which can eventually lead to rupture are expected. From Fig. Assuming this Tg of approximately 100 °C stress-rupture is unlikely to happen. 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). But it was observed as part of this work that time-dependent failure happens at even room temperature. 2004. 4. results in the rupture of the material after a certain time.. Sherby–Dorn timehydration/temperature parameters have been successfully obtained for this purpose. 2004. the state of water in the membrane changes from bound water to bulk-like free water as it gets humidified from a dry state.A. At lower temperature and drier conditions. Chemical Reviews 104 (10). Nafion(R) perfluorinated membranes in fuel cells. which are semi-crystalline polymers. the stress-rupture process proceeds more slowly. / Mechanics of Materials 42 (2010) 678–685 in Figs. 4535–4585. Bulk free water seems to accelerate the rupture behavior compared to loosely and tightly bound water but even at those dry states. Banerjee. References Mauritz. 1993). It should be noted that the glass transition temperature of NafionÒ in the literature has been reported to be around 100 °C (Mauritz and Moore. even at stress levels considerably lower than the yield stress (15–50% ry).5–10) shown in Fig. it is not clear whether the existence of water clusters in the hydrated NafionÒ (which are softer compared to the polymer backbone) makes disentanglement creep of the molecular chains easier or if these water molecules work as barriers against chain slippage and inhibit disentanglement and the eventual rupture.B. excessive deformation and possible long-term rupture have to be accounted for in engineering design of automotive fuel cell membranes even at dry conditions. The creep behavior of polymers is known to be complicated at intermediate temperatures where the behavior is rubbery (slightly above Tg). D. when subjected to a constant load. Physical Properties for Nafion. As mentioned before. this more general form of temperature-hydration equivalence will not be reported here. In this way the Sherby– Dorn parameter for any given stress.E..

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