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ORG
Water-Mediated Transport in Ion-Containing Polymers
Michael A. Hickner
Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802
Correspondence to: M. A. Hickner (E-mail: hickner@matse.psu.edu)
Received 3 October 2011; accepted 3 October 2011; published online 17 October 2011
DOI: 10.1002/polb.22381
ABSTRACT: Water-mediated ion conduction enables high con-
ductivity in hydrated polymer membranes commonly used in
electrochemical devices. Understanding the coupling of the
absorbed water with the polymer matrix and the dynamics of
water inside the polymer network across the full range of
length scales in the membrane is important for unraveling the
structure–property relationships in these materials. By consid-
ering the water behavior in ion-containing polymers, next-gen-
eration fuel cell membranes are being designed that exceed
the conductivity of the state-of-the-art materials and have opti-
mized conductivity and permeability that may be useful in
other types of devices such as redox flow batteries. Water–
INTRODUCTION Polymer membranes are important func-
tional components of low-temperature fuel cells and electro-
lyzers. The scientific and engineering push for alternative
energy conversion and storage technologies has intensified
efforts to develop new ion-containing membranes that dis-
play high conductivity (10
1 S cm
1 or greater) with low or
no water absorption. However, water is an excellent medium
for fast ion conduction; thus, the most successful approaches
to new materials that display ionic conductivities high
enough for application in devices have water uptakes of usu-
ally 10 wt % or greater. The water behavior in ion-conduct-
ing membranes underpins their transport properties, espe-
cially in tradeoff relationships between ion conductivity and
molecular or ion permeability and permselectivity. In many
cases, if higher conductivity is desired, more water must be
absorbed into the membrane which promotes larger molecu-
lar and ion diffusion coefficients.
In these types of materials, the functionalized polymer intro-
duces excess ions into the water phase in the membrane.
The concentration of ions in the membrane contributes to
the conductivity (ri) by:
ci Di z2i F 2
ri ¼ (1)
RT
where ci is the concentration of ions that contribute to the
conductivity, zi is their charge, and Di is the diffusion coeffi-
V
C 2011 Wiley Periodicals, Inc.
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REVIEW
polymer associations can be exploited to tune the transport
and mechanical property tradeoffs in these polymers. Measure-
ments of water motion provide important criteria for assessing
the factors that control the performance of these types of mate-
rials. This review article discusses current understanding
of water behavior in ion-containing polymers and the rela-
tionship between water motion and ion and molecular
transport. VC 2011 Wiley Periodicals, Inc. J Polym Sci Part B:
Polym Phys 50: 9–20, 2012
KEYWORDS: charge transport; diffusion; hydrogen bonding; ion-
omers; morphology
cient of the ions that give the conductivity response. For pro-
ton exchange membranes (PEMs), which are single ion
conductors, the proton concentration in the membrane can be
expressed as cHþ. In most cases, the activity of the protons or
the concentration of free protons in the membrane is not
known;1 therefore, the analytical proton concentration in the
membrane, as determined by titration of the sulfonate groups,
is usually sufficient as an approximation to cHþ to estimate the
effective proton diffusion coefficient. For a membrane with a
proton conductivity of 10
1 S cm
1 and a proton concentra-
tion of about 1 M, the effective proton diffusion coefficient is
on the order of 3  10
5 cm2 s
1, which can be compared to a
proton diffusion coefficient of 10
4 cm2 s
1 in liquid water.
The diffusion or mobility of protons in these materials is not
quite as high as in bulk water, but most measurements of the
water behavior and ion and small molecule diffusion coeffi-
cients are indicative of liquid-like dynamics.2
The polymer, in essence, provides a framework for the
absorbed water. Thus, understanding the water sorption
properties of these materials and studying the water–poly-
mer interactions provides basic mechanistic information on
the behavior of the membranes. The fundamental studies of
water motion in these types of polymers help to rationalize
the transport properties of materials with new polymer com-
positions or ionic domain structures. This understanding can
then be used to boost the performance of next-generation
materials for application in devices. Instead of designing and
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Michael Hickner is the Virginia S. and Philip L. Walker, Jr. Faculty Fellow and an Assistant
Professor of Materials Science and Engineering at The Pennsylvania State University.
Hickner’s work has been recognized by Office of Naval Research and Army Research Office
Young Investigator Awards and a Presidential Early Career Award in Science and
Engineering (PECASE). He has co-authored five US and international patents and over 70
peer-reviewed publications with more than 3200 citations.

optimizing materials toward a nebulous goal of ‘‘higher con-
ductivity,’’ considering the interplay between polymer chemi-
cal structure, adsorbed water, and ion transport may give
researchers in this area an additional tool for predictive
design of these systems.
The archetypal ion-containing polymer used as a PEM in fuel
cells and other types of electrochemical devices is NAFIONV
R
influence the material’s transport properties. Different con-
ceptual frameworks have been used to describe the water–
polymer associations in a range of hydrophilic polymers.
Terms such as ‘‘state of water’’ or ‘‘free, loosely bound, and
tightly bound’’ help to describe the distribution of physical
and chemical environments that water experiences in a
hydrophilic polymer network. In practice, an observable

property of the water such as its T1 relaxation time, self-dif-

(a product of DuPont) and its related structures, which are
fusion coefficient, or vibrational frequency of a characteristic
generally classified as poly(perfluorosulfonic acid)s (PFSAs).
mode is needed to quantify how water is held within the
These perfluorinated polymers have tethered sulfonic acid
polymer and in many cases the water inside a polymer mem-
groups that render the materials hydrophilic and increase
brane shows different signatures than bulk water.
the proton concentration in the membrane to achieve high
conductivity. Much research has been devoted to exploring The preceding discussion of morphology and water dynamics
the details of the arrangement of hydrophilic and hydropho- in water-absorbing, ion-containing polymers is decidedly
bic components of PFSAs in the solid state, particularly in separate from polymer-mediated ion transport, for example,
the context of deciphering their proton conduction proper- in Li-ion battery polymer electrolytes, where the ion motion
ties. This ionic domain morphology is thought to give rise to is coupled tightly to the polymer segmental dynamics.12
NAFIONV’s high ionic conductivity, high water permeability,
R
Water as the medium of ion transport leads to thermally
and other interesting properties. The nanophase morphologi- activated transport where the temperature-dependent con-
cal structure in fuel cell membranes is indeed an important ductivity can be described by an Arrhenius-type activation
factor in their performance as the ionic nanophases provide energy. For polymer-mediated ion conductors, the conductiv-
the ‘‘pipes’’ through which water and ions move. However, ity is often described by a Vogel-Fulcher-Tammann depend-
the connectivity and size of these ionic domains does not ence on temperature. In many cases, the conductivity of
fully explain the ion conduction behavior of these materials.
Many of the new classes of ion-containing polymers designed
to supplant PFSAs are based on aromatic backbones. There
are distinct differences in the ionic domain structure of
sulfonated poly(aromatic) membranes compared to PFSAs.
Foremost, the ability of the ions to cluster in the stiffer-
chained poly(aromatic) membranes is poor which leads to
smaller ionic domains than what are observed in PFSAs, Fig-
ure 1. This domain structure and the chemical properties of
the polymer have a direct influence on the absorbed water
mobility as evidenced by the self and Fickian diffusion coeffi-
cients of water and the deuterium T1 relaxation times meas-
ured as a function of hydration for each type of material.3,5,6
There have been many studies of NAFIONV’s ionic domain
R

structure,7–10 and comparisons to aromatic polymers have

revealed some of the structural origins of the differences in
conductivity between these two classes of ion-conducting
polymers.11 However, there is no direct ionic domain struc-
ture to conductivity relationship when materials with differ-
ent polymer backbones are considered. Interesting insights
to explain the differences in transport properties between
PFSAs and aromatic polymers have arisen from exploring FIGURE 1 Backbone chain schematics, transmission electron
how the water rotational and translational motion, or in micrographs, ion concentrations, and water self-diffusion co-
short, the water binding and dynamics, in the membrane efficients for PFSA and sulfonated aromatic PEMs.3,4

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FIGURE 2 Proton (n) and water (h) diffusion coefficients as a
function of hydration number. Adapted from Ref. 20.
polymer-based ion conductors can be scaled by the Tg of the
material, which collapses data from polymers with different
Tgs onto a characteristic curve.13 Deviations from Tg scaling
in polymer-mediated ion conductors can be due to increased
free ion content,14 phase separation and morphology,15
or increased density of ion donors or acceptors.16 Similar
observations have been made for the temperature depend-
ence of ionic liquids where the long-range molecular
dynamics controls the temperature-dependent conductivity
response.17–19
The purpose of this review is to highlight the important
insights and tools that have facilitated our understanding of
ion transport in water-absorbing membrane and further the
discussion of water–polymer interactions in materials that
rely on the presence of water for high transport rates. The
relationship between water mobility and proton conductivity
will be discussed. Different length-scale measurements for
water mobility will be described and sections are included
on the effect that water has on molecular transport proper-
ties and mechanical properties. Finally, recommendations are
given for how to take the fundamental knowledge developed
for proton transport in fuel cell membranes and extend
these concepts to new types of ion-containing membranes
and applications.
WATER MOTION AND PROTON CONDUCTIVITY
Seminal studies on PEM fuel cell (PEMFC) materials have
revealed the basic phenomena that are important to consider
when dealing with proton conductivity in water-absorbing sys-
tems. The diffusion coefficient of protons, calculated from the
Nernst–Einstein relationship and measured conductivity values,
is greater than the self-diffusion coefficient of water, deter-
mined by pulsed-field gradient nuclear magnetic resonance
(PFG-NMR) self-diffusion coefficient measurements, at high lev-
els of hydration (Fig. 2).20,21 When minimally hydrated, less
than three to four water molecules per excess proton, the water
and protons move in concert as evidenced by their similar diffu-
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REVIEW
sion coefficients. However, when sufficient hydration is present,
the proton diffusion coefficient is much greater than diffusion
coefficient of the surrounding water medium and proton ‘‘hop-
ping’’ is evident. This high hydration case in a NAFIONV mem-
R
brane is similar to what is observed in bulk liquid water where
the excess proton diffusion coefficient exceeds the self-diffusion
coefficient of water by factor of 5.11
As water is added to a membrane, the signatures of water
rotational and translational mobility increase. Measurements
of the 2H T22
1 and the self-diffusion coefficient of water by
PFG-NMR11,20 show that water is more mobile for higher
water to acid group ratios. The water:acid molar ratio is
termed the hydration number (k or wo). It is tempting to
invoke hopping-type transport when the rotational dynamics
of water are slow. However, the above experimental meas-
urements demonstrate that fast water rotation is required to
achieve hopping. Otherwise, at low hydration numbers, the
hydronium or H2nþ1On (hydronium plus excess waters) must
diffuse through the water matrix and hopping is minimized.
Water plays a special role in the context of proton conduc-
tion because of its amphotericity. The dual role of water as a
proton donor (as hydronium) and proton acceptor coupled
with its fast rotational dynamics imparts high ionic conduc-
tivities to water-absorbing polymers as long as the materials
remain hydrated and there exists sufficient acid concentra-
tion to create a number of excess protons. Other amphoteric
molecules such as phosphoric acid23 and triazole/imidaz-
ole16,24,25 conduct protons with a hopping-type mechanism,
but their larger molecular structures and thus lower rota-
tional dynamics and higher viscosities lead to significant
depressions in their proton conductivity compared to water.
The fast dynamics of proton transport in water is contrasted
with the slower molecular dynamics of the polymer mole-
cules themselves. Paddison and Zawodzinski26 studied the
side chain of NAFIONV and concluded that although the sul-
R
fonate group can freely rotate, the rest of the side chain is
rather stiff. Also, the perfluoroether side chain of NAFIONV
R
is hydrophobic and likely exists in a coiled configuration in
the hydrated polymer. Thus, the flexibility and molecular
motion of the side chain likely plays a minor role in the pro-
ton conduction process. However, the topology and flexibility
of the ion-containing polymer determines the ability of the
ionic nanophase to self-assemble into ordered domains. The
difficulty in deconvoluting the morphology is in part due to
the subtle changes in morphology that can occur with even
minor variations in polymer chemical structure.
In many applications, ions must move through a 10–150-lm-
thick membrane, which is at least three orders of magnitude
greater than the 1–10-nm-size ionic domains observed for
many systems. Clearly, ionic conduction across a membrane
is a multilength-scale problem from the atomic-scale hydro-
gen bonding dynamics between water molecules, to the ionic
domains that may contain thousands of water molecules, to
the micron length scales that the protons must traverse.
Thus, a variety of techniques are required to probe the water
motion over a range of length and time scales to more
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FIGURE 3 Water self-diffusion coefficient for NAFIONV R (~),
random poly(aromatic) (h), and block poly(aromatic) (n) PEMs.
Adapted from Ref. 39.
completely understand the role that water plays in mediating
ion transport in these materials.
Vibrational spectroscopy has been used to probe the hydro-
gen bond dynamics of water bound in NAFIONV.27,28 In
R
Falk’s work, the DAO stretch in hyrogen-oxygen-deuterium
(HOD) was used to quantify the hydrogen bonding environ-
ment of water in Na-form NAFIONV.29 This vibrational signa-
R
ture is convenient as the DAO stretch appears in a relatively
featureless region of the mid-IR spectrum at about 2509
cm
1, and there are no complications with interpretation of
the DAO stretch as compared to HAO due to lack of Fermi
resonance of DAO bonds. Moilanen et al.30 observed a high
frequency shoulder for DAO in NAFIONV at a frequency of
R
2708 cm
1. The water associated with this stretch was
interpreted to be in strong contact with the hydrophobic
portion of the NAFIONV membrane. The main DAO peak fre-
R
quency was dependent on the hydration of the membrane
and shifted from 2590 cm
1 at a k ¼ 1 to 2553 cm
1 at a k
¼ 9 as result of the relative populations of water changing
as the membrane became more hydrated. This type of mea-
surement yields interesting information on the distribution
of water environments, but a vibrational frequency is diffi-
cult to correlate to rotational or translational diffusion coeffi-
cients, which may be more relevant to transport processes.
Similar insights into NAFIONV–water interactions have been
R
gained from fluorescence spectroscopy and UV–vis adsorp-
tion of fluorescent probe dyes.31–33
Ultrafast spectroscopy has been used to make measurements
of the multiple hydrogen bond environments of water in
NAFIONV membranes.30,34 The vibrational lifetimes in
R
NAFIONV membranes showed two components with values
R
between 2 and 11 ps for hydration numbers between 1 and
7.5, which compares to a vibrational lifetime of HOD in bulk
water of 1.7 ps with a single exponential decay. Interestingly,
the vibrational lifetime experiments show that the character-
istic relaxation times of fast and slow relaxing water both
change as a function of hydration. This result indicates that
12 JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2012, 50, 9–20
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the character of each type of water or the population of envi-
ronments occupied by water changes as the membrane is
hydrated. This assertion is supported by poor single expo-
nential or two component fits (bulk water and k ¼ 1 water)
to the relaxation data and shows that the distribution of
water across multiple hydrogen bonding environments
changes with hydration. These changes in the water–polymer
interactions could be due to the character of the water–
NAFIONV contacts at the hydrophilic/hydrophobic interface
R
evolving as a function of hydration.
NMR relaxation measurements such as T1 probe the local
rotational mobility of water within a sample. 2H T1 values
between 5 and 200 ms have been measured in a range of
PEMs imbibed with 2H2O, which correlate to water rota-
tional rate constants on the order of 107 to 1010 s
1, simi-
lar to values found in supercooled liquid water.35,36 These
values compare to an 2H T1 of 400 ms for ambient pressure
liquid 2H2O at 292 K with a rotational rate constant of 2.8
 1011 s
1.37 2H T1 measurements show a strong correla-
tion to the hydration number and conductivity for
NAFIONV.22 Lee et al.5 showed that sulfonated aromatic
R
polymers showed lower 2H T1 values than those observed
in PFSAs at equivalent hydration numbers. For instance at a
k ¼ 5 for NAFIONV 117 the 2H T1 was 80 ms and for a sul-
R
fonated Radel sample at k ¼ 5 the 2H T1 was 20 ms which
resulted in depressed conductivity for sulfonated Radel.
These authors hypothesized that the ionic domain structure
had a significant influence on the observed results.
PFG-NMR measurements have been used extensively to mea-
sure water self-diffusion on the 50 ms and longer time
scales. In a 1D experiment, the length scale over which the
diffusion coefficient is measured is given by:
pffiffiffiffiffiffiffiffi
l¼ 2Dt : (2)
Typical water self-diffusion coefficients in PEMs are on the
order of 1  10
10 to 1  10
8 cm2 s
1, which gives diffu-
sion lengths of 1–10 lm. This size scale is clearly larger than
the nanoscale features of the ionic domain morphology in
PFSAs or the ionic domains in a block copolymer-based
PEMs; however, good correspondence between chemical
structure and the water self-diffusion coefficient has been
observed.
Roy et al.38,39 reported that block copolymers display higher
water self-diffusion coefficients than their random analogs
(Fig. 3). In random systems, the self-diffusion coefficient
measured by PFG-NMR declined steadily with increasing dif-
fusion time. At long diffusion times, the self-diffusion coeffi-
cients in NAFIONV and block copolymers were not a function
R
of diffusion length. The high conductivity in block copoly-
mers is thought to be due to their higher concentration
of ionic groups in the functionalized domains and the
connectivity of the phases. However, the block copolymer
architecture also appears to have an influence on the water
behavior, which is intimately tied to their proton conduction
properties.
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Li et al.40 showed that orientation in extruded NafionV 112
R
and dispersion cast NAFION (NRE)-212 membranes could be
detected through measurements of 2H NMR quadrupole cou-
pling. The residual quadrupole splittings are related to the
orientational order parameter where the motion of water in
the ionic domains is biased by the orientation of the ionic
domains. Biaxial orientation in the plane of the film was
observed in the extruded membranes, but the dispersion
cast samples had uniaxial orientation in the thickness direc-
tion of the sample. Hou et al.41 used both 2H quadrupole
splitting and pulsed field gradient diffusion measurements to
explore the anisotropy of block copolymer PEMs over differ-
ent length scales. The 2H splitting measurements probe
order on about the 0.4 lm length scale, where diffusion
measurements probe larger length scales as discussed above.
These results demonstrate that the nature and number of
defects and the local ordering of the material over multiple
length scales can affect different measurements of water
motion. More combined studies of structural order including
defect type and density and water and ion mobility will help
to clarify the role that defects play in the transport processes
in these types of materials.
The PFG-NMR technique rigorously measures the water self-
diffusion coefficient (Dself), which is related to the Fickian
diffusion coefficient (DFick) through:
 
@lnðaw Þ
DFick ¼ Dself ; (3)
@lnðkÞ
where aw is the activity of water, so qln(aw)/qln(k) describes
the hydration of the membrane with relative humidity (RH).
Fickian diffusion coefficients for water in these types of poly-
mers can be derived from dynamic water sorption experi-
ments or concentration gradient diffusion experiments. As
the water motion in sorption or concentration cell experi-
ments is due to a concentration gradient, these measure-
ments probe the Fickian diffusion coefficient and cannot be
compared directly to PFG-NMR self-diffusion coefficients
unless the water uptake properties are known.
Hallinan and Elabd42 used attenuated total reflection-FTIR
sorption measurements to quantify the water uptake proper-
ties of NAFIONV during small and large step-changes in RH.
R
These authors found that a Fickian diffusion model described
most small RH step change experiments, for example, from
43% to 56% RH, but for dry membranes or large steps in RH,
for example, from 0% to 22% RH or 0% to 100% RH, the
uptake curves were non-Fickian. The authors were able to
decrease the mass transfer resistance at the vapor–membrane
interface by increasing the velocity of the gas phase surround-
ing the membrane, which is critical for recovering the correct
value of the diffusion coefficients. Water permeation experi-
ments under steady-state concentration gradients can also
give insight into the water mobility of membranes as they are
exposed to different hydration conditions.43,44 However, per-
forming these types of experiments for small gradients in
water activity is important to maintain consistent hydration
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throughout the membrane for accurate determination of the
diffusion coefficient at a known hydration value.
Siu et al.45 showed that the water associations with the poly-
mer may be beneficial in promoting conductivity under
freezing conditions. On freezing PEMs to
40  C, the conduc-
tivity dropped by four orders of magnitude, and the activa-
tion energy of proton conduction increased from 0.15 to 0.4
eV. Appreciable conductivity in the frozen samples was
thought to stem from the water that was still tightly associ-
ated with the acid groups in the samples and did not show
any thermal transitions around 0  C in DSC experiments. Ma
et al.46 observed a water self-diffusion coefficient of 4 
10
11 m2 s
1 at 240 K using PFG-NMR for membranes ini-
tially equilibrated at 98% RH. This value compares to a
water self-diffusion coefficient of 2  10
10 m2 s
1 at 273
K. Although this work demonstrates that absorbed water in
PFSAs was moving more slowly in the membranes below
0  C compared to membranes at higher temperatures, there
was enough mobility to promote proton transport. Other
studies of water mobility at low temperatures showed step
changes in the water self-diffusion coefficient at low temper-
atures that were attributed to freezing events.47,48 These
membranes were probably more hydrated than the samples
studied by Ma et al., which lead to some portion of the water
in the membrane freezing. These studies of the water mobil-
ity at sub-zero temperatures demonstrate that the water–
polymer associations observed in PEMs show a wide range
of behaviors and have a significant influence on the trans-
port properties, even under conditions where bulk water is
frozen.
Dielectric spectroscopy has been used to explore the motion
of water in hydrated PEMs. Paddison et al.49 showed that
the dielectric constant of NAFIONV increased with hydration
R
number and decreased with increasing frequency, similar to
that of liquid water. In sulfonated poly(aromatic) samples,
the measured dielectric constant was a weaker function of
hydration number than what was observed for the PFSA
samples.50 Kreuer11 showed that the dielectric constants
measured in each case are a reflection of the ionic nano-
phase morphology of the material. Additionally, the dielectric
constant as a function of water volume fraction extrapolated
to 64 in NAFIONV at a water volume fraction of unity where
R
a value of 20 was observed for the sulfonated poly(aromatic)
sample. The dielectric response is reflective of the lower
water mobility observed in sulfonated poly(aromatic) sam-
ples compared to PFSAs. Lu et al.51 resolved different popu-
lations of water in NAFIONV membranes using dielectric
R
spectroscopy. Gigahertz relaxations were observed reflecting
water with bulk-like properties in addition to a process that
had a lower dielectric relaxation frequency response. The
dielectric strength of these two processes showed an
increase with hydration number indicating that the popula-
tions of water molecules giving rise to each process
increased with hydration number. A process with kilohertz
relaxations was also assigned to the rotational motions of
the hydrated sulfonate groups and their first hydration
spheres.51,52 Shifts in the relaxation frequencies to higher
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ferential scanning calorimetry experiments, which were cor-

FIGURE 4 Thermal signature of water in the membrane corre-
lates to proton conductivity (*) and methanol permeability
(l). Data taken from Ref. 4.
values reflected a larger population of faster moving water
as the hydration numbers were increased.
There are a variety of methods for understanding the dy-
namics of water and its distribution of environments when
absorbed in ion-containing membranes. PFG-NMR has the
advantage of a direct measurement of the water self-diffu-
sion coefficient, but it is difficult to extract distribution infor-
mation from this type of measurement. Additionally, the
length scale over which the measurement is probing the dy-
namics of water must be considered. Vibrational and dielec-
tric spectroscopy can extract information on the different
environments that water experiences in the material, but the
length-scale dependence of the measurements, the exchange
of water between different microenvironments, and the
meaningful parameters for proton transport are still being
studied for a range of different PEMs. Comprehensive meas-
urements tying conductivity values and measurements of
water motion will further the community’s understanding of
proton transport in these types of ion-containing polymers
and this basic knowledge can be extended to study ion and
molecular transport beyond proton transport.
related to increased water mobility. The activation energies
for transport also declined with increased heats of fusion of
water leading the researchers to conclude that more rapidly
diffusing water could be linked to faster molecular diffusion
of the solutes. The ionic domain size and connectivity was
not sufficient to explain these differences in the transport
properties of the membranes and the measurement of a sig-
nature of water binding seemed to bridge the understanding
of transport across chemically dissimilar materials. However,
it must be stressed in this study that the ionic domains
were studied in their dry state. TEM or scattering of dry
samples is often performed out of convenience, but techni-
ques to measure the size and connectivity of the hydrated
domains for a range of polymers are becoming more com-
monplace.53–56
The concept of electrochemical selectivity57 or the perme-
ability-normalized conductivity is useful for quantifying the
tradeoff between the different transport properties of inter-
est for a given application. However, this type of figure of
merit can have shortcomings, especially for materials that
show high selectivity, but may have very low absolute values
of conductivity.58 Thus, a minimum conductivity must be
first defined for a given application, and then candidate
materials can be selected once the primary goal of conduc-
tivity is met. Many sulfonated aromatic polymers show
increased relative selectivity for proton conduction versus
methanol permeation compared to PFSAs. This increase in
selectivity can be interpreted both by considering the rela-
tive size of the ionic domains in each system and by visualiz-
ing how the water is distributed throughout these different
sized phases (Fig. 5). It has been shown that the permittivity
within an ionic pore changes radially.59–61 The high dielectric
constant in the center of the pore gives rise to high rates of
water and solute transport. Therefore, larger pores contain
water that is less associated with the polymer, and high
transport rates result. This situation not only increases pro-
ton conductivity but also can significantly increase methanol
and water transport.
Xu et al.62 were able to increase the selectivity of PEMs
through tuning the ion content of crosslinked polymers. In

TRANSPORT OF WATER AND SMALL MOLECULES

The water motion in fuel cells membranes is often measured

to interpret the proton conductivity of the materials, but the
water dynamics also have a pronounced impact on the trans-
port of water and small molecules in fuel cell membranes.
Hickner et al.4 correlated the thermal signatures of water
absorbed in a series of sulfonated poly(phenylene)s to the
transport of methanol (Fig. 4) and glucose through the mem-
branes. For highly sulfonated poly(phenylene)s, the diffusion
of methanol and glucose was greater than for NAFIONV
R

membranes. The ionic domains as observed by transmission

electron microscopy (TEM) were not as well organized in
the sulfonated aromatic polymers as they appeared in
NAFIONV; however, the absorbed water in the samples with
R
FIGURE 5 Down-pore view of ionic domains in PFSAs and sul-
high transport rates showed increased heats of fusion in dif- fonated poly(aromatic) PEMs.

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 WWW.POLYMERPHYSICS.ORG
this work, the authors were able to connect the increased
electrochemical selectivity of their materials with a lower
thermal signature of water by calorimetry experiments. For a
PEM with an ion exchange capacity (IEC) of 0.97 mequiv g
1
and a water uptake of 19 wt %, a relative selectivity of 22
was obtained while maintaining a conductivity of 0.048 S
cm
1. The low water thermal signature and high selectivity
was the result of the small ionic domains in these materials
and perhaps some added polarity due to the presence of the
urethane bonds at the crosslink junctions.
Hickner and Pivovar63 correlated the water self-diffusion coef-
ficient, electro-osmotic drag, relative selectivity, and backbone
stiffness for a variety of PEMs. The observation of electro-
osmotic drag being correlated with the relative selectivity is
interesting because this connection emphasizes the linkage
between water motion and the other transport properties of
the membrane. Electro-osmotic drag is a function of the num-
ber of water molecules transported with each proton across
the membrane. For membranes with significantly confined
water, the electro-osmotic drag values will be low. However,
for membranes with less water–polymer associations, the vis-
cous drag of the proton as it moves through the ionic domains
results in more water transport in concert with the proton
and thus a higher electro-osmotic drag coefficient. Hickner
and Pivovar’s correlation demonstrates that more mobile
water is tied with lower electrochemical selectivity.
Interpreting the transport properties of PEMs through
insights into the mobility and binding of water absorbed in
the polymer is a useful method for understanding the trade-
off in properties that are prevalent in these types of materi-
als. In many cases, if an increase in conductivity is desired,
the diffusion of methanol and water will increase as well,
which is not always favorable for a given application. The
permeability of methanol can be suppressed in many PEMs
but often at the expense of ionic conductivity. Even though
ion conducting and molecular diffusion occurs through the
aqueous ionic domains in the material, the transport prop-
erty tradeoffs can be optimized because the migration of
ions depends on the ionic concentration in the sample but
the molecular diffusion does not. For instance, Xu et al.64
were able to maintain a high degree of mobile water in
NAFIONV/sulfonated poly(silsesquioxane) composite samples
R
by increasing the IEC; however, the selectivity was improved
even as the water uptake of the materials was increased.
This unusual trend in properties was due to maintaining
high ion exchange capacities and hence conductivities in the
materials due to the inclusion of the sulfonated filler, but the
filler also provided some blockage of the ionic domains thus
preventing methanol permeability through the material. This
type of strategy will be useful going forward in optimizing
the transport property tradeoffs in other types of mem-
branes for various applications.
POLYMER RELAXATION DURING UPTAKE AND
MECHANICAL PROPERTIES
The dynamic motion of the polymer molecules do not make a
primary contribution to proton motion under conditions of
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REVIEW
steady-state water content (except possibly at very low hydra-
tion), but during changes in water uptake, polymer relaxation
plays a significant role in determining the rate of water swel-
ling or deswelling. Various models have been proposed for
how polymer structure at the polymer/vapor interface controls
water transport into a membrane.65 The difference in water
uptake of a membrane from the vapor or liquid phase with
unit activity (saturated vapor or liquid water at the same tem-
perature) has been ascribed to a hydrophobic surface layer
that develops in PFSAs when exposed to dry conditions or low
activity water vapor. This Schroeder’s paradox has been
invoked to explain the interfacial resistance to slow water dif-
fusion into the membrane from the vapor phase. Onishi
et al.66 provided evidence that observations of Schroeder’s par-
adox are primarily governed by the equilibration time of the
sample in the vapor phase and thus emphasized that polymer
dynamics, even at extremely long time scales, control, in part,
the water uptake of these types of materials.
Relaxation dynamics of the polymers are evident during
dynamic water uptake experiments. Quantitative expressions
for the relaxation dynamics have been developed by Hallinan
and Elabd67 using a diffusion-relaxation model for NAFIONV
R
adsorption. In this work, the authors demonstrated that by
minimizing the vapor–polymer boundary layer thickness dur-
ing the water uptake experiments, the sorption curves could
be described by a coupled Fickian diffusion process and a poly-
mer relaxation expression that likely occur on similar time-
scales. For various models, the calculated diffusion coefficients
were similar and spanned values of 2  10
7 to 9  10
7
cm2 s
1 over the full range of water activities. The self-diffu-
sion coefficient of water in ion-containing polymers increases
systematically with hydration number (see Fig. 1). The Fickian
diffusion coefficients, however, display a maximum at interme-
diate hydration.5,68,69 This difference in the shape of the self-
diffusion and Fickian diffusion coefficients is due to the shape
of the sorption relationship with water activity (eq 3).
Satterfield et al.70 reported creep rates of dry and hydrated
NAFIONV membranes over 1000 min. Hydrated samples
R
were observed to creep quickly at short times due to their
plasticization by water, and dry samples have slower creep
rates, but showed long-time relaxations. Interestingly, the
swelling pressures measured during in situ hydration of the
membrane showed relaxation on the timescale of the
mechanical creep experiments. Results for the swelling prop-
erties of the membranes in this work were discussed in the
context of the competing energies of solvation of the ionic
groups and the energy required to swell the polymer matrix.
Interesting effects have been observed for the creep and me-
chanical properties of NAFIONV with low water contents.71–73
R
Under specific conditions of temperature and water activity,
NAFIONV can undergo antiplasticization, where the addition
R
of water increases the tensile modulus of the membrane. The
mechanism of this antiplasticization is not entirely clear, but it
may be due to microstructural changes in the polymer or ioni-
zation/bonding interactions of the sulfonic acid groups on
small additions of water.
JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2012, 50, 9–20 15
 REVIEW
Harrison et al.74 reported that the modulus of a disulfonated
poly(arylene ether sulfone) membrane was one order of
magnitude higher than that of NAFIONV but declined precipi-
R
tously with hydration. Similar observations have been made
by Fujimoto et al.75 for sulfonated poly(phenylene)s where
the Young’s modulus of NAFIONV declined by a factor of four
R
for hydrated samples, but the modulus of the sulfonated
poly(phenylene) dropped by a greater percentage due to a
larger plasticization effect. Under hydrated conditions, the
modulus of sulfonated aromatic polymers is generally
greater than that of PFSAs. The difference in mechanical
properties between materials narrows under hydrated condi-
tions due to the greater extent of plasticization of aromatic
polymers by water. The aromatic polymers are more plasti-
cized because of the greater extent of water–polymer inter-
actions in non-perfluorianted samples as compared to PFSAs.
Kim et al.76 showed that the Kelley–Bueche equation (a vari-
ant of the Fox equation) described the decrease in the Tg of
NAFIONV and disulfonated poly(arylene ether sulfone)s
R
membranes up to a certain water content. For NAFIONV the
R
Tg strongly decreased with increasing water content and fol-
lowed the Kelley–Bueche equation up to a bulk water uptake
of 5 wt %. The drop in Tg was more severe for the disulfo-
nated poly(arylene ether sulfone) sample and the Tg depres-
sion followed the Kelley–Bueche equation up to nearly 20 wt
% water uptake. At higher water contents than these critical
values, the Tg of each material departed from the prediction
of plasticization and was only weakly influenced by the fur-
ther addition of water. The authors hypothesized that the
critical value of water uptake for each material was con-
trolled by the amount of water–polymer interactions for a
given sample. As the disulfonated poly(sulfone) material had
small domains and a polarizable backbone, it had more con-
tact between the polymer and water which increased the
critical value of water uptake. NAFIONV with its perfluori-
R designing a material for a specific use.
nated backbone and well-defined ion domain structure was
not as plasticized by water and instead the water was col-
lected in the ionic nanophase of the material.
An important aspect of a membrane is its ability to withstand
mechanical deformation during device assembly or operating
stresses.77 Many ion-containing aromatic polymers have
higher moduli than what is observed for PFSAs, but the elon-
gation properties of aromatic polymer rarely exceed 30–50%
in the wet state, where NAFIONV’s elongation to break is
R
about 170% and does not change significantly from wet to
dry conditions.75 The poor elongation properties of many
PEMs is demonstrated by their inability to withstand wet–dry
cycling. In this type of test, the membrane is mechanically
constrained, and the RH surrounding the membrane is cycled
on the timescale of minutes between wet (usually 80% RH or
higher) and dry (usually 20% RH or lower) conditions. Vari-
ous PFSAs and reinforced PFSAs can approach or exceed
thousands or tens of thousands of cycles in this type of test.
However, few aromatic polymers have demonstrated good
performance under these conditions. The low oxygen perme-
ability of sulfonated aromatic polymers increases their resist-
ance to chemical attack by reactive oxygen species,78 but the
16 JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2012, 50, 9–20
WWW.POLYMERPHYSICS.ORG
deficiencies of aromatic polymers in mechanical properties
are a major concern for long lifetime devices. The synthesis of
block copolymer PEMs with soft blocks may be one route to
materials with greater toughness and elongation properties,
but synthesizing these types of materials with chemical moi-
eties that can withstand the electrochemical stresses and reac-
tive species in an operating device is a technical challenge.
The mechanical stabilization of the membrane is important to
preserve the morphology of the water-filled ionic domains that
contribute to high transport rates in these types of membranes.
Additionally, too much water uptake by the polymer can dilute
the concentration of ionic groups and lower the resulting con-
ductivity.79 Kim et al.80 measured the disruption of the ionic do-
main morphology of NAFIONV and disulfonated poly(arylene
R
ether sulfone) proton conducting membranes and correlated
these microscopic changes to the overall membrane swelling
and proton conductivity. The authors proposed an ‘‘upper limit
use temperature’’ that describes the maximum temperature at
which the polymer will not over-swell when exposed to liquid
water. This concept can be extended to polymers that swell
highly at room temperature, an upper swelling parameter, and
provides guidelines for the ideal concentration of ions in the
membrane in the swollen state. In other work, Kim et al.81
showed that even though the hydrated ion concentration can
decline for samples that uptake significant amounts of water,
the proton conductivity can continue to increase up to a point
even though the ion concentration in the sample decreases.
This increase in conductivity, even under declining proton con-
centration, is due to faster proton transport through the aque-
ous phase that displays more rapid water rotation and diffusion
with the increased water uptake. These observations lead to the
conclusion that there is no one descriptor of high conductivity
in PEMs, but the ionic domain morphology, water–polymer
interactions, and ion concentration must all be weighed when
Dynamic water uptake has been investigated in submicron
NAFIONV films. Kongkanand82 ascribed the slow water uptake
R
of nm-thick films to the hydrophobic interface layer that com-
monly features in Schroeder’s paradox arguments to explain
the water uptake of thick (>20 lm) films. However, relaxation
may also make a significant contribution to the slow uptake
dynamics, especially for these thin films with very short diffu-
sion lengths. In the absence of structural data to confirm and
quantify the structure and composition of the interface layer,
it is difficult to separate interfacial transport resistance and
slow uptake dynamics due to polymer relaxation.
Understanding how nanometer-scale thick films of ion-con-
taining polymers absorb water and probing the water self-
diffusion, conductivity, and ionic domain morphology in
these thin films are important in understanding how these
polymers behave in high surface area porous electrodes. In
these electrode structures, the ionomer is generally distrib-
uted as thin films throughout the electrode layer as a com-
posite with the catalyst particles. The function of many elec-
trochemical devices relies on a delicate balance of ion
conductivity, electrical conductivity, reactant and product
molecular transport, and exposure of the reactive sites.
 WWW.POLYMERPHYSICS.ORG
Currently in fuel cells, the electrode is a complex mixture of
components without the appearance of regular order,83 with
perhaps just one notable exception that has demonstrated
excellent performance but still has shortcomings in terms of
its ability to operate under freezing conditions.84 Extending
studies of the structure–function relationships of bulk ion-
containing membranes to nanometer-scale thin films85,86 will
promote more rational design of polymer composite electro-
des and promote new tools and concepts to understand their
performance.
CONCLUSIONS AND DIRECTIONS
As the use of ion-containing polymers are expanded to new
uses and new technologies, specific focus on the role of
water in determining these polymers’ transport, permselec-
tivity, and mechanical properties will help to accelerate their
development. Specifically, development of materials for alka-
line fuel cells that require hydroxide (OH
) polymeric con-
ductors and redox flow batteries where high proton conduc-
tivity and low vanadium ion crossover is desired can benefit
from the body of knowledge surrounding proton conducting
membranes for fuel cells.
Alkaline membrane fuel cells are important because they
have the potential to free fuel cell technology from the cost
constraints of precious metal catalysts. Catalyst corrosion
may not be as severe in fuel cells with a high internal pH as
compared to the more well-known acidic PEMFCs, and the
membrane-based architecture affords facile device and sys-
tem operation. Yan and Hickner87 have outlined the critical
relationship between bicarbonate conductivity and water
uptake for a series of poly(sulfone)-based anion exchange
membranes (AEMs). A strong correlation was observed
between the bulk water uptake of a series of AEMs and their
bicarbonate conductivity, regardless of IEC. The methanol
permeability also scaled proportionately with the bulk water
uptake and the activation energies of ion conduction and
methanol permeability were inversely related to the amount
of water in the membrane. It is possible that the hopping
properties of hydroxide will reveal different trends as has
been observed with bicarbonate (which does not undergo
hopping transport), but rigorous measurements of hydroxide
conductivity remain difficult due to rapid adsorption of CO2
in AEMs.
Interestingly, the water self-diffusion in AEMs appears to
scale differently with ion content compared to the relation-
ships observed for PEMs (Fig. 6).3,88 NAFIONV has a high
R to preserve the integrity of the cation for membranes in hy-
water self-diffusion coefficient because of its large ionic
domains. The difference in water association with cationic
polymers compared to anion polymers may be similar to
that measured in cationic and anionic reverse micelles.
Dokter et al.89 have shown that water interacts less strongly
with ions in CTAB (cetyltrimethylammonium bromide, a cati-
onic quaternary ammonium-based surfactant) reverse
micelles compared to water in AOT (sodium bis(2-ethy-
thexyl) sulfosuccinate, an anionic sulfonate-based surfactant)
reverse micelles. The difference in water hydrogen bonding
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REVIEW
FIGURE 6 Water self-diffusion coefficients of NAFIONV
R (~),
sulfonate (n) and quaternary ammonium (l) functionalized
poly(aromatic) membranes. Data taken from Ref. 3.
in the presence of anions versus cations was invoked to
explain the differences in the two systems. Similar physics
may be at play in quaternary ammonium-containing AEMs in
comparison to sulfonated PEMs, which could drive different
relationships in their water uptake and ion conductivity
properties.
It is likely that other studies of AEMs have uncovered similar
trends in the water uptake.90–92 However, more focus on the
basic structure–property relationships of these materials is
needed if their conductivity and water uptake properties are
to be further optimized. There also exists the interesting
potential to study the influence of polymer architecture93,94
and cation type95,96 in these types of materials, which will
expand the fundamental knowledge surrounding the proper-
ties of ion-containing polymer membranes with tethered cat-
ions. The hydration/conductivity tradeoff is critical to opti-
mize in AEMs, but hydration may be important for avoiding
degradation of the cation as demonstrated by Chempath
et al.97 Sulfonated polymers are known to degrade when
they are stored in anhydrous conditions or at high tempera-
tures for significant amounts of time in the acidic form.
There is much less degradation observed for sulfonated
membranes in the sodium or tetrabutyl ammonium neutral-
ized form. The quaternary ammonium functionality of AEMs
is less stable than sulfonate groups, so hydration strategies
droxide or bicarbonate (that becomes hydroxide at higher
temperatures under low pCO2 conditions) forms are a consid-
eration when designing membranes for a specific use. Stor-
age of these materials in their chloride form appears to miti-
gate any degradation due to the weak nucleophilicity of the
chloride anion.
Redox flow batteries are a viable technology for grid-scale
energy storage and can serve as buffering capacity for wide-
spread renewable energy deployment. In vanadium redox
flow batteries (VRFBs), the redox reactions that store and
JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2012, 50, 9–20 17
 REVIEW
discharge electrical energy are balanced by the flow of pro-
tons across a membrane separating the anolyte and catholye
containing V2þ/V3þ and V4þ/V5þ reversible redox species.
High proton conductivity of the membrane lowers the resis-
tive contributions to the efficiency loss in these types of
devices, but vanadium ion diffusion through the membrane
must be prevented. Transport of the vanadium redox species
across the membrane causes capacity fade during reversible
cycling of the battery. The redox activity of the electrolytes
can be regenerated, but maintenance of the electrolyte
causes downtime of the energy storage device and adds
maintenance costs to the overall system. As grid-scale energy
storage devices are multi MW-class systems, any additional
fixed or operating expenses must be kept to an absolute
minimum.
In one study by Kim et al.,98 NAFIONV-based cells experienced
R
a capacity loss of 13 mA h per cycle over 40 cycles compared
to a 6.4 mA h per cycle decline over an equivalent number of
cycles for VRFBs with sulfonated poly(sulfone) RADELV mem-
R
branes. The sulfonated poly(sulfone) membrane displayed six
times less V4þ ion transport than NAFIONV which was the ori-
R
gin of its low capacity fade. So far, there are no studies of
how the water binding in ion-conducting membranes influen-
ces the vanadium crossover in VRFBs or transport processes
in different types of flow batteries, such as iron-chromium or
zinc-bromine.99 However, the trends in the comparison of va-
nadium ion transport in NAFIONV membranes and sulfonated
R
aromatic PEMs appears to be similar to what has been
observed for methanol transport (Fig. 5). The biggest caveat
thus far in applying membranes other than PFSAs to VRFBs
appears to be the increased degradation observed in the case
of sulfonate poly(sulfone) membranes.100 New, more intrinsi-
cally stable polymers and membrane engineering strategies101
will help to alleviate the lifetime problems of non-PFSA mate-
rials, but the demand for tens of thousands of hours of cycle
life will remain a challenge.
To conclude, there are many facets to the design of new ion-
containing membranes for electrochemical and water treat-
ment applications.102 This review article has emphasized the
role that water–polymer associations play in controlling the
properties of these materials, but the effect of ionic domain
morphology and other factors such as charge concentration
in these systems influence the water behavior and ultimately
couple to the transport properties. There is no single, simple
predictor of conductivity and permeability in ion-conductiv-
ity membranes, but investigations of the water behavior
have opened up areas of fundamental interest and technolog-
ical importance and provide one set of design criteria for
optimizing these materials for a specific purpose.
ACKNOWLEDGMENTS
M.A.H. thank the Penn State Materials Research Institute, the
Penn State Institutes of Energy and the Environment, the U.S.
Army Research Office (W911NF-08-1-0282 and W911NF-11-1-
0411), the U.S. Office of Naval Research (N00014-08-1-0730 and
N00014-10-1-0875), and the U.S. National Science Foundation
18 JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2012, 50, 9–20
WWW.POLYMERPHYSICS.ORG
(CBET-0932740) for support of his group’s research in the syn-
thesis, properties, and applications of ion-containing polymers.
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