European Polymer Journal 40 (2004) 13091316

EUROPEAN
POLYMER
JOURNAL
www.elsevier.com/locate/europolj

Vibrational and thermal characterization of Naon

membranes substituted by alkaline earth cations
La
ercio Gomes Lage, Patr
cia Gomes Delgado, Yoshio Kawano

Departamento de Quimica Fundamental, Instituto de Qu
mica, Universidade de S~ao Paulo, Av. Prof. Lineu Prestes 748,
Caixa Postal 26077, CEP 05513-970, S~ao Paulo, SP, Brazil
Received 24 December 2003; received in revised form 10 February 2004; accepted 17 February 2004
Available online 9 April 2004

Abstract
The vibrational spectra of Naon membranes with alkaline earth cations as counterions have been obtained by
photoacoustic infrared spectroscopy (PASIR) and Fourier transform Raman spectroscopy (FT-Raman). The symmetrical stretching band of the sulfonate group (
1060 cm1 ) decreases with increasing atomic mass of the countercation, excepting for Mg2 , in both techniques. The thermal behavior of Naon membranes by means of dierential
scanning calorimetry (DSC) curves showed a dependence on the water content and a similar prole between NaonMg2 and -Ca2 , and between Naon-Sr2 and -Ba2 , for the rst scanning curve. An ageing eect was also observed on
Naon by DSC curves. High-resolution thermogravimetry (TG) curves under nitrogen atmosphere showed similar
decomposition proles. It was determined from TG curves that there is a decreasing water content with increasing ionic
radius of cation, and the thermal stability increasing from Naon-Mg2 to -Ba2 .
2004 Elsevier Ltd. All rights reserved.
Keywords: Naon ; Peruorosulfonated ionomers; Photoacoustic infrared spectroscopy; FT-Raman; DSC; TG

1. Introduction
Naon is a peruorosulfonated ionomer that possesses high chemical, mechanical and thermal stability,
due to a polytetrauoroethylene (PTFE) backbone with
a side chain terminated in a sulfonated cation exchange
site in its structure. It is used mainly as membranes in
chlor-alkali cells for the production of chlorine and
caustic soda and also as membrane fuel cells [1]. The
detailed characterization of Naon membrane is essential for the development of its technological applications.
The use of alkaline earth cations as counterions of
Naon has been investigated [28]. Steck and Yeager [2]
have measured the selective coecient for ion exchange
in as-received and expanded Naon membrane per-

Corresponding author. Tel.: +55-11-3091-2165; fax: +5511-3815-5579.

E-mail address: ykawano@iq.usp.br (Y. Kawano).

formed for alkali metal ions and alkaline earth ions. Xie
and Okada [3] have determined the water transport
behavior in Naon in the acid, alkaline, and alkaline
earth forms. The water transport behavior is related to
the surface charge density, hydration enthalpy of the
cations, and the water content in membrane. It is shown
that the protons are transported in a dierent mechanism compared to the other cations. The size of micropores in Naon was also calculated by Xie and
Okada [3] using the xed charge theory, and it is
dependent of the cation, ranging from 0.76 to 1.3 nm. It
is also demonstrated that the membrane is cationselective. A re-evaluation of these results were published
later [4], showing that the electrostatic interaction between the cation and water dipoles and the size of cations are important factors to be considered.
Pineri et al. [5,6] have studied the swelling of acid
Naon and Naon with dierent counter-cations (Na ,
Cu2 , Fe3 ) by thermal analysis, mechanical and
spectroscopic experiments. They have shown that the

0014-3057/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2004.02.021

1310

L. Gomes Lage et al. / European Polymer Journal 40 (2004) 13091316

endothermic and exothermic DSC peaks appear and

these can be interpreted in terms of desorptionsorption
during the thermal cycling.
Asaka et al. [7] have investigated the water state inside Naon and the ionic conductivity of the membranes
with dierent counterions, including alkaline earth cations. The ionic conductivity depends on the size of the
cation and the freezable water content, estimated from
DSC curves. The non-freezable water is considered to
interact strongly with the sulfonate groups.
Shi and Anson [8] have studied the dehydration of
Naon induced by cation exchange and showed that the
alkaline earth cations investigated (Mg2 and Ca2 )
expelled 37 water molecules per exchanged cation,
respectively.
Goswami et al. [9] have measured the self-diusion
coecients of some cations in Naon. It was observed
dierent trends for monovalent and divalent cations.
The selectivity sequence of the cations having the same
charge obeys the sequence of decreasing radii of the
hydrated ions, following the reverse trend of the selfdiusion coecient, that is governed by the water uptake capacity of the membrane.
Mauritz and Rogers [10] have proposed a model of
equilibrium hydration states of clustered ionomer
membranes.
Falk [11] has studied the IR spectra of partly deuterated water in the hydrated Naon membrane and
showed two distinct bands corresponding to two dierent environments of the OH groups: OH  O and O
H  CF2 . Quezado et al. [12] have studied the IR spectra
of Naon membrane in various cationic forms to characterize the wateranioncation interactions at low
water contents.
Xie et al. [13] have studied the IR spectra of fully hydrated Naon membranes with dierent countercations.
It was observed a shift in the stretching and bending
bands of water, as well as in the symmetrical stretching of
sulfonate groups, as a function of the cation exchanged.
Ostrowska and Narebska [14,15] have investigated the
acid Naons IR spectra at dierent degrees of hydration.
The behavior of sulfonic groups in Naon was related to
their degree of hydration: the more hydrated the membrane, the more dissociated and strongly hydrated the
sulfonic groups are. When the membrane is thoroughly
dried, most of the sulfonic groups are undissociated,
interacting with each other by hydrogen bonds. Iwamoto
et al. [16] has also studied the role of water in acid Naon
membranes by IR. It was observed some spectral features
upon drying Naon: two absorption bands weaken with
progressive dehydration (
3415 and 1730 cm1 ) and
other two bands intensify (
29002740 and 2200 cm1 ),
and the presence of two isosbestic points at 3027 and
2043 cm1 . These features were associated with the
equilibrium between water, hydronium ions (H3 O ),
sulfonate (SO
3 ) and sulfonic acid (SO3 H) groups.

The thermal stability of Naon membrane has been

studied by several authors [1727], especially the membrane in acid form [1719,23,26,27]. Surowiec and
Bogoczek [17] have investigated the thermal stability of
Naon in air atmosphere, as well as its products of
decomposition, by simultaneous TG-DTA analysis,
infrared (IR) spectroscopy and ion-exchange capacity
determinations. The decomposition proceeded in three
stages, the rst one being water loss, the second one the
sulfonic groups loss, and the last one the oxidative
destruction of the peruorinated matrix. Chu et al. [18]
have studied the eect of heating platinum foils coated
with Naon lms at various temperatures, by IR spectroscopy, observing the loss of sulfonic groups up to 300
C. Mauritz et al. [1921] have used the TG, DSC and
TG-IR, to investigate the thermal behavior of microand nanocomposites of Naon and organic modied
silicon (ORMOSIL) compounds, showing that the latter
improved the thermal stability of the former, inhibiting
the SO2 evolution. The thermal decomposition of Nafion membrane was also monitored via TG-IR by Wilkie
et al. [22] and via TG-MS by Samms et al. [23] and
mechanisms of decomposition were proposed: a radicalar and an anionic one. As the rst forming product
was the same on both mechanisms, it could be possible
to occur a branch into one and another pathway. The
decomposition products of Naon was also determined
by Du Pont [24], heating the sample in a stainless steel
tube in air atmosphere, and quantifying them by IR,
being them the same as determined in [2123], except for
the SiF4 , which was not observed. It was also shown by
Wilkie et al. [22], Kawano and co-workers [25,26], and
Feldheim et al. [27] that the TG curve prole was affected by exchanged countercations. Feldheim et al. [27]
have reported the dependence of the thermal stability of
Naon on the countercation (alkali metal and alkyl
ammonium). The decomposition temperature of Naon
was inversely dependent on the eective size of the exchanged cation. Kawano and co-workers [26] have
investigated the thermal decomposition of acid Naon
and Naon substituted by alkaline cations, showing that
the thermal stability, residue and water content depends
on the ionic radii of the cation exchanged. It was also
calculated the lifetime of Naon-Cs , and this ionomer
can resist up to 2 h at 300 C.
The aim of this work is to study the behavior of
Naon membrane neutralized by divalent cations concerning the water uptake, vibrational spectroscopy and
thermal stability. This research was undertaken to
compare with the results of the Naon substituted by
monovalent cations [26].
2. Experimental
Naon-117 1100 equivalent weight, with thickness of
0.177 mm (E.I. Du Pont de Nemours Co., purchased

L. Gomes Lage et al. / European Polymer Journal 40 (2004) 13091316

from Aldrich) was received in the acid form. In this

work it was used only the as-received Naon membrane,
without any previous treatment. The substitution of
counterions was performed as follows: the membranes
were stirred for 24 h with the alkaline earth chloride
(Mg2 , Ca2 , Sr2 and Ba2 ) aqueous solution of concentration 0.25 mol dm3 , at ambient temperature, followed by washing with deionized water and drying the
supercial water with lter paper.
Photoacoustic infrared spectra were recorded from
500 to 4000 cm1 in a Bomem FT-IR DA3.16 spectrometer coupled to a MTEC photoacoustic cell model
200, with helium as purging gas and a coalrubber
composite as the reference material. The resolution used
was 4 cm1 , the movable mirror speed was 0.05 cm s1 ,
and the number of co-added scans was 64.
Raman spectra were collected in a Bruker FTS 100/S
spectrometer with a Nd-YAG continuous laser (k0
1064 nm) and power of 100 mW, ranging from 200 to
2000 cm1 , spectral resolution of 4 cm1 , and 64 coadded scans.
The TG experiments were performed under nitrogen
atmosphere at 100 cm3 min1 on a TA Instruments HiResTM TGA 2950 interfaced to the Thermal Analyst
2000 software. Sample mass was in the range of 2.00
3.50 mg, the crucible used was made of platinum, and
the temperature range was from ambient to 700 C.
TGA were used in high-resolution variable heating
rate temperature program. The high-resolution TG
mode in the dynamic rate uses as an approach a mathematical function that relates the rate of change of
sample mass to the sample heating rate [28,29]. As the
rate of change of sample mass increases, the heating rate
is decreased, being the result a lowered heating rate
through the decomposition step. Three experimental
parameters need to be selected to perform a dynamic
heating rate experiment: the initial (maximum) heating

1311

rate, the resolution index and the sensitivity. The

increasing resolution implies in a lower heating rate and
consequently an increasing separation of close events of
mass loss, as well as the experiment time. For the
experiments conducted here, the initial heating rate was
20 C min1 , whereas the setting for resolution was 3 and
the sensitivity 1 (default value). These parameters were
selected to obtain well-resolved mass loss steps as well as
to avoid long analysis time.
The DSC curves were obtained on a TA Instruments
DSC 10 interfaced to the Thermal Analyst 2000 software, in the following conditions: heating rate of 10
C min1 , semi-hermetic aluminum crucibles, nitrogen as
purge gas at 30 cm3 min1 , temperature range from )50
to 350 C. Aged samples of Naon, kept in dark closed
asks during two years, were subject to two dierent
procedures: (a) for the cation exchanged Naon, rehydration for 24 h, under stirring; and (b) for the acid
Naon, cation exchange with the respective alkaline
earth chloride solution for 24 h, under stirring.

3. Results and discussion

3.1. PASIR
The photoacoustic infrared spectra of Naon with
exchanged alkaline earth cations are shown in Fig. 1. It
is observed that there is a decrease in the relative
intensities for the stretching (bands A and B, near 3690
and 3500 cm1 , respectively) [11,12] and bending (
1630
cm1 ) bands of water, present inside the membrane, as
the atomic mass of the countercation increases. The
frequency (wavenumbers) of the stretching A band of
water decreases as the ionic radius increases, as observed
by Quezado et al. [12]; the increase of ionic radius may
induce polymer contraction, increasing the interaction

1
Mg2+

Intensity /a.u.

Ca2+

-1

-2

Sr2+

-3
Ba2+

4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800

600

Wavenumbers / cm-1

Fig. 1. PASIR spectra of Naon substituted by alkaline earth cations (from top to bottom): Mg2 ; Ca2 ; Sr2 ; and Ba2 .

1312

L. Gomes Lage et al. / European Polymer Journal 40 (2004) 13091316

Table 1
Vibrational bands wavenumbers for Naon membrane in alkaline earth form (m: stretching, d: bending), ionic radius [3] of the
countercation (r) and hydration enthalpies (Dhidr H) [3] of alkaline earth countercations

Sample
mH2 O A/cm1
mH2 O B/cm1
dH2 O /cm1
mSO3  /cm1
mSO3  /cm1
r/A
Dhidr H/
Naon-M2
kJ mol1
PASIR
PASIR
PAS-IR
PAS-IR
FT-Raman
Mg2
Ca2
Sr2
Ba2

3690
3689
3677
3676

3483
3488
3508
3504

1643
1628
1628
1617

1061
1069
1066
1064

1061
1064
1067
1066

0.65
0.99
1.13
1.35

1920
1552
1476
1359

accordance with Xie and Okada [13], as shown in Table

1. The weakening of the interactions between the sulfonate groups and the cations raises the frequency
(wavenumber) of the band, being the Mg2 an exception. Probably the highly hydration degree of Mg2 is
the responsible for this eectwhen comparing the
hydration enthalpy and ionic radius of Mg2 to the
other alkaline earth (Table 1), there is a large dierence
between them. The asymmetrical stretching of sulfonate
groups is overlapped with the CF2 stretching bands,
which are large and very strong, and dicult to analyze.

of the water molecules with the uorocarbon polymer

matrix. The frequency of the stretching band B decreases
as the ionic radius decreases, indicating that the smaller
the cation the stronger the interaction with water, by
hydrogen bonding; in the bending bands of water, the
observed eect was opposite. It is known that hydrogen
bonding aects these bands in this fashion, and the shift
in the bending bands is much smaller than in the
stretching bands [13]. It is proposed that the water
competes with the cations to occupy the cluster of the
membrane, and the smaller the cation the greater the
water content inside the membrane. Xie and Okada [3]
have proposed that the larger the charge density of a
cation, the larger the water volume transport, i.e., in
cations with the same charge, the larger the ionic radius,
the smaller the charge density. Shi and Anson [8] have
shown by quartz crystal microgravimetry that as Ca2
ions enter the membrane, they expelled more water
molecules than Mg2 ions do, so the water content is
greater in the membranes with smaller cations with the
same charge.
The stretching bands of sulfonate group (SO
3 ) are
also shifted under the inuence of the cation. The symmetrical stretch band (near 1060 cm1 ) is shifted to
lower wavenumbers as the radius of cation raises,
excepting for Mg2 (Table 1). These observations are in

3.2. FT-Raman
The symmetrical stretching band of sulfonate at

1060 cm1 is shifted under the inuence of cation,
following the same trend as in the IR spectra, with
Naon-Ca2 as an exception, as shown in Table 1 and
Fig. 2. As in the IR spectra, it is observed bands in the
region of 13651380 cm1 (CF stretch), 1298 cm1 (CF2
asymmetrical stretch),
1214 cm1 (CF2 symmetrical
stretch),
1176 cm1 (SO
3 asymmetrical stretch), 1060
cm1 (SO
symmetrical
stretch), 971 cm1 (COC
3
1
stretch), 803 cm (CS stretch), 731 cm1 (CC stretch),
and the bands at 373384 cm1 (CF2 bend), and 313292
cm1 (CF2 twist). The Raman spectra are similar to

0.01
Mg2+

Intensity/a.u.

0
Ca2+

-0.01

- 0.02

Sr2+

- 0.03
Ba2+

- 0.04
1500

1400

1300

1200

1100

1000

900

800

700

Wavenumbers/cm

600

500

400

300

200

-1

Fig. 2. FT-Raman spectra of Naon substituted by alkaline earth cations (from top to bottom): Mg2 ; Ca2 ; Sr2 ; and Ba2 .

L. Gomes Lage et al. / European Polymer Journal 40 (2004) 13091316

1313

Raman spectra of monovalent cations substituted Nafion membrane [13].

3.3. DSC
It is observed in DSC curves of exchanged Naon
two kinds of transitions: one series of low temperature
transitions, from )30 to 40 C; and another transition in
the region of 100200 C. The nature of the rst kind of
transition was studied by Pineri et al. [5,6] and Asaka
et al. [7], relating to the water transitions.
Table 2 exhibits the cluster transition temperatures
after the rst and the second run under nitrogen atmosphere. This transition is interpreted as a cluster loss of
water, accompanied by a polymer contraction [2], with a
resulting increase in entropy. It is observed one transition upon heatingthe cluster transition that occurs in
this region. In the case of Naon substituted by alkali
cations the very weak melting peak appear at higher
temperature [25]. In the second DSC scanning, right
after the rst run, it is not observed the cluster transition
in the same temperature region, due to no time for
reabsorption of water. After some days, however, this
peak reappears, due to water reabsorption. This peak
clearly reappears after the immersion of the membrane
in deionized water, but slightly shifted to a lower temperature region.
Pineri et al. [5,6] and Asaka et al. [7] have observed
the supercooling of water and its melting on DSC
curves, during a cooling/heating cycle, in the temperature region of )30 to 10 C. This prole was not observed in the present work.
From Fig. 3 and Table 2 it is observed that the peak
in the rst run DSC curves of Naon-Mg2 and NaonCa2 appear at temperatures higher than those for
Naon-Sr2 and Naon-Ba2 . In the second run (Fig.
4), after water reabsorption, all the curves showed almost the same prole, with Naon-Mg2 and NaonCa2 transition being shifted to the lower temperature
region near to that of Naon-Sr2 and Naon-Ba2
transition temperatures. This hysteresis eect for the rst
two cations in the second run, which transitions return
to temperatures as low as the second pair of cations
(Sr2 and Ba2 ), could be interpreted as that the rst two
cations, as they possess the minor ionic radius and,
consequently, major water content inside the cluster,
Table 2
Cluster transition peak temperatures for the rst and second
runs of DSC of Naon in alkaline earth form
Sample
2

Naon-Mg
Naon-Ca2
Naon-Sr2
Naon-Ba2

T rst run/C

T second run/C

192
193
129
132

129
118
122
123

Fig. 3. DSC curves of Naon substituted by alkaline earth

cations (from top to bottom): Mg2 ; Ca2 ; Sr2 ; and Ba2 (rst
run at 10 C min1 ).

Fig. 4. DSC curves of Naon substituted by alkaline earth

cations (from top to bottom): Mg2 ; Ca2 ; Sr2 ; and Ba2
(second run at 10 C min1 ).

would aect the cluster transition with temperature

raising. It is also observed that the rehydration of a
membrane or an acid Naon exchanged by divalent
cations show similar proles.
It was also observed that, after two years, all the DSC
curves of exchanged Naon have the same behavior as
in the second run of the previous curves (Fig. 5 and
Table 3). Rehydration of the exchanged Naon or a new

1314

L. Gomes Lage et al. / European Polymer Journal 40 (2004) 13091316

exchange made in the same previous conditions did not

aected the prole of the DSC curves. It seems that
Naon membranes, after some time stored, it loses water, producing an irreversible rearrangement in the
interactions inside the membrane.
Almeida and Kawano [30] have observed the eect of
ageing in Naon samples by UVVIS spectra. They have
shown that the water content in Naon membranes with
dierent exchanged cations is the responsible for the
variation observed in the electronic absorption spectra.
The high the water content, the more notable the eect
will be.

Probably the rst water loss changes irreversibly the

structure of the Naon, which observable eect is the
decrease in the temperature of transition. Even after
rehydrated, the behavior of Naon is dierent from the
starting membrane. After two years, it is observed that
the rehydrated aged sample and the cation-exchanged
aged Naon behave in the same way, in terms of cluster
transition temperature.
3.4. TG
The thermal decomposition prole in nitrogen
atmosphere is shown in TG/DTG curves in Figs. 6 and
7, respectively. From these curves and data in Table 4,
the water content diminishes and the residue quantity
raises with the raising of ionic radius of cation. The
prole of the TG curves is altered by the exchanged
cation (Fig. 6). The thermal stability of Naon raises
with the atomic radius of the cation, which could be
explained by the reduction of water content and a
greater interaction between the sulfonate groups and the
cations with greater ionic radius. Besides the water loss,
the TG curves of Naon presented two steps of weight
loss for the cation exchanged membrane. The rst step
of decomposition of Naon-Mg2 occurs at a lower
temperature (near 370 C), as well as its behavior in
vibrational spectra, indicates that the mechanism of
decomposition is dierent from the other cation exchanged membranes.
In the literature [22,23] is pointed out some mechanisms of Naon thermal decomposition, especially in the
acidic form. In the rst step of decomposition, excluding
the water loss, there is a breaking in the CS bonds and
COC. In the second step there is a break in the PTFE
chain (the main chain). It is noted that in the rst step
there is water, sulfur dioxide and carbon dioxide loss.

Fig. 5. DSC curves of aged Naon substituted by alkaline earth

cations (from top to bottom): Mg2 ; Ca2 ; Sr2 ; and Ba2 (rst
run at 10 C min1 ).

Table 3
Cluster transition peak temperatures for the rst run of DSC of
(a) rehydrated aged Naon membranes in alkaline earth form
and (b) cation-exchanged aged Naon membranes
Sample
2

Naon-Mg
Naon-Ca2
Naon-Sr2
Naon-Ba2

T (a)/C

T (b)/C

128
131
129
127

110
107
109
114

Fig. 6. TG curves in nitrogen of Naon substituted by alkaline

earth cations: (d) Mg2 ; ( ) Ca2 ; ( ) Sr2 ; and (}) Ba2 (20
C min1 , resolution 3).

L. Gomes Lage et al. / European Polymer Journal 40 (2004) 13091316

Fig. 7. DTG curves in nitrogen of Naon substituted by

alkaline earth cations: (d) Mg2 ; ( ) Ca2 ; ( ) Sr2 ; and (})
Ba2 (20 C min1 , resolution 3).

Table 4
Weight loss of water, temperature of initial decomposition
(after water loss) and residue quantity at 700 C

1315

transitions could be related to the water transition and

the higher temperature transitions to the cluster transition. The former transitions are prominent in the DSC
curves of Naon-Mg2 and Ca2 and are very weak or
absent in the Naon-Sr2 and Ba2 membranes. The cluster transition temperatures show an interesting behavior
related to the ageing of Naon membrane. The hydrated
or exchanged (for the rst time) membranes have typical
DSC curves. Some time later the membrane loses water
molecules and irreversibly changes its cluster structure.
The rehydrated membrane shows a distinct DSC curve,
usually with the cluster transition peak being shifted to a
lower temperature region. This shift is higher for membranes with high water content.
TG curves showed that the water content decreases
with the atomic radius of the countercation increasing.
The residue content increases with increasing the atomic
mass of the alkaline earth cation.
As we used only the as-received sample some eect
could be expected if the present work were repeated on
previously treated Naon membrane.

Sample

water/%

Ti /C

Residue/%

Acknowledgements

Naon-Mg2
Naon-Ca2
Naon-Sr2
Naon-Ba2

6
5
4
3

362
417
433
436

9
10
12
12

L.G. Lage (proc. 98/14982-8), P.G. Delgado (proc.

01/13087-0) and Y. Kawano thank FAPESP for nancial support.

There is also the formation of hydrogen uoride, silicon

uoride and carbonyl uoride, explained by a radical
mechanism elsewhere [23]. However, in alkali salt
membranes, the mechanism of degradation seems to be
dierent, because it was not observed the formation of
sulfur dioxide, maybe due to a stronger interaction between the cation and the sulfonate group, protecting it
from the decomposition. This seems to be happen in the
Naon-Mg2 membrane, while for the other cations the
interaction is not so great to avoid evolution of SO2 , due
to the prole of the TG curves.

4. Conclusions
PASIR spectra showed that the water content decrease with increasing atomic radius of alkaline earth
cations. PASIR and FT-Raman data of symmetric
stretching of sulfonate groups shifted to lower wavenumber region as the atomic radius of cation raises,
excepting for Mg2 . This exception is explained based
on hydration enthalpy of the Mg2 , which is much larger
than the other cations.
DSC curves of exchanged Naon showed two types
of transition: one in the range of )30 to 40 C and another in the range of 100200 C. The lower temperature

References
[1] Doyle M, Rajendran G. Peruorinated membranes. In:
Vielstich W, Gasteiger HA, Lamm A, editors. Handbook
of fuel cellsfundamentals, technology and applications,
vol. 3. New York: John Wiley & Sons; 2003. p. 35195.
[2] Steck A, Yeager HL. Water sorption and cation-exchange
selectivity of a peruorosulfonate ion-exchange polymer.
Anal Chem 1980;52(8):12158.
[3] Xie G, Okada T. Water transport behavior in Naon 117
membranes. J Electrochem Soc 1995;142(9):305762.
[4] Okada T, Xie G, Gorsth O, Kjelstrup S, Nakamura N,
Arimura T. Ion and water transport characteristics of
Naon membranes as electrolytes. Electrochim Acta
1998;43(24):37417.
[5] Escoubes M, Pineri M, Robens E. Applications of coupled
thermal analysis techniques to thermodynamic studies of
water interactions with a compressible ionic polymer
matrix. Thermochim Acta 1984;82(1):14960.
[6] Pineri M, Volino F, Escoubes M. Evidence for sorption
desorption phenomena during thermal cycling in highly
hydrated peruorinated membranes. J Polym Sci, Polym
Phys 1985;23(10):200920.
[7] Asaka K, Fujiwara N, Oguro K, Onishi K, Sewa S. State
of water and ionic conductivity of solid polymer electrolyte
membranes in relation to polymer actuators. J Electroanal
Chem 2001;505(12):2432.
[8] Shi M, Anson FC. Dehydration of protonated Naon
coatings induced by cation exchange and monitored by

1316

[9]

[10]

[11]
[12]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

L. Gomes Lage et al. / European Polymer Journal 40 (2004) 13091316

quartz crystal microgravimetry. J Electroanal Chem

1997;425(12):11723.
Goswami A, Acharya A, Pandey AK. Study of selfdiusion of monovalent and divalent cations in Naon-117
ion exchange membrane. J Phys Chem B 2001;105(38):
9196201.
Mauritz KA, Rogers CE. A water sorption isotherm model
for ionomer membranes with cluster morphologies. Macromolecules 1985;18(3):48391.
Falk M. An infrared study of water in peruorosulfonate
(Naon) membranes. Can J Chem 1980;58(14):1495501.
Quezado S, Kwak JCT, Falk M. An infrared study of
waterion interactions in peruorosulfonate (Naon)
membranes. Can J Chem 1984;62(5):95866.
Xie G, Okada T. Fourier transform infrared spectroscopy
study of fully hydrated Naon membranes of various
cations forms. Z Phys Chem 1998;205:11325.
Ostrowska J, Narebska A. Infrared study of hydration
and association of functional groups in a peruorinated
Naon membranepart 1. Colloid Polym Sci 1983;261(2):
938.
Ostrowska J, Narebska A. Infrared study of hydration and
association of functional groups in a peruorinated Naon
membranepart 2. Colloid Polym Sci 1984;262(4):30510.
Iwamoto R, Oguro K, Sato M, Iseki Y. Water in
peruorinated sulfonic acid Naon membranes. J Phys
Chem B 2002;106(28):69739.
Surowiec J, Bogoczek R. Studies on the thermal stability of
the peruorinated cation-exchange membrane Naon-417.
J Therm Anal 1988;33(4):1097102.
Chu D, Gervasio D, Razaq M, Yeager EB. Infrared
reectance absorption spectroscopy (IRRAS). Study of the
thermal stability of peruorinated sulphonic acid ionomers
on Pt. J Appl Electrochem 1990;20(1):15762.
Stefanithis ID, Mauritz KA. Microstructural evolution of
a silicon oxide phase in a peruorosulfonic acid ionomer

[20]

[21]

[22]

[23]

[24]

[25]
[26]

[27]

[28]
[29]

[30]

by an in situ solgel reaction3. Thermal analysis studies.

Macromolecules 1990;23(8):2397402.
Deng Q, Moore RB, Mauritz KA. Naon/(SiO2 , RMOSIL, and dimethylsiloxane) hybrids via in situ solgel
reactions: characterization of fundamental properties. J
Appl Polym Sci 1998;68(5):74763.
Deng Q, Wilkie CA, Moore RB, Mauritz KA. TGA-FTi.r.
investigation of the thermal degradation of Naon and
Naon/[silicon oxide]-based nanocomposites. Polymer 1998;
39(24):596172.
Wilkie CA, Thomsen JR, Mittleman ML. Interaction of
poly(methyl methacrylate) and Naons. J Appl Polym Sci
1991;42(4):9019.
Samms SR, Wasmus S, Savinell RF. Thermal stability of
Naon in simulated fuel cell environments. J Electrochem
Soc 1996;143(5):1498504.
Du Pont Technical Information. Naon PFSA Products
safe handling and use of peruorosulfonic acid products.
NAE 2002;301:14.
Almeida SH, Kawano Y. Thermal behavior of Naon
membranes. J Therm Anal Cal 1999;58(3):56977.
Lage LG, Delgado P, Kawano Y. Thermal stability and
decomposition of Naon membranes with dierent cations
using high-resolution thermogravimetry. J Therm Anal
Calorim 2004;75:52130.
Feldheim DL, Lawson DR, Martin CR. Inuence of the
sulfonate countercation on the thermal stability of Naon
peruorosulfonate membranes. J Polym Sci, Polym Phys
1993;31(8):9537.
Gill PS, Sauerbrunn SR, Crowe BS. J Therm Anal 1992;
38(3):25566.
Zanier A. High-resolution TG for the characterization of
diesel fuel additives. J Therm Anal Calorim 2001;64:377
84.
Almeida SH, Kawano Y. Ultraviolet-visible spectra of
Naon membrane. Eur Polym J 1997;33(8):130711.