Journal of Non-Crystalline Solids 522 (2019) 119520

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Journal of Non-Crystalline Solids

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

Protonic conductivity and thermal properties of cross-linked PVA/TiO2 T

nanocomposite polymer membranes
⁎
G.M. Aparicioa, R.A. Vargasb, P.R. Buenoc,
a
Universidad Autónoma de Occidente, Grupo de Investigación en Nuevos Sólidos con Aplicación industrial, GINSAI, Cali, Colombia
b
Universidad del Valle, Grupo de Transiciones de fase en sistemas no metálicos, Cali, Colombia
c
Instituto de Química, Departamento de Físico-Química, Universidade Estadual Paulista (UNESP), CEP. 14800-060 Araraquara, São Paulo, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Nanocomposite polymer membranes based on PVA/TiO2 were prepared by a solution casting method.
Polymer membrane Glutaraldehyde solution (GA) was used as linking agent to improve the chemical, thermal and physical prop-
PVA erties of the membranes. The degree of cross-linking was varied by changing the reaction time. The phase
TiO2 behavior of the membranes was examined by thermogravimetric analysis (TGA) and differential scanning ca-
Ionic conductivity, thermogravimetric
lorimetry (DSC). High resolution SEM micrographs show that the TiO2 nanoparticles are homogeneously dis-
Differential scanning calorimetry, lifetime
persed, whilst the PVA crosslinks with the inorganic phase and fill in the gap between the nanoparticles. The
ionic conductivity measurements were studied by impedance spectroscopy in the radio frequency range between
5 kHz to 5 MHz. Proton conductivity increases by several orders of magnitude with increasing cross-linking
reaction time, reaching a maximum of 0.016 Scm−1 at 130 °C for the PVA/TiO2 composition of 1:12%, which
was cross-linked for 42 h and then immersed in a 32 wt% KOH solution for 24 h. The ionic activation energy of
the prepared membranes ranged from 0.038 KeV to 0.121 KeV. This result was carried out to obtain an esti-
mation of the desorption time of water in the range from room temperature to the decomposition temperature
around 500 °C.

1. Introduction
Solid electrolytes (SE) have received considerable attention from
scientists of condensed matter [1–34] due to these materials presenting
complex new processes in solid state ionic diffusion and because they
may replace conventional aqueous electrolytes in many electrochemical
applications, such as batteries, supercapacitors and fuel cells [18–21].
In recent years there has been increasing interest in the synthesis and in
establishing structure-properties relationships of SEs [22–34]. Among
solid ionic conductors, the solid polymer electrolytes (SPE) membranes
have been the subject of much effort to understand the dynamics of
mobile ions in materials with disordered structure [25–30]. Synthesis,
structural modification and blending of existing SPEs, as well as or-
ganic/inorganic composite membranes preparation are among the most
successful approaches to improve their mechanical, electrical, and
thermal properties [1–3,12,22,23].
The most commonly used membranes as solid electrolyte in elec-
trochemical devices such as proton exchange membrane (PEM) fuel cell
are the perfluorosulfonic acid (PFSA) membranes [27], commercially
referred as Nafion® membrane. However, cheaper and easier prepared
membranes other than the costly Nafion are urgently needed for wide
application in fuel cell (FC) technology. Reduction of membrane cost
could be achieved by using non-fluorinated polymer electrolytes. From
commercial point of view, Polyvinyl alcohol (PVA) is a possible can-
didate to be used as PEM because of its low cost, good chemical sta-
bility, film-forming ability, and high hydrophilicity and availability of
cross-linking sites to create a stable membrane with good mechanical
properties and selective permeability to water [2]. Moreover, PVA has
high dielectric strength, good charges storage capacity and dopant-de-
pendent electrical and optical properties. It has carbon chain backbone
with hydroxyl groups attached to methane carbons. These OH groups
can be a source of hydrogen bonding and hence assist the formation of
polymer composites [2].
Alkaline solid polymer electrolytes based either on polyethylene
oxides (PEO) or PVA have been studied for application on NieCd,
NieZn [1,2], and Ni–MH secondary battery systems [3,4]. In these
studies, ionic conductivity as high as 10−3 Scm−1 at room temperature
was achieved in the PEO-KOH polymer electrolyte. Yang and Lin
[14,15] studied and prepared the alkaline polymer electrolytes based
on PEO-PVA-KOH for use on Ni-MH [5] and Zn – air batteries [6,8,9].

⁎
Corresponding author.
E-mail address: paulo-roberto.bueno@unesp.br (P.R. Bueno).

https://doi.org/10.1016/j.jnoncrysol.2019.119520
Received 1 March 2019; Received in revised form 9 June 2019; Accepted 10 June 2019
0022-3093/ © 2019 Elsevier B.V. All rights reserved.
G.M. Aparicio, et al.
Lewandowski et al. [16] synthetized PEO-KOH polymer electrolyte for
electric double layer capacitors.
The addition of ceramic filler into polymer matrix has proved to
reduce the glass transition temperature (Tg) and the crystallinity of the
polymer, and also allow the increase of the amorphous phases of
polymer matrix, then increase the ionic conductivity [17,21,22,24,25].
These experimental results indicated improvements in the ionic con-
ductivity, thermal, and mechanical properties as the different ceramic
fillers are added into solid polymer electrolyte (SPE). The reason for the
increase of ionic conductivity of nanocomposite polymer electrolyte
was explained by the fact that the ceramic particle fillers in the polymer
matrix created some defects and free volume at interface between the
ceramic particle and the polymer chain [25].
In the case of the PFSA membranes, the water content into mem-
branes is an important factor to increase the ion conductivity [32,33].
However, the excess of water absorption usually results in a higher
degree of membrane swelling, which leads to a decrease in the me-
chanical properties. Swollen PFSA ionomers have a phase-separated
morphology, where the water and ions form hydrophilic domains se-
parated from the hydrophobic polymer matrix. The hydrophobic poly-
tetrafluoroethylene (PTFE) backbone of the ionomer membrane main-
tains the structural integrity and the ionic (sulfonic acid) groups can
attach to water molecules. Thus, in the presence of water, hydrophilic
water-filled ionic domains, or pores, are formed enabling ion con-
ductivity.
In the case of PVA, the conformation, orientation of the OH groups,
and chemical bonding might play an important role in both surface
wettability of a PVA membrane and interaction of its polymer chain
with constitutional water. Besides of this, this polymer can easily in-
teract with inorganic salts and acid to form an ionic conductor in a
polymer matrix. Our previous findings indicate that the chemical and
proton transport properties of PVA/H3PO2 membranes are both directly
linked to a two-phase structure, where liquid-like H3PO2/H2O na-
noclusters expand to hold water molecules during swelling, whereas the
solid-like polymer backbone maintains the structural stability [28–30].
Theoretical support of ion conduction in the solid state is based on
the phenomenology of crystalline defects and jumps of ions between
sites created by the network or matrix of the material [35].
In this work, we studied nanocomposites polymeric cross-linked
PVA-based, in which particles of TiO2 are dispersed within the poly-
meric matrix, in order to know its thermal stability and its behavior as
ionic conductor, after it previously be immersed in a solution KOH
aqueous.
DSC and TGA were used to analyze the thermal stability and phase
behavior of cross-linked PVA/TiO2 composite polymer membranes.
High resolution SEM micrographs (FEG-MEV) were used to verify the
insertion and distribution of the TiO2 nanoparticles in the PVA matrix.
The ionic conductivity of alkaline PVA/TiO2 composite polymer
membranes was measured by impedance spectroscopy. The results al-
lowed us to classify the obtained polymeric electrolyte, as a good no-
minee to be selected as proton exchange membrane for fuel cells.
2. Experimental
2.1. Preparation of the nanocomposite PVA/TiO2 polymer membranes
We used 98% hydrolyzed PVA (Aldrich), with a degree of poly-
merization between 13,000 and 23,000 and nano-sized TiO2 fillers with
an average diameter of 21 nm (99% pure, Acros Organics) as starting
materials. Membranes with weight ratio (X wt%) of PVA/TiO2, 1: X wt
% where 0 < X < 20 were prepared. Preparation of the solid polymer
composites was carried out by adding TiO2 particles to the PVA viscous
aqueous solutions prepared as described in Ref. [17] and stirring con-
tinuously at 65 °C for 2 h under an air atmosphere with a relative hu-
midity of 65%. The resulting viscous solution was poured into a glass
container. After one week, we obtained smooth, uniform and thin
2
Journal of Non-Crystalline Solids 522 (2019) 119520
(between 0.2 and 0.3 mm thickness) membranes. The aspect of the
membranes with TiO2 particles showed a translucent white coloration
and they were mechanically robust.
2.2. Cross-linked and ionization of PVA/TiO2 composite polymer
membranes
After casting the prepared membranes with a PVA/TiO2 con-
centration, they were cross linked with glutaraldehyde. For that they
were immersed in a solution of 5 wt% glutaraldehyde (GA, 75% content
in distilled water, Fisher Across), 0.5 vol% HCl (used as a catalyst,
Panreac) and acetone for the cross-linking reaction at 40 °C for different
times, i.e., 18, 24 and 42 h. To activate the ion-conducting capability of
the cross-linked PVA/TiO2 composite membranes, they were immersed
in 32 wt% KOH solutions for at least 24 h before electrical measure-
ments were conducted [24].
2.3. Surface morphology, thermal analysis and impedance spectroscopy
A high-resolution SEM equipment (FEG-MEV) was used to examine
the surface morphology, interfacial characteristics and failure me-
chanism in the evaluation of adhesion and distribution of the TiO2
nanoparticles in the PVA matrix. The membranes were previously
coated with graphite to correct their transparency. Micrographs were
taken from both sample's faces and profile expanded to various mag-
nifications. DSC thermal analysis was done using a TA instruments DSC
Q2000 system, measurements were made on increasing temperatures
from 30 to 350 °C, at a heating rate of 10 °C/min in a N2 atmosphere
with about 10 mg sample. TGA thermal analyses were carried out using
a TA instruments TGA Q500 system. Measurements were made on in-
creasing temperature from 30 to 350 °C, under N2 atmosphere at a
heating rate of 10 °C/min with about 10 mg samples.
Conductivity measurements on the PVA/TiO2 composite polymer
membranes were measured using an AC impedance methodology.
Cross-linked PVA/TiO2 composite samples were immersed into 32 wt%
KOH solutions for at least 24 h before conductivity tests were made.
Alkaline PVA/TiO2 composite polymer membranes were sandwiched
between cylindrical stainless steel, ion-blocking electrodes, each of
8 mm diameter. The two-electrode cell was mounted on a ProboStat
sample holder connected to an impedance analyzer. Impedance spectra
were recorded at isotherms between 25 and 140 °C, using a frequency
range between 5 Hz and 5 MHz and an excitation signal of 50 mV.
Possible nonlinear effects were checked at amplitudes up to 100 mV
over the entire frequency range for a typical cell. No significant dif-
ference in the complex impedance plots were noted. The experimental
temperatures were changed at intervals of 5 °C and the corresponding
isotherm was maintained within ± 0.1 °C during each frequency-scan
by the temperature-controlled shielded chamber, under an atmosphere
of dry nitrogen.
3. Results and discussion
3.1. Surface morphology
SEM photomicrographs for the PVA/TiO2, 1:12 wt% composite
polymer membranes at different magnifications, that were cross-linked
by 5 wt% GA solutions at 40 °C for different times, are show in the
Fig. 1. In all pictures, the filler nanoparticles can be distinguished from
the polymeric matrix, although different sizes of TiO2 aggregates are
also evident. Fig. 1(a) show the SEM picture of the raw membrane
(without crosslink) in a length scale of 100 μm. It is clearly seen that the
TiO2 particles are dispersed well within the PVA polymer matrix. Other
membranes with the compositions prepared showed similar morphol-
ogies as those show in Fig. 1(a). Fig. 1(b) shows the sample crosslinked
by GA during 18 h in a length scale of 1 μm. The square flat grain of
approximately 1 μm side corresponds to an impurity, identified by EDX
G.M. Aparicio, et al. Journal of Non-Crystalline Solids 522 (2019) 119520

Fig. 1. Micrographs of scanning electron microscopy of high resolution (FEG-MEV) for PVA/TiO2 1:12 wt% composite polymer membranes: (a) without cross-linking
at 200×; (b) cross-linked membrane in GA for 18 h, 20,000× (c) cross-linked membrane in GA for 42 h, 2000× (d) sample ionized in KOH for 24 h, 10,000× (e)
cross-linked membrane in GA for 42 h and ionized in KOH for 24 h, 5000 × .

analysis as a NaCl crystal. Fig. 1(c) shows the sample crosslinked by GA appearance as with a superficial plasticizer, as in Fig. 1 (e) for the
for 42 h in a length scale of 10 μm, resulting in a more uniform and composite that has link crossing in GA for 42 h and ionization in KOH
homogeneous membranes with the TiO2 nanoparticles well dispersed, for 24 h, in a length scale of 1 μm.
although some aggregates or chunks are still randomly distributed on
the top surface. Fig. 1 (d) shows the ionized membrane in KOH for 24 h
in a length scale of 1 μm, and it is observed that it acquires an

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G.M. Aparicio, et al. Journal of Non-Crystalline Solids 522 (2019) 119520

Fig. 2. DSC curves for: (a) pure PVA; PVA/TiO2 1:12 wt% composite polymer
membrane without cross-linking; (c) cross-linked membrane in GA during 42 h;
(d) membrane without cross-linking that was immersed in KOH during 24 h; (e)
cross-linked membrane in GA during 42 h and then immersed in KOH during
24 h.
Fig. 3. TG and the corresponding temperature derivative DTG curves of PVA/
3.2. Thermal analysis TiO2 1:12 wt% composite polymer membranes: (a) without crosslink; cross-
linked membranes for (b) 18 h, (c) 24 h and (d) 42 h. Temperature range be-
DSC curves of the PVA membrane and the PVA/TiO2, 1:12 wt% tween 30 and 450 °C.
composite polymer membranes that were cross-linked by 5 wt% GA
solutions at 40 °C for different times, are shown in Fig. 2. It is well composite polymer membranes without cross-linking (Figs. 2(b) and
resolved in DSC curves for the pure PVA membrane and the raw 3(a), respectively), it is clear that the onset of decomposition of the non-
membrane (without crosslink) with concentration PVA/TiO2, 1:12 wt%, crosslinked membranes takes place at about 250 °C. Besides of this, it is
Figs. 2(a) and (b), respectively, an endothermic peak at about 210 °C, also evident from the DSC results, Fig. 2(a) and (b), that the crystalline
which corresponds to the melting temperature (Tm) of PVA polymer. part of PVA is still present in the PVA/TiO2, 1:12 wt% composite
Moreover, decomposition of these membranes is evident at higher polymer membranes without cross-linking and that decomposition of
temperatures with onset at about 250 °C. On the other hand, DSC curves both of them occurs above 250 °C.
for the membranes with the same filler concentration of 1:12 wt% that Comparing the DSC and TGA results for the PVA/TiO2, 1:12 wt%
were cross-linked in GA during 42 h, Fig. 2(c), shows a small and ir- composite polymer membranes that were cross-linked in GA during
regular endothermic region with an onset temperature at about 150 °C, 42 h (Figs. 2(c) and 3(d), respectively), it is clear that the decomposi-
and no subsequent decomposition region up to 400 °C. tion at about 250 °C has been inhibited, although the rate of weight loss
When the membranes are immersed in KOH without any previous increased with increasing cross-linking time, Fig. 3(b)–(d). Besides of
cross-linking process, the endothermic peak associated with the melting this, it is also evident from the DSC results, Fig. 2(c), that the cross-
of crystalline part of PVA is now observed at lower temperature, at linked PVA/TiO2, 1:12 wt% composite polymer membrane becomes
about 170 °C, while the onset temperature of decomposition is about more amorphous.
200 °C. A quite different thermal behavior to those previously shown by Comparing the weight loss at temperature in which it might be at-
the other membranes is observed for the membrane that was previously tributed to the release of constitutional water, for example between 150
cross-linked in GA for 42 h and immersed in KOH for 24 h, whose de- and 200 °C, it is clearly observed that crosslinking time determines the
composition started at about 150 °C with no clear indication of melting degree of crosslinking which can be measured by the decrease of
of PVA. swelling degree of the membranes (see Table 1). Dependence of
Fig. 3 shows the TG and the corresponding temperature derivative
DTG curves of the freshly prepared membranes (without previous
Table 1
thermal treatment) of the PVA/TiO2, 1:12 wt% composite polymer Crosslinking time dependence of the weight percentage of the PVA/TiO2;
membranes that were cross-linked by 5 wt% GA solutions at 40 °C for 1:12% composite polymer membranes with and without KOH ionization at
different times. In all the curves is observed a continuous weight loss T1 = 160 °C and T2 = 190 °C, respectively.
between 25 and approximately 150 °C, which we attribute to the re-
Composite polymer Weight percentage (%)
moval of bounding water. It is quite apparent that water removal in this
membranes
temperature range increases with increasing crosslinking time. On T1 (160 °C) T2 (190 °C)
subsequent increasing temperature, all samples show a faster variation
of weight loss, but the raw sample (Fig. 3(a)) undergoes a step variation Without KOH 24 h in Without KOH 24 h in
KOH KOH
corresponding to a total weight loss of about 55%, with an onset tem-
perature at approximately 250 °C, while those membranes that were PVA/TiO2;1:12 wt% 93.0 89.6 90.0 86.9
crosslinked (Fig. 3(b)–(d)) show a continuous rate of weight loss, whose PVA/TiO2;1:12 wt% + 92.0 86.9 90.0 84.7
total loss at 250 °C increases with increasing cross-linking time, being 18 h en GA
PVA/TiO2;1:12 wt% + 89.0 89.1 80.0 87.5
about 15, 25 and 30% for the membranes that were cross-linked during
24 h en GA
18, 24 and 42 h, respectively. PVA/TiO2;1:12 wt% + 83.0 88.1 75.0 81.1
Comparing the DSC and TGA results for the PVA/TiO2, 1:12 wt% 42 h en GA

4
G.M. Aparicio, et al.
Fig. 4. TG and the corresponding temperature derivative DTG curves of PVA/
TiO2 1:12 wt% composite polymer membranes: (a) without crosslinking, (b)
without crosslinking and after being immersed into KOH for 24 h; crosslinked
membranes for (c) 18 h, (d) 24 h and (e) 42 h and after being immersed into
KOH for 24 h. Temperature range between 30 and 450 °C.
swelling degree of the membranes on crosslinking time is shown in
Fig. 3 (as measured by the water weigh loss at 190 °C).
The results of TGA measurements for composite polymer mem-
branes that were cross-linked by 5 wt% GA solutions at 40 °C for dif-
ferent times, but after immersing them into the KOH solution for 24 h,
are shown in Fig. 4. As it was observed for the membranes without the
KOH activation Fig. 4(a), all curves show a continuous weight loss
between 25 and approximately 175 °C, which we attribute to the re-
moval of bounding water. However, it is quite apparent in these
membranes that water removal in this temperature range does not
appreciably change with increasing crosslinking time. Moreover, it is
also observed that all membranes immersed in KOH undergo a step
variation corresponding to a total weight loss of about 25% at tem-
peratures around 225 °C, less than that of the decomposition tempera-
ture for composite membrane without crosslink and KOH activation
that occurs at 250 °C, Fig. 4(a). It is important to note that the weight
loss of this group of membranes with crosslinking, which lose about
25% of their weight, is much less than the loss of weight at the site
membrane without crosslinking and activation of KOH whose loss
reaches 55%. % of its weight, which indicates the favorable effect of
crosslinking on its rate of decomposition reaction.
From the thermal analysis of prepared membranes, it is clearly
observed that crosslinking time determines the degree of crosslinking
which is reflected mainly on their phase behavior. As the crosslinking
time increases, the degree of crystallinity of the membranes is reduced
or become more amorphous, and their thermal stability and swelling
degree is increased.
3.3. Impedance spectroscopy
Figs. 5 (PVA/TiO2; 1:12 wt%) and 6 (PVA/TiO2; 1:12 wt%) show
typical Nyquist plots –Z" vs. Z', for impedance measurements of the
alkaline blend PVA/TiO2 composite polymer membrane with the
1:12 wt% composition, activated with KOH and crosslinked in GA for
42 h. Spectra were recorded at various isotherms between 30 and
130 °C. The spectra consist typically of two well defined regions: a low-
frequency region characterized by a monotonically decreasing curve
with increasing frequency followed by high frequency region
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Journal of Non-Crystalline Solids 522 (2019) 119520
Fig. 5. Nyquist plots of PVA/TiO2; 1:12 wt% composite polymer membrane
crosslinked in GA during 42 h and KOH ionization during 24 h. Isotherms
measured between 30 °C and 130 °C.
Fig. 6. Nyquist plots of PVA/TiO2; 1:20 wt% composite polymer membrane
crosslinked in GA during 42 h and KOH ionization during 24 h. Isotherms
measured between 30 °C and 130 °C.
characterized by an arc approaching the origin at the higher frequency
region. The low frequency region are typically non-vertical spikes at-
tributed to the stainless steel (SS) blocking electrodes/solid polymer
electrolyte interface, while the high frequency arc is related to con-
duction process in the bulk of the membrane. Analysis of the spectra
yields information about the electrical response of the membranes
tested, such as bulk resistance, Rb, from which the DC conductivity, σ,
can be calculated by using the formula σ = d/ARb, where d is the
thickness and A is the contact area of the samples.
Figs. 7–10 show the temperature dependence of the DC ionic con-
ductivity, log σ vs. 1000/T for the alkaline PVA/TiO2 nanocomposite
polymer membranes with TiO2 weight ratio ≤20 wt%, that were cross-
linked by 5 wt% GA solutions at 40 °C for different times. The electro-
lyte polymers belong to the solid state ion conductors, in which the
ionic conduction occurs above the glass transition temperature and
obeys the Arrhenius model which shows the dependence of the con-
ductivity with the temperature according to eq. 1:
σ = σoExp (−Ea/ kB T ) (1)
where σo is the pre-exponential factor, Ea is the activation energy and
kB is the Boltzmann constant. This model offers a good representation of
the relationship between ionic conductivity and temperature, generally
for cases where the ion-chain interaction of the polymer is very weak
[36]. Based on least square analysis of the corresponding data, the
Arrhenius model logσ = log σ0 − 0, 43Ea/kBT fits well all the plots, if a
low-temperature segment of each data plot is selected. Table 2 gives the
activation energy, Ea, as calculated from the fitting parameters. Note
that there is a low dispersion of Ea as a function of the TiO2 filler
content and crosslinking time, oscillating between 6.02 × 10−21 KeV
and 1.94 × 10−18 KeV. However, the DC conductivity is very sensible
for these preparation conditions of these membranes.
G.M. Aparicio, et al. Journal of Non-Crystalline Solids 522 (2019) 119520

Fig. 9. logσ vs. 1000/T,for the alkaline PVA/TiO2 nanocomposite polymer

Fig. 7. logσ vs. 1000/T,for the alkaline PVA/TiO2 nanocomposite polymer membranes with TiO2 weight ratio ≤ 20 wt%, that were cross-linked by 5 wt%
membranes with TiO2 weight ratio ≤ 20 wt%, that were cross-linked by 5 wt% GA solutions at 40 °C for 42 h.
GA solutions at 40 °C for 18 h.

Fig. 10. logσ vs. 1000/T,for the alkaline PVA/TiO2 1:12 wt% nanocomposite
polymer membranes, that were cross-linked by 5 wt% GA solutions at 40 °C for
Fig. 8. logσ vs. 1000/T,for the alkaline PVA/TiO2 nanocomposite polymer
18 h, 24 h and 42 h and then immersed in KOH for 24 h.
membranes with TiO2 weight ratio ≤ 20 wt%, that were cross-linked by 5 wt%
GA solutions at 40 °C for 24 h.
Table 2
Activation energy, Ea, for PVA/TiO2, 1: X wt% where 0 < X < 20.
On the other hand, the highest DC ionic conductivity values among
the membranes within the whole range of TiO2 prepared concentration Polymeric 18 h GA + 24 h 24 h GA + 24 h 42 h GA + 24 h
(≤ 20 wt%) was obtained for PVA/TiO2; 1:12 wt% crosslinked for 42 h, nanocomposites KOH KOH KOH
reaching about 0.016 Scm−1 at 130 °C and 0,00199 Scm−1 at 30 °C. It
Ea (KeV) Ea (KeV) Ea (KeV)
can be clearly seen from Fig. 10 that the DC ionic conductivity de-
creases with decreasing crosslinking times, at 130 °C for example the PVA/TiO2; 1:2 wt% 0,060 0,061 0,056
conductivities of the membranes with 12 wt% of TiO2, with crosslinking PVA/TiO2; 1:5 wt% 0,104 0,073 0,064
PVA/TiO2; 1:7 wt% 0,077 0,062 0,065
and ionized during 24H, were approximately 0.016 0.023 and 0.025
PVA/TiO2; 1:10 wt% 0,075 0,038 0,097
Scm−1 for 42H, 18H and 24H, respectively. Nonetheless, for longer PVA/TiO2; 1:12 wt% 0,057 0,078 0,113
crosslinking reaction time than 42 h, as it was observed from the FEG- PVA/TiO2; 1:15 wt% 0,069 0,091 0,121
MEV microscope scanning of high-resolution, the membranes start to PVA/TiO2; 1:17 wt% 0,054 0,068 0,058
exhibit surface failure that affect their mechanical strength and the PVA/TiO2; 1:20 wt% 0,097 0,078 0,089

ionic transport.
These results can be attributed to the fact that the dispersion of the
polymer interface. The free volume in the polymer allows charged
TiO2 nanoparticles in the PVA-base polymer allows, by their size,
molecules or proton-type vehicles (H3O+, OH−) to move easily. The
morphology and scattering properties, generate some defects or va-
ionic carrier is provided by immersing the composite in the KOH so-
cancies at the nanoparticles-polymer chains interfaces. On the other
lution for 24 h. Additionally, in swollen membranes, the distance be-
hand, crosslinking the prepared nanocomposites with GA, that was used
tween polymer chains increase, which also promote ionic carriers to
as linking agent and formed during 42 h, generates a free volume in the
pass across the membrane freely, leading to increase of membrane's

6
G.M. Aparicio, et al.
Fig. 11. Effect of the concentration of TiO2 on the conductivity values of the
polymer composition with PVA base.
ionic conductivities.
Table 2 summarizes the activation energies obtained for membranes
plotted in Fig. 6a–d, making use of the Arrhenius equation with values
that vary from 0,038 to 0,121 KeV, which is in accordance with the
literature, as reported by Sunandanna (2004) [34] for ionic conductors,
also agrees with the values reported by Jurado (2013) [37] for poly-
meric composites based on PVA; and with the values reported by Vil-
legas (2014) [38] for composites of the same nature.
Chun-Chen Yang [24] reported studies for PVA/TiO2 polymer
membranes with TiO2 concentrations on the polymer basis of 2 wt%,
5 wt%, 10 wt%, 15 wt% and 20 wt%; although the values of the ionic
conductivities that they found are in the order of our results; the acti-
vation energies found by them are quite different from ours, they report
values between 11 KJ/mol and 20 kJ/mol; these in KeV units would
give too much in comparison with the literature and with our results.
In terms of ionic conductivity, they report similar values obtained
by us. Yang [24] obtained a conductivity value for the concentration
2 wt% of the order of 0.0056 Scm−1; for 20 wt% of the order of 0.0120
Scm−, for 10 wt% of the order of 0.0528 Scm−1 and for 20 wt% of the
order of 0.0472 Scm−1, at 30 °C.
This discrepancy for the 1:2 wt% compositions are attributed to
different environmental conditions of preparation, mainly promoting
differences in crosslinking times and thermal treatments of the mem-
branes after the KOH ionization (in our case the ionized membranes
where dried under an inert atmosphere during 20 days), so swelling
degrees were certainly different.
It is important to see the effect of the concentration of TiO2 on the
polymeric base PVA as seen in Fig. 11, since this can give an indication
of the range in which better conductivity values can be expected, Yang
[24] studied the concentrations of 2 wt%, 5 wt%, 10 wt%, 15 wt%, and
20 wt%, but when observing in our results the concentration 15 wt%
always has lower values of conductivity than the concentration of 20 wt
%., effect that Yang could not observe since he did not analyze the
concentration 12% wt, additionally and maintaining the polymeric
properties of the composition, the concentration 12% wt, presents very
good conductivity values for a range of temperatures between 30 °C and
130 °C.
Although in some temperatures the concentration of PVA/TiO2,
1:20 wt% could present a higher value in conductivity, we propose
PVA/TiO2, 1:12% as a candidate for highly conductive polymer com-
posites, taking into account that the texture of the membranes with
20 wt% loses mechanical properties, this is because They have more
TiO2 ceramic material. Additionally, 12 wt% in all the times to link
crossing presents better conductivities.
7
Journal of Non-Crystalline Solids 522 (2019) 119520
4. Conclusions
Crosslinked PVA/TiO2; 1:X% with 0 < X < 20, composite polymer
membranes were prepared by a solution casting method. Crosslinking
reaction changes the polymer network: with increasing crosslinking
time, it can be noted that the structures become more amorphous and
less compact, having more accessible free volume for a liquid-like KOH
conducting phase to penetrate; therefore, the ionic conductivity is
about of the order of 10−3 S cm−1 at ambient temperature and 0.016
3 S cm−1 at 130 °C for the 42 h crosslinked PVA/TiO2; 1:12% alkaline
membrane. Moreover, the crosslinked PVA/TiO2 composite membranes
show greater thermal stability (as indicated in DSC's and TGA's results).
It is clearly remarkable that ionic conductivity of these PVA-based
composite membranes depend on swelling degree which are influenced
by the presence of hydrophilic groups and the distance of polymer
chains in membrane matrix, which are increased with GA crosslinking
reaction times and there is the dispersion of TiO2 nanoparticles into the
membranes that has a critical concentration of PVA/TiO2 of 1:12 wt%.
Acknowledgement
The authors express their gratitude to the Autonoma de Occidente
University of Cali Colombia, Valle University of Cali Colombia and
Universidade Estadual Paulista (UNESP) in São Paulo for making pos-
sible the realization of this work.
Declaration of interests
None.
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