Polymer-Plastics Technology and Engineering

ISSN: 0360-2559 (Print) 1525-6111 (Online) Journal homepage: http://www.tandfonline.com/loi/lpte20

Molecular dynamics of carboxymethyl κ/ι-hybrid

carrageenan films doped with NH4I

Fernando G. Torres, Junior Arroyo, Ricardo Alvarez, Sol Rodriguez, Omar

Troncoso & Daniel López

To cite this article: Fernando G. Torres, Junior Arroyo, Ricardo Alvarez, Sol Rodriguez,
Omar Troncoso & Daniel López (2018): Molecular dynamics of carboxymethyl κ/ι-hybrid
carrageenan films doped with NH4I, Polymer-Plastics Technology and Engineering, DOI:
10.1080/03602559.2018.1542713

To link to this article: https://doi.org/10.1080/03602559.2018.1542713

Published online: 05 Nov 2018.

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POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING
https://doi.org/10.1080/03602559.2018.1542713

Molecular dynamics of carboxymethyl κ/ι-hybrid carrageenan films doped with

NH4I
Fernando G. Torresa, Junior Arroyoa, Ricardo Alvareza, Sol Rodrigueza, Omar Troncoso a
, and Daniel Lópezb
a
Department of Mechanical Engineering, Pontificia Universidad Católica del Perú (Lima 32 Perú), Lima, Perú; bInstitute of Polymer Science
and Technology, Spanish Council for Scientific Research (ICTP-CSIC), Madrid, Spain

ABSTRACT ARTICLE HISTORY

The effect of carboxymethylation and NH4I incorporation on the molecular dynamics of carragee- Received 14 May 2018
nan films was studied. Broadband Dielectric Spectroscopy (BDS) assessed the presence of α and β Revised 4 September 2018
relaxation processes. The effect of NH4I content was analyzed using the Havriliak-Negami model Accepted 27 October 2018
and parameterizing the temperature dependence of the relaxation times according to the Vogel- KEYWORDS
Fulcher-Tammann-Hesse (VFTH) equation. The glass transition temperature was found to decrease Carrageenan;
with the increase of NH4I content. These results suggest that carboxymethylation and the salt carboxymethylation;
doping treatment increase the molecular mobility of NH4+ ions, making the films suitable for the ammonium iodide doping;
development of solid electrolytes for energy storage applications. solid electrolytes

Tg for each sample

Samples relaxation times

Tg decreases Segmental
at high NH4I flexibility
content improves

1. Introduction Previous studies have explored the potential of carra-

geenan-based films as solid electrolytes for electrochemi-
Carrageenans are a family of anionic polymers extracted
cal cell applications.[8–10] Because of the inherent low
from marine red algae that share a common backbone;
conductivity of carrageenan, chemical treatments like
alternating (1→3)-linked β-D-galactopyranose and
carboxymethylation are necessary to enhance the mobility
(1→4)-linked α-D-galactopyranose. There are three pri-
of charges. Tranquilan-Aranilla et al.[11] synthesized for
mary types of carrageenans: kappa (κ) carrageenan, iota
the first time carboxymethyl carrageenan. They found
(ι) carrageenan and lambda (λ) carrageenan. The position
that carboxymethylation increases the degree of substitu-
and number of ester sulfate groups, as well as the content
tion of hydroxyl groups, enhancing ionic conductivity.
of 3,6-anhydro-galactose, differentiates these three types
Mobarak et al.[9] found that the conductivity for carbox-
of carrageenan.[1] In nature, carrageenan is usually found
ymethyl κ-carrageenan was 2.0 × 10−4 S cm−1, in compar-
as a mixture of different polysaccharides, such as hybrid
ison to 5.3 × 10−7 S cm−1 for κ-carrageenan. Jumaah
κ/ι or κ/λ carrageenan, and other more complex forms.[2]
et al.[12] reported that the conductivity for carboxymethyl
Carrageenans have been extensively used biomedical
ι-carrageenan was 4.87 × 10−6 S cm−1. Shamsudin et al.[13]
applications[3], in food preparation[4, 5], mobility control
improved the ionic conductivity of carboxymethyl κ-
agents[6] and pharmaceutical developments.[7]
carrageenan by adding an ionic liquid, increasing the

CONTACT Fernando G. Torres fgtorres@pucp.pe Department of Mechanical Engineering, Pontificia Universidad Católica del Perú (Lima 32 Perú), Av.
Universitaria 1801, Lima 32, Lima, Perú
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpte.
© 2018 Taylor & Francis Group, LLC
2 F. G. TORRES ET AL.
ionic conductivity up to 5.76 × 10−3 S cm−1. The ionic
conductivity of carboxymethyl carrageenan can be further
increased with the addition of salt. Mobarak et al.[10] used
lithium nitrate (LiNO3). They found that the ionic con-
ductivity of carboxymethyl κ-carrageenan with 30% of
salt was 5.51 × 10−3 S cm−1. Che Balian et al.[14] added
lithium iodide (LiI) to a carboxymethyl κ-carrageenan
/carboxymethylcellulose combination, obtaining
a maximum conductivity of 3.89 × 10−3 S cm−1 with
30% of lithium iodide.
Plasticizers are organic molecules with high dielec-
tric constant and low vapor pressure. Their small size
allows them to occupy intermolecular spaces between
chains, reducing secondary forces between them and
increasing the free volume. As a consequence, the glass
transition temperature is reduced, improving the flex-
ibility of the biopolymer.[14,15] Moreover, they increase
the amorphous phase content and dissociate ion
aggregates[16], favoring ion transport mechanisms and
thus improving the ionic conductivity. As
a consequence, different studies have taken advantage
of their properties for improving ionic conductivity.
Mattos et al.[17] plasticized amylopectin-rich starch
with glycerol, obtaining a stable conductive material
with 1.1 × 10−4 S cm−1 at 30°C. Machado et al.[18]
plasticized hydroxyethylcellulose/LiCF3SO3 with 58%
glycerol, reporting a conductivity value of
1.07 × 10−5 S cm−1 at 30°C.
Broadband Dielectric Spectroscopy (BDS) is
a versatile technique widely used to study the molecular
dynamics of polymers. In the case of polymer electro-
lytes, it has been observed that dielectric spectroscopy
can be used to i) describe the ion transport behavior, ii)
obtain information about ionic and molecular interac-
tion in the solid polymer and iii) understand polymer
relaxation processes[19] such as segmental, secondary or
terminal relaxations. Previous studies have used BDS to
study molecular dynamics of carrageenan. Ikeda et al.-
[20]
identified interface polarization, characterized by
large values of the real part of the dielectric permittivity
at lower frequencies. Sanchis et al.[21] reported the
appearance of α-relaxation on dielectric loss isochrones.
Similarly, they indicated the presence of β-relaxation at
low temperatures and high frequencies. Zhu et al.[22]
found three relaxation processes: α, β, and βwet, the
latter assigned to segmental chain motions associated
with water molecules. However, there is a lack of infor-
mation regarding the dielectric behavior of carboxy-
methyl carrageenan films and carboxymethyl
carrageenan films doped with NH4I. As far as the
authors are concerned no previous characterization of
carboxymethyl carrageenan films has been carried out
using BDS.
Because of the potential applications of carrageenan
films as polymeric electrolytes, we have focused on the
analysis of the molecular dynamics of carboxymethyl κ/
ι-hybrid carrageenan films doped with NH4I. The effect
of the carboxymethylation treatment and salt concen-
tration on the thermal stability and molecular dynamics
was evaluated. The results will provide useful informa-
tion for the development of new solid electrolytes
derived from carrageenan to be used in the electronic
devices such as charge accumulators, batteries and
photovoltaic cells, among others.
2. Experimental
2.1. Carrageenan extraction
Chondracanthus Chamissoi was extracted from the
Peruvian coast. The red algae were washed and later
stored at 2°C. The extraction methodology used was
previously established by Tuvikene et al.[23] and applied
in our previous study.[24] The process was carried out in
a basic medium, refluxing the red algae in a 0.1M NaOH
solution for 4 h at 85–90°C. Isopropyl alcohol was added
to the suspension at 1:1 proportion, and then oven-dried
at 40°C for 24 h. The precipitate was repeatedly washed
to remove impurities and remnants of salt.
2.2. Carboxymethylation treatment
The carboxymethylation procedure is based on the
method established by Tranquilan-Aranilla et al.[11]
with some modifications. 1 g of carrageenan was
diluted in 100 ml of water at 90°C under magnetic
stirring for 1 h. Next, 10 ml of NaOH (40% w/w) was
added to the carrageenan solution to promote an alkali
activation. This medium was under magnetic stirring
for 1 h. Then, 0.62 g of chloroacetic acid was added,
and the mixture kept under magnetic stirring for 4 h at
40°C. The final step was the precipitation of carboxy-
methyl carrageenan with 100 ml of isopropanol alcohol.
The precipitated carboxymethyl carrageenan was
washed three times until the total removal of NaOH
and, then, dried in a vacuum oven at 40°C for 24 h.
Dried samples were stored in a desiccator.
2.3. Elaboration of films
Ammonium iodide (15%, 25%, and 35%) salt and gly-
cerol (15%) were precisely weighted and diluted in
100 ml of aqueous solution of acetic acid 0.5%. The
suspension was magnetically stirred for 2 h and then
sonicated for 20 min for disrupting possible agglomera-
tions. 1g of carboxymethyl κ/ι carrageenan was added

to the suspension and dispersed under stirring for 1 h
at 90°C. The final solution was poured onto Petri dishes
and dried in an oven at 40◦C for 24 h until film
formation. Carboxymethyl carrageenan films without
ammonium iodide and glycerol were also prepared for
comparison.
2.4. Morphological characterization
Samples were cryo-fractured and dried for 24 h in an
oven at 40°C. Field Emission Scanning Electron
Microscopy (FE-SEM) tests were carried out in
a Hitachi SU 8000 FE-SEM microscope at high vacuum
with a voltage of 25 kV.
2.5. Thermal analysis
Thermogravimetric measurements were performed
on TA Q500 equipment (TA Instruments, USA).
Samples weighing 2–5 g were heated from 30°C –
800°C at 10 °C/min and purged with a N2 atmo-
sphere at a flow rate of 20 ml/min.
2.6. Fourier Transform Infrared Spectroscopy
(FTIR)
A Perkin Elmer Spectrum One FTIR equipped with
a universal ATR sampling accessory was used. Eight
scans per sample were recorded in the 550–4000 cm−1
spectral range with a resolution of 4 cm−1.
2.7. X-Ray Diffraction (XRD)
XRD patterns were recorded at room temperature on
a BRUKER D8- FOCUS diffraction system, using Cu
Kα (λ = 1.5406 Å) radiation. The samples analysis over
2θ covered a range of 10° - 60° with a sampling interval
of 0.02°.
2.8. Broadband Dielectric Spectroscopy (BDS)
The isothermal and isochronal relaxation spectra were
determined using a Novocontrol Broadband Dielectric
Spectrometer (Hundsagen, Germany) consisting of an
Alpha analyzer to perform measurements from 1 × 10−1
to 1 × 107 Hz. The data acquisition was carried out under
an inert N2 atmosphere from −40°C to 40°C. Previous
studies have reported the Tg value of carrageenan samples
using different techniques. Martins et al.[25] used
Dynamical Mechanical Analysis (DMA) to determine
the glass transition temperature of κ-carrageenan, obtain-
ing a value between 0–10°C. Mitsuiki et al.[26] found Tg
values above 0°C using DSC and DMA tests. Sanchis
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 3
et al.[21] reported a Tg value around −50°C using
Dielectric relaxation spectroscopy. The temperature
range used in this study was chosen to assess the glass
transition temperature and avoid other transitions that
take place at high temperatures, such as melting tempera-
ture, reported around 170°C for pure κ-carrageenan.[26]
A Novocontrol Quatro cryo-system controlled the tem-
perature transition with a precision of 0.1 K. The samples
were disk-shaped sheets of around 1.2 mm in thickness
and 20 mm in diameter, according to micrometer screw
measurements. They were mounted in a dielectric cell
between two parallel gold-plated electrodes. The samples
were initially dried at 40°C in a vacuum oven until reach-
ing a constant weight. The acquisition started at the high-
est temperature, to minimize the possible effect of
moisture.
Based on the standard permittivity formalism, the
dielectric curves were fitted using the Havriliak-Negami
(HN) empirical model[27]:
Δε
ε
HN ðωÞ ¼ ε1 þ  γ (1)
1 þ ðiωτ HN Þβ
where ε1 is the unrelaxed permittivity, εs is the relaxed
permittivity, Δε is the strength relaxation defined as εs -
ε1 , and τHN is the characteristic relaxation time which
presents a temperature dependence.
The temperature dependence of the relaxation times
corresponding to the cooperative α-relaxation is usually
parameterized in terms of the Vogel-Fulcher-Tammann-
Hesse (VFTH) equation.[28,29] This equation is often
used when there is a temperature regime below which
the segmental relaxation time of polymers becomes infi-
nitely slow.[30] Since the mobility of ions is expected to
be controlled by the segmental motion, the relaxation
time is expected to have temperature dependence.[28]
 
B
τ ¼ τ 0 exp (2)
T  Tv
where τ0 is the relaxation time at infinite temperature,
B is a material parameter related to the activation
energy, and Tv is the Vogel temperature. A nonlinear
regression algorithm developed using MATLAB soft-
ware, MathWorks Inc., Natick, Massachusetts, United
States allowed calculating the required parameters.
3. Results and discussion
3.1. Morphological characterization
The analysis of FE-SEM images evidenced the effect on
the morphology of κ/ι-hybrid carrageenan by the addi-
tion of glycerol and ammonium iodide. Hybrid
4 F. G. TORRES ET AL.

carrageenan of type κ/ι displays a surface with high
roughness (Figure 1a), in agreement with reports of
Barahona et al.[31] The presence of folds and rough
areas is attributed to the immiscible mixture of carra-
geenan type κ and ι[32], produced by inherent differ-
ences between types.
Figure 1b shows the cross-section of the carboxy-
methyl κ/ι-hybrid carrageenan membrane. This surface
evidenced a slight change in comparison to the κ/ι-
hybrid carrageenan morphology. This difference can
be accounted to the carboxymethylation process,
which partially modifies the degree of miscibility of
carrageenan.
The films of carboxymethyl κ/ι-hybrid carrageenan
doped with ammonium iodide salt and glycerol
(Figure 1c–d) display a smoother cross-section than
pure carrageenan membranes. The reduction of folds
may be accounted for the addition of glycerol and
NH4I, which have plasticizing properties.[33] The
addition of a plasticizer would improve the solubility
of the components and reduce the degree of immis-
cibility of the different carrageenan types (κ and ι).
Thus, the morphology of the samples varies from an
original rough surface (pure carrageenan) to
a smoother and more continuous cross-section sur-
face (carboxymethyl carrageenan doped with salt).
3.2. Thermal characterization
TGA curves describe the thermal decomposition
behavior of the films (Figure 2). The thermal decom-
position of carboxymethyl κ/ι-hybrid carrageenan
with x-NH4I (x= 15%, 25%, and 35%) present three
stages. The first degradation step occurs between
30–150°C, and is attributed to water desorption,[34]
showing a higher weight loss at a lower salt concen-
tration (30% for NH4I). The second degradation step
takes place between 150–300°C, and is related to the
degradation of ester sulfates and functional groups of
the carrageenan chain.[35] Finally, the last region
between 300–600°C, corresponds to the carbonization
of the matrix. This process leaves approximately 40%
of the initial mass for the composites with 15% and
25% of NH4I, while this percentage increases to 50%
for the composites with 35% of NH4I, showing
a remarkable thermal stability. Those values are in

(a) (b)

(c) (d)
Figure 1. FE-SEM images of the films. (a) Pure carrageenan membrane with augmentation of 5000x. (b) Carboxymethyl carrageenan
with augmentation of 5000x. (c) Carboxymethyl carrageenan with glycerol and 15% of ammonium iodide salt with augmentation of
10000x. (d) Carboxymethyl carrageenan with glycerol and 35% of ammonium iodide salt with an augmentation of 5000x. It can be
noticed a cross-section modification from rough to a smoother surface.

Figure 2. Thermograms of carboxymethyl κ/ι-hybrid carragee-
nan with 15% glycerol and different NH4I salt concentrations
(15%, 25% and 35%).
agreement with TGA reports for other composites
based on carrageenan.[36–38]
3.3. Fourier Transform Infrared Spectroscopy
(FTIR)
FTIR spectroscopy was used for the identification of the
vibrational modes of κ/ι-hybrid carrageenan based
films. Figure 3 displays the infrared spectrum obtained
for κ/ι- hybrid carrageenan, carboxymethyl κ/ι-hybrid
carrageenan, and carboxymethyl κ/ι-hybrid carragee-
nan with different NH4I salt contents. The FTIR spec-
trum of κ/ι carrageenan shows peaks of weak intensity.
The peaks located at 3400 and 3200 cm−1 correspond to
the hydroxyl groups (OH) stretching vibration.[39] The
peak at 1220 cm−1 is associated with the O = S = O
Figure 3. FTIR spectra for carboxymethyl carrageenan with different concentration of ammonium iodide salt. Pure carrageenan and
carboxymethyl carrageenan present peaks at characteristics wavelengths. The spectra for carboxymethyl carrageenan with 15%, 25%
and 35% of ammonium iodide salt and 15% of glycerol show notorious peaks that indicate a preservation of the carboxymethyl
carrageenan functional groups.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 5
stretching vibration, which corresponds to the ester
sulfate group (SO3−).[40] The peak located at
1050 cm−1 belongs to C-OH and C-O-C vibration
groups stretching vibration.[41] The peak at 920 cm−1
of weak intensity reveals the C-O-C vibration corre-
sponding to 3,6-anhydro-D-galactose.[42] At 840 cm−1,
the peak appears due to C-O-S galactose-4-sulfate
stretching vibration, a characteristic feature of iota-
carrageenan.[43] The peak at 700 cm−1 is due to the
glucose ring stretching vibration.
The carboxymethylation process uses chloroacetic
acid, which is responsible for changing the functional
groups of the polymer and, thus, originate the appear-
ance of additional peaks in comparison with non-
carboxymethylated samples. The carboxymethylation
treatment modifies the functional groups of κ/ι carra-
geenan. The peaks placed at 1600 cm−1 and 1450 cm−1
are related to COO− variations, which are
a characteristic of carboxymethyl κ/ι carrageenan.[12]
The spectra obtained for carboxymethyl κ/ι carragee-
nan – xNH4I show the same peaks of the pure carbox-
ymethyl κ/ι carrageenan samples. Thus, the addition of
ammonium iodide salt at different concentrations did
not affect the functional groups of carboxymethyl κ/ι
carrageenan.
3.4. X-Ray Diffraction
The XRD spectra of the κ/ι-hybrid carrageenan sample
revealed the presence of 2 peaks (Figure 4). The most
pronounced peak (2θ = 20°) is a characteristic for
polysaccharides. The other peak (2θ = 29°) corresponds
to traces of contaminants, especially the presence of
NaCl from the substances used in the extraction of
6 F. G. TORRES ET AL.
Figure 4. X-Ray diffraction curves for carboxymethyl carrageenan with different concentration of ammonium iodide salt. Pristine
carrageenan and carboxymethyl carrageenan present peaks at characteristics angles. Carboxymethyl carrageenan with 15%, 25%
and 35% of ammonium iodide salt show a reduction in the peak at 2θ ~ 20°, evidencing the improvement of the amorphous
content of the composite.
carrageenan, such as NaOH.[37,44] There is no evidence
of additional peaks indicative of crystalline materials.
Therefore, κ/ι-hybrid carrageenan has shown an amor-
phous nature, as reported before.[44]
The diffractogram of carboxymethyl κ/ι-hybrid carra-
geenan showed the reduction of the maximum intensity
at 2θ ~ 20°, indicating an improvement of the amorphous
properties. The free space created promotes the contin-
uous segmental motion of the polymer chains.[12] Thus,
the increase in free volume and segmental movement of
chains may enhance the migration of ions favoring con-
ductivity, a hypothesis that will be studied through
Broadband Dielectric Spectroscopy analysis.
The peak at 2θ ~ 45° is associated with sodium
chloroacetate, a remnant of the carboxymethylation
process. This peak was also observed in the carboxy-
methyl carrageenan – xNH4I spectra but with a reduced
intensity, due to the washing stage performed during
the samples preparation.
The addition of 15% of NH4I generated no new
peaks in the samples. However, the addition of 25%
and 35% of NH4I generated two peaks at 2θ ~ 29° and
2θ ~ 33°. Those peaks become larger with increasing
NH4I content, and can be accounted for undissociated
salt molecules.[33] Simultaneously, the elevation at 2θ
~ 20° continued to drop, indicating an improvement in
the amorphous nature of the composite with higher salt
concentration.
3.5. Broadband dielectric spectroscopy
Figure 5 depicts the variation of the real part and the
imaginary part of the dielectric permittivity along with
temperature variation for several isochrones. There is
a distinguishable variation in the tendency of ε’ for
carboxymethyl κ/ι-hybrid carrageenan in comparison
to the composites doped with ammonium iodide salt.
The former presents a slight increase with increasing
temperature, after which it experiences a sudden
increase, reaching the highest value at around 25°C.
The isochrones of ε’ for all samples doped with NH4
I show similar behavior, presenting a step-like increase
which starts at temperatures around −36 °C, finally
reaching a pseudo-plateau. On the other hand, the
imaginary part of the dielectric permittivity for carbox-
ymethyl κ/ι-hybrid carrageenan describes
a monotonically increasing behavior as the temperature
increases. The step-like region can be associated with
the contribution of two conductive processes: dipolar
orientation and diffusion of charge carriers.[15,21]
The frequency dependence of the real and imagin-
ary part of the complex permittivity is shown in
Figure 6 for isothermals ranging −40°C to 40°C in
steps of 10°C. This frequency dependence can be due
to three different processes: i) molecular dipoles reor-
ientation, ii) propagation of charge carriers and iii)
charges at interface generating the sample/electrode
polarization. Figure 6 shows that ε’ exhibits an incre-
ment at low frequencies, attributed to electrode
polarization.[28,45–48] The ions in the solid electrolyte,
under the influence of the external field, tend to
move toward the sample/electrode interface and give
rise to this phenomenon. In the middle region of the
frequency range, ε’ exhibits a pseudo-plateau which
corresponds to dipole relaxation.[28] After this step-
like region, ε’ decreases with increasing frequency,
reaching a plateau at high frequencies (~ 106–
107 Hz). In general, it is observed that the higher
ammonium iodide salt concentration the polymer
contains, the higher the maximum value ε’ reaches.
 POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 7

(a) (e)

(b) (f)

(c) (g)

(d) (h)

Figure 5. Isochronal permittivity curves for temperatures between −40◦C to 40◦C. Real part of the dielectric permittivity (ε’) curves
for (a) carboxymethyl carrageenan, (b) CM-KC with 15% of NH4I, (c) CM-KC with 25% of NH4I and (d) CM-KC with 35% of NH4I. The
imaginary part of the dielectric permittivity (ε”) curves for (e) carboxymethyl carrageenan, (f) CM-KC with 15% of NH4I, (g) CM-KC
with 25% of NH4I and (h) CM-KC with 35% of NH4I.
B2 show [/NBS]?>: 10.3Hz, f3: 117Hz, f4: 1340Hz, f5: 10.2KHz, f6: 390KHz, f7: 2.96MHz and f8: 10MHz.

On the other hand, ε” present two dipolar relaxa-
tion processes. The primary (glass) α-relaxation,
given by long segments of the polymer chain, takes
place at low frequencies and displaces to high fre-
quencies with increasing temperature. The second-
ary (sub-glass) β-relaxation process, produced by
side groups motion, is seen at high frequencies.[21]
The α-relaxation process is broader for the compo-
sites than for pure matrix in the dielectric spectra,
which is in agreement with previous reports.[48,49]
The β-relaxation slightly overlaps the contribution
of the α-relaxation as the temperature increases. The
ammonium iodide salt increases the imaginary part
of the dielectric permittivity, which results more
evident with increasing temperature.
The real component of the complex conductivity
allows analyzing the conductive behavior of the sam-
ples, which was calculated in terms of the dielectric
permittivity according to σ*(ω) = iω· e0· ε*(ω), where
e0 makes reference to the vacuum permittivity. At
8 F. G. TORRES ET AL.

(a) (e)

(b) (f)

(c) (g)

(d) (h)

Figure 6. Isothermal permittivity curves for a wide range of frequencies. The real part of the dielectric permittivity (ε’) curves for (a)
carboxymethyl carrageenan, (b) CM-KC with 15% of NH4I, (c) CM-KC with 25% of NH4I and (d) CM-KC with 35% of NH4I. The
imaginary part of the dielectric permittivity (ε”) curves for (e) carboxymethyl carrageenan, (f) CM-KC with 15% of NH4I, (g) CM-KC
with 25% of NH4I and (h) CM-KC with 35% of NH4I.

low frequencies, the real conductivity for all samples
at the same temperature tends to present nearly lin-
ear frequency dependence[50] and an increasing trend
with increasing frequency. In particular, carrageenan-
based samples doped with NH4I adopted a frequency
independent behavior as the frequency increases,
which can be an indication of higher contribution
from DC compared with AC conductivity after
a certain threshold. This behavior differs from that
shown by pure carrageenan and carboxymethyl
carrageenan samples since they were strongly depen-
dent on frequency throughout the whole range. The
predominance of DC conductivity over AC conduc-
tivity for doped carrageenan composites can be more
clearly seen in Figure 7a, at 40°C around 104 Hz.
Then, the results suggest that the addition of ammo-
nium iodide salt, the selection of adequate tempera-
tures and frequencies above 104 Hz make the samples
to improve their conductivity, achieving the highest
value of 4.41 × 10−4 S cm−1.
 POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 9

(a) (b)

Figure 7. (a) Conductivity for a range of frequencies at 40◦C. (b) Conductivity for a range of frequencies at 0◦C.

For a better visualization of the NH4I effect on the
polymer matrix, an alternative formalism based on elec-
tric modulus was used. This modulus is defined as M*
(ω) = 1/ε*(ω). Sometimes this representation results
advantageous since variations in large values of permit-
tivity at low frequencies are minimized. Thus, inconve-
niences due to electrode nature and contact, charge
injection phenomena, and impurities conduction effects
can be resolved or even neglected[51]; although disadvan-
tages such as transform a featureless and frequency-
independent quantity into a frequency-dependent one,
or present more peaks than existing relaxation processes
can make the interpretation rather uncertain.[52,53]
Because of the nature of the variables analyzed here,
these disadvantages do not affect the subsequent analysis.
Figure 8a presents the temperature dependence of ε”
and M’ at 77.1 KHz. It can be identified the presence of
the α-relaxation process which is related to the glass
transition temperature Tg. The β-relaxation should be
placed at the left of the glass-transition temperature[54],
therefore it is not displayed in the diagram. The peak
height corresponding to M’ slightly increases by
increasing salt concentration (from 0.11 to 0.16).
Since most polymer researchers agree that the α-
relaxation process corresponds to segmental
motion[28], it can be concluded that the addition of
NH4I promotes the segmental motion in the composite.
A similar trend is depicted in Figure 8b, where the
increase of ε” at low frequencies is expressed by M’ as
peaks.[21]
The effect of ammonium iodide salt content on the
carrageenan-based samples was also analyzed using the
Havriliak-Negami (HN) model for the dielectric per-
mittivity formalism. This analysis allowed establishing
a temperature-dependent relaxation map, shown in
Figure 9. The temperature dependence of the relaxation
times was parameterized according to the Vogel-
Fulcher-Tammann-Hesse (VFTH) equation. The para-
meters obtained are presented in Table 1. An estima-
tion of the glass transition temperature was obtained
from the relaxation times map (Figure 9), considering
τmax = 100 s[55,56], a convention when working with the
permittivity formalism.
The glass transition temperature for the samples
decreased with the increase of ammonium iodide salt
content. Since Tg is related to the segmental flexibility
of the matrix,[57,58] the result could indicate an
improvement in the segmental flexibility of the poly-
meric chains.[59,60] It is also in agreement with litera-
ture reports[33] and is attributed to the plasticizing
effect of the salt in the host polymer structure, weak-
ening dipole interactions and promoting an easy proton
transport inside the polymer matrix, suggesting
a conductivity enhancement.
The values obtained for the relative free volume (φg/B)
at glass temperature, given by

α conductivity

(a) (b)

Figure 8. (a) Imaginary part of the dielectric permittivity and electric modulus for a range of temperatures at 77.1 KHz. (b) The
imaginary part of the dielectric permittivity and electric modulus for a broad range of frequencies at 0°C.
10 F. G. TORRES ET AL.

Figure 9. Temperature dependence of the relaxation time for carrageenan based samples with different NH4I salt concentrations
(15% (circle), 25% (up triangle) and 35% (cross)). Dashed lines represent the corresponding fitting.

Table 1. VFTH fit parameters associated with the glass transition The apparent activation energy was obtained
temperature. according
Parameter/Sample CMC-15% NH4I CMC-25% NH4I CMC-35% NH4I
τ0(s) 1.15 × 10−21 1.33 × 10−19 9.59 × 10−18


M(K) 5200 4618 3072
Ea Tg ¼ 2:303RmTg (5)
Tν(K) 118.02 126.88 144.64
Tg(K) 222.96 216.45 214.77 where R= 8.31 × 10−3 K J/(K · mol). This value increases
φg/B 0.0202 0.0194 0.0228
m 45.72 54.1 58.24 with filler content increment for the carrageenan based
Ea (Tg) K J · mol-1 195.05 224.1 239.39 samples. For evaluating the suitability of the solid biopo-
lymer electrolyte for electrochemical applications, the
dielectric loss tangent (tan(δ)) should be analyzed.[47]
Tg  Tν
φg =B ¼ (3) The dielectric loss tangent curves for the composites
B
developed are frequency dependent (Figure 10). Also,
indicate that the addition of salt generated the increase the electrode polarization frequency peak shift toward
of empty space inside the material. These results are in higher frequencies as temperature increases.
agreement with X-ray findings since amorphous mate- The peak observed for tan(δ) curves corresponds to
rials present a larger amount of free space than ordered electrode polarization relaxation frequency fEP. It acts
materials (crystalline), enhancing conductivity. as a threshold, where lower frequencies region in the
The dynamic fragility index m (Equation 4) charac- dielectric spectra corresponds to electrode polarization,
terizes how fast the material dynamics changes as the and higher frequencies region corresponds to bulk
temperature approaches the glass transition material.[30,63] At low frequencies, the charge carriers
temperature[61] were aggregated in the electrodes surface, creating
a sort of electrical double layer that blocks and hinders
B the mobility of cations. The peak shifting at higher
m¼   2 (4) temperatures indicates a lower capability to form such
2:303Tg 1  Tν Tg layer, mainly due to the enhancement of ion dissocia-
tion and re-association processes.[64]
Typical values for the dynamic fragility index are An adequate material for electrochemical applica-
approximately m= 16 for strong systems and m= 200 tions should present both high real part of the dielectric
for fragile ones, whereas the minimum fragility index permittivity (ε’) and low dielectric loss tangent (tan
reported in this study was 45.72 (a value that becomes (δ)).[47] For the sake of simplicity, the values for ε’
slightly higher with increasing salt content, up to and tan(δ) at 1 KHz are summarized in Table 2.
58.24), showing a slight deviation from strong system By calculating the ratio between the real part of the
behavior. Also, the material is expected to have a strong dielectric permittivity and the dielectric loss tangent for
resistance against structural degradation when all samples, the maximum quotient between them (that
heated.[62] is, highest ε’and lowest tan(δ)) was obtained for
 POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 11

(a) (b) (c)

Figure 10. Dielectric loss tangent for a wide range of frequencies for carboxymethyl hybrid carrageenan with 15% of NH4I,
carboxymethyl hybrid carrageenan with 25% of NH4I and carboxymethyl hybrid carrageenan with 35% of NH4I at −40°C (a), 0 °C
(b) and 40 °C (c).

Table 2. Comparison of dielectric loss tangent and real part of indicating an improvement of the segmental flexibility
the dielectric permittivity values for all samples at −40◦C, 0◦C, of polymeric chains and the thermal stability of the
and 40◦C. samples, respectively.
Sample tan(δ) ε’
The ionic conductivity was dependent on the NH4
−40°C Carrageenan (C) 0.002 0.851
CMC 0.01 3.08 I incorporation in the matrix. The analysis of the
CMC-15% NH4I 0.2 1.9 dielectric permittivity showed that carrageenan-based
CMC-25% NH4I 0.03 1.37
CMC-35% NH4I 0.34 2.81 composites doped with 35% NH4I present simulta-
0°C Carrageenan (C) 0.129 1.04 neously the highest ε’ value and the lowest tan(δ)
CMC 0.059 4.35
CMC-15% NH4I 4.92 31.1 value. The carboxymethylated samples with 35% of
CMC-25% NH4I 14.7 1070 NH4I exhibited the highest ionic conductivity found
CMC-35% NH4I 7.7 1320
40°C Carrageenan (C) 0.193 1.57 in this study: 4.41 × 10−4 S cm−1. Based on the results,
CMC 0.066 4.34 it can be concluded that carboxymethyl κ/ι-hybrid car-
CMC-15% NH4I 0.944 9.96 × 104
CMC-25% NH4I 1.82 2.24 × 104 rageenan composites doped with NH4I, are suitable
CMC-35% NH4I 1.41 1.71 × 105 materials for the development of new biopolymer-
based electrolytes for electrochemical applications.

carboxymethyl κ/ι-hybrid carrageenan with 35% of

ammonium iodide salt content, which suggests that
the material can be potentially useful for electrochemi-
cal applications.
4. Conclusions
The effect of the carboxymethylation treatment and
NH4I content on the structure and molecular dynamics
of carrageenan-based films was investigated. FE-SEM
studies showed that carboxymethylation slightly
improved the carrageenan miscibility degree, further
improved by the addition of NH4I. TGA results evi-
denced a direct dependence between the NH4I content
in the samples and the final percentage of initial mass
as temperature increases. FTIR spectra revealed the
modification of functional groups as a consequence of
carboxymethylation. The FTIR peaks remained
unchanged after salt addition and confirmed the inter-
actions between ammonium ions and carbonyl groups,
as well as between ester groups and sulfate groups in
the composite. The glass transition temperature
decreased from 222.96 K to 214.77 K, and the dynamic
fragility index increased with increasing NH4I content,
Acknowledgments
This work was supported by the Vice-Rectorate for Research
of the Pontificia Universidad Católica del Perú, the National
Council of Science, Technology and Technological
Innovation of Peru (CONCYTEC/FONDECYT) and The
National Innovation Program for Competitiveness and
Productivity (INNOVATE-PERU) of the Peruvian Ministry
of Production.
Disclosure statement
No potential conflict of interest was reported by the authors.
Notes on contributor
Prof. Fernando G. Torres obtained his Ph.D. degree in
Polymer Engineering at the University of Manchester, UK.
He is a full professor at the Department of Mechanical
Engineering, Pontifical Catholic University of Peru and
Head of the Laboratory of Polymers and Bionanomaterials.
His research interests are focused on the structure-property
relationships in biomaterials and developing new functional
bionanocomposites
12 F. G. TORRES ET AL.
ORCID
Omar Troncoso http://orcid.org/0000-0001-9621-2435
References
[1] Necas, J.; Bartosikova, L. Carrageenan. Vet. Med. 2013,
58, 187–205. DOI: 10.17221/VETMED.
[2] Jiao, G.; Yu, G.; Zhang, J.; Ewart, H. S. Chemical
Structures and Bioactivities of Sulfated
Polysaccharides from Marine Algae. Mar. Drugs.
2011, 9(2), 196–223. DOI: 10.3390/md9020196.
[3] Kumar, A.; Madhusudana Rao, K.; Haider, A.;
Han, S. S.; Son, T. W.; Kim, J. H.; Oh, T. H.
Fabrication and Characterization of Multicomponent
Polysaccharide/Nanohydroxyapatite Composite
Scaffolds. Polym. Plast. Technol. Eng. 2017, 56(9),
983–991. DOI: 10.1080/03602559.2016.1247279.
[4] Sagiri, S. S.; Anis, A.; Pal, K. Review on Encapsulation
of Vegetable Oils: Strategies, Preparation Methods, and
Applications. Polym. Plast. Technol. Eng. 2016, 55(3),
291–311. DOI: 10.1080/03602559.2015.1050521.
[5] Regand, A.; Go, H. D. Structure and Ice
Recrystallization in Frozen Stabilized Ice Cream
Model Systems. Food. Hydrocoll. 2003, 17(1), 95–102.
DOI: 10.1016/S0268-005X(02)00042-5.
[6] Darmayanti, M. G.; Radiman, C. L. Synthesis and
Characterization of Kappa-Carrageenan-Graft-
Acrylamide for Enhanced Oil Recovery Application.
Polym. Plast. Technol. Eng. 2015, 54(3), 259–264.
DOI: 10.1080/03602559.2014.976917.
[7] Liu, J.; Zhan, X.; Wan, J.; Wang, Y.; Wang, C. Review
for Carrageenan-Based Pharmaceutical Biomaterials:
Favourable Physical Features versus Adverse
Biological Effects. Carbohydr. Polym. 2015, 121,
27–36. DOI: 10.1016/j.carbpol.2014.12.044.
[8] Arof, A.; Shuhaimi, N.; Alias, N.; Kufian, M.; Majid, S.
Application of Chitosan/Iota-Carrageenan Polymer
Electrolytes in Electrical Double Layer Capacitor
(EDLC). J. Solid State Electrochem. 2010, 14,
2145–2152. DOI: 10.1007/s10008-010-1050-8.
[9] Mobarak, N.; Ramli, N.; Ahmad, A.; Rahman, M. Y. A.
Chemical Interaction and Conductivity of
Carboxymethyl κ-carrageenan Based Green Polymer
Electrolyte. Solid State Ion. 2012, 224, 51–57. DOI:
10.1016/j.ssi.2012.07.010.
[10] Mobarak, N.; Jumaah, F.; Ghani, M.; Abdullah, M. P.;
Ahmad, A. Carboxymethyl Carrageenan Based
Biopolymer Electrolytes. Electrochim. Acta. 2015, 175,
224–231. DOI: 10.1016/j.electacta.2015.02.200.
[11] Tranquilan-Aranilla, C.; Nagasawa, N.; Bayquen, A.;
Rosa, A. D. Synthesis and Characterization of
Carboxymethyl Derivatives of Kappa-Carrageenan.
Carbohydr. Polym. 2012, 87, 1810–1816. DOI:
10.1016/j.carbpol.2011.10.009.
[12] Jumaah, F.; Mobarak, N.; Ahmad, A.; Ghani, M.;
Rahman, M. Y. A. Derivative of Iota-Carrageenan as
Solid Polymer Electrolyte. Ionics. 2015, 21, 1311–1320.
DOI: 10.1007/s11581-014-1306-x.
[13] Shamsudin, I.; Ahmad, A.; Hassan, N. H.; Kaddami, H.
Biopolymer Electrolytes Based on Carboxymethyl Ҡ-
Carrageenan and Imidazolium Ionic Liquid. Ionics.
2016, 22, 841–851. DOI: 10.1007/s11581-015-1598-5.
[14] Che Balian, S. R.; Ahmad, A.; Mohamed, N. S. The
Effect of Lithium Iodide to the Properties of
Carboxymethyl κ-carrageenan/Carboxymethyl
Cellulose Polymer Electrolyte and Dye-Sensitized
Solar Cell Performance. Polymers. 2016, 8, 163. DOI:
10.3390/polym8050163.
[15] Karbowiak, T.; Hervet, H.; Léger, L.; Champion, D.;
Debeaufort, F.; Voilley, A. Effect of Plasticizers (Water
and Glycerol) on the Diffusion of a Small Molecule in
Iota-Carrageenan Biopolymer Films for Edible Coating
Application. Biomacromolecules 2006, 7, 2011–2019.
DOI: 10.1021/bm060179r.
[16] De Freitas, J. N.; Nogueira, V. C.; Ito, B. I.; Soto-
Oviedo, M. A.; Longo, C.; De Paoli, M. A.;
Nogueira, A. F. Dye-Sensitized Solar Cells and Solar
Module Using Polymer Electrolytes: Stability and
Performance Investigations. Int. J. Photoenergy. 2006,
2006, 1–6. DOI: 10.1155/IJP/2006/75483.
[17] Mattos, R. I.; Tambelli, C. E.; Donoso, J. P.;
Pawlicka, A. NMR Study of Starch Based Polymer Gel
Electrolytes: Humidity Effects. Electrochim. Acta. 2007,
53, 1461–1465. DOI: 10.1016/j.electacta.2007.05.061.
[18] Machado, G. O.; Ferreira, H. C. A.; Pawlicka, A.
Influence of Plasticizer Contents on the Properties of
HEC-based Solid Polymeric Electrolytes. Electrochim.
Acta. 2005, 50, 3827–3831. DOI: 10.1016/j.
electacta.2005.02.041.
[19] Pradhan, D. K.; Choudhary, R.; Samantaray, B. Studies
of Dielectric Relaxation and AC Conductivity Behavior
of Plasticized Polymer Nanocomposite Electrolytes. Int.
J. Electrochem. Sci. 2008, 3, 597–608.
[20] Ikeda, S.; Kumagai, H. Dielectric Analysis of Sol− Gel
Transition of κ-carrageenan with Scaling Concept.
J. Agric. Food Chem. 1998, 46(9), 3687–3693. DOI:
10.1021/jf980170j.
[21] Sanchis, M. J.; Carsí, M.; Culebras, M.; Gómez, C. M.;
Rodriguez, S.; Torres, F. G. Molecular Dynamics of
Carrageenan Composites Reinforced with Cloisite Na
+ Montmorillonite Nanoclay. Carbohydr. Polym. 2017,
176, 117–126. DOI: 10.1016/j.carbpol.2017.08.012.
[22] Zhu, D.; Guo, Q.; Zheng, Z.; Matsuo, M. Thermal and
Dielectric Investigations on the Blends of κ-carrageenan
and Nano-Structured Polyaniline. Synth. Met. 2014, 187,
165–171. DOI: 10.1016/j.synthmet.2013.11.003.
[23] Tuvikene, R.; Truus, K.; Vaher, M.; Kailas, T.; Martin, G.;
Kersen, P. Extraction and Quantification of Hybrid
Carrageenans from the Biomass of the Red Algae
Furcellaria Lumbricalis and Coccotylus Truncatus. Proc.
Estonian Acad. Sciences, Chem. 2006, 55, 40–53.
[24] Rodriguez, S. A.; Weese, E.; Nakamatsu, J.; Torres, F.
Development of Biopolymer Nanocomposites Based on
Polysaccharides Obtained from Red Algae
Chondracanthus Chamissoi Reinforced with Chitin
Whiskers and Montmorillonite. Polym. Plast. Technol.
Eng. 2016, 55(15), 1557–1564. DOI: 10.1080/
03602559.2016.1163583.
[25] Martins, J. T.; Cerqueira, M. A.; Bourbon, A. I.;
Pinheiro, A. C.; Souza, B. W.; Vicente, A. A.
Synergistic Effects between κ-carrageenan and Locust
Bean Gum on Physicochemical Properties of Edible

Films Made Thereof. Food Hydrocoll. 2012, 29(2),
280–289. DOI: 10.1016/j.foodhyd.2012.03.004.
[26] Mitsuiki, M.; Yamamoto, Y.; Mizuno, A.; Motoki, M.
Glass Transition Properties as a Function of Water
Content for Various Low-Moisture Galactans.
J. Agric. Food Chem. 1998, 46(9), 3528–3534. DOI:
10.1021/jf9709820.
[27] Havriliak, S.; Havriliak, S. J. Dielectric and Mechanical
Relaxation in Materials: Analysis, Interpretation and
Application to Polymers; Hanser, Munich. 1997.
[28] Schönhals, A.; Kremer, F. Analysis of Dielectric
Spectra. In Kremer, F.; Schönhals, A. (Ed.s),
Broadband Dielectric Spectroscopy. Springer: Berlin,
Heidelberg, 2003.
[29] Boyd, R.; Smith, G. Polymer Dynamics and Relaxation;
Cambridge University Press, New York. 2007.
[30] Klein, R. J.; Zhang, S.; Dou, S.; Jones, B. H.;
Colby, R. H.; Runt, J. Modeling Electrode Polarization
in Dielectric Spectroscopy: Ion Mobility and Mobile
Ion Concentration of Single-Ion Polymer Electrolytes.
J. Phys. Chem. 2006, 124(14), 1449. DOI: 10.1063/
1.2186638.
[31] Barahona, T.; Prado, H. J.; Bonelli, P. R.;
Cukierman, A. L.; Fissore, E. L.; Gerschenson, L. N.;
Matulewicz, M. C. Cationization of Kappa-And iota-
carrageenan–Characterization and Properties of
Amphoteric Polysaccharides. Carbohydr. Polym. 2015,
126, 70–77. DOI: 10.1016/j.carbpol.2015.02.053.
[32] Nanaki, S.; Karavas, E.; Kalantzi, L.; Bikiaris, D.
Miscibility Study of Carrageenan Blends and
Evaluation of Their Effectiveness as Sustained Release
Carriers. Carbohydr. Polym. 2010, 79, 1157–1167. DOI:
10.1016/j.carbpol.2009.10.067.
[33] Hema, M.; Selvasekerapandian, S.; Hirankumar, G.;
Sakunthala, A.; Arunkumar, D.; Nithya, H. Structural
and Thermal Studies of PVA: NH4I. J. Phys. Chem.
Solids. 2009, 70(7), 1098–1103. DOI: 10.1016/j.
jpcs.2009.06.005.
[34] Nakamura, K.; Nishimura, Y.; Hatakeyama, T.;
Hatakeyama, H. Thermal Properties of Water
Insoluble Alginate Films Containing Di-And Trivalent
Cations. Thermochim. Acta. 1995, 267, 343–353. DOI:
10.1016/0040-6031(95)02491-3.
[35] Zarina, S.; Ahmad, I. Biodegradable Composite Films
Based on κ-carrageenan Reinforced by Cellulose
Nanocrystal from Kenaf Fibers. Bioresour. 2014, 10
(1), 256–271. DOI: 10.15376/biores.10.1.256-271.
[36] Mohamadnia, Z.; Zohuriaan-Mehr, M. J.; Kabiri, K.;
Jamshidi, A.; Mobedi, H. Ionically Cross-Linked
Carrageenan-Alginate Hydrogel Beads. J. Biomater.
Sci. Polym. 2008, 19(1), 47–59. DOI: 10.1163/
156856208783227640.
[37] Rhim, J. W.; Wang, L. F. Preparation and
Characterization of Carrageenan-Based Nanocomposite
Films Reinforced with Clay Mineral and Silver
Nanoparticles. Appl. Clay Sci. 2014, 97, 174–181. DOI:
10.1016/j.clay.2014.05.025.
[38] Prasad, K.; Meena, R.; Siddhanta, A. K. Microwave-
Induced Rapid One-Pot Synthesis of κ-carrageenan
-g-PMMA Copolymer by Potassium Persulphate
Initiating System. J. Appl. Polym. Sci. 2006, 101(1),
161–166. DOI: 10.1002/(ISSN)1097-4628.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 13
[39] Yuen, S. N.; Choi, S. M.; Phillips, D. L.; Ma, C. Y.
Raman and FTIR Spectroscopic Study of
Carboxymethylated Non-Starch Polysaccharides. Food
Chem. 2009, 114, 1091–1098. DOI: 10.1016/j.
foodchem.2008.10.053.
[40] Gómez-Ordóñez, E.; Rupérez, P. FTIR-ATR
Spectroscopy as a Tool for Polysaccharide
Identification in Edible Brown and Red Seaweeds.
Food Hydrocoll. 2011, 25, 1514–1520. DOI: 10.1016/j.
foodhyd.2011.02.009.
[41] Paluszkiewicz, C.; Stodolak, E.; Hasik, M.;
Blazewicz, M. FT-IR Study of Montmorillonite–
Chitosan Nanocomposite Materials. Spectrochim. Acta
A Mol. Biomol. Spectrosc. 2011, 79, 784–788. DOI:
10.1016/j.saa.2010.08.053.
[42] Van de Velde, F.; Pereira, L.; Rollema, H. S. The
Revised NMR Chemical Shift Data of Carrageenans.
Carbohydr. Res. 2004, 339, 2309–2313. DOI: 10.1016/
j.carres.2004.07.015.
[43] Van de Velde, F.; De Ruiter, G. A. Carrageenan.
Biopolymers Online. 2005. DOI: 10.1002/3527600035.
bpol6009.
[44] Han, P.; Sun, Y.; Jia, S.; Zhong, C.; Tan, Z. Effects of
Light Wavelengths on Extracellular and Capsular
Polysaccharide Production by Nostoc Flagelliforme.
Carbohydr. Polym. 2014, 105, 145–151. DOI: 10.1016/
j.carbpol.2014.01.061.
[45] Ishai, P. B.; Talary, M. S.; Caduff, A.; Levy, E.;
Feldman, Y. Electrode Polarization in Dielectric
Measurements: A Review. Meas. Sci. Technol. 2013,
24(10), 102001. DOI: 10.1088/0957-0233/24/10/102001.
[46] Yuan, J. K.; Yao, S. H.; Dang, Z. M.; Sylvestre, A.;
Genestoux, M.; Bai1, J. Giant Dielectric Permittivity
Nanocomposites: Realizing True Potential of Pristine
Carbon Nanotubes in Polyvinylidene Fluoride Matrix
through an Enhanced Interfacial Interaction. J. Phys.
Chem. C. 2011, 115, 5515–5521. DOI: 10.1021/
jp1117163.
[47] Arjmand, M.; Ameli, A.; Sundararaj, U. Employing
Nitrogen Doping as Innovative Technique to
Improve Broadband Dielectric Properties of Carbon
Nanotube/Polymer Nanocomposites. Macromol.
Mater. Eng. 2016, 301, 555–565. DOI: 10.1002/
mame.v301.5.
[48] Hedvig, P.;. Dielectric Spectroscopy of Polymers; Adam
Hilger Ltd: Bristol, UK, 1977.
[49] Katana, G.; Fischer, E. W.; Hack, T.; Abetz, V.;
Kremer, F. Influence of Concentration Fluctuations
on the Dielectric. alpha.-Relaxation in Homogeneous
Polymer Mixtures. Macromolecules. 1995, 28(8),
2714–2722. DOI: 10.1021/ma00112a017.
[50] Jonscher, A. K.;. The ‘Universal’dielectric Response.
Nature. 1977, 267, 673–679.
[51] Bakr, A. A.; North, A.; Kossmehl, G. Charge Carrier
Hopping in Poly (Arylene Vinylenes). Eur. Polym. J.
1977, 13, 799–803. DOI: 10.1016/0014-3057(77)
90025-8.
[52] Hairetdinov, E. F.; Uvarov, N. F.; Patel, H. K.
Disadvantages of Electric Modulus Formalism in
Description of Electrical Relaxation in Solids.
Ferroelectrics. 1996, 176, 213–219. DOI: 10.1080/
00150199608223611.
14 F. G. TORRES ET AL.
[53] Elliott, S. R.;. Use of the Modulus Formalism in the
Analysis of Ac Conductivity Data for Ionic Glasses.
J. Non. Cryst. Solids. 1994, 170, 97–100. DOI:
10.1016/0022-3093(94)90108-2.
[54] Crompton, T. R.;. Physical Testing of Plastics; Smithers
Rapra, Shawbury. 2012.
[55] Angell, C. A.;. Perspective on the Glass Transition.
J. Phys. Chem. Solids. 1988, 49, 863–871. DOI:
10.1016/0022-3697(88)90002-9.
[56] Shinyashiki, N.; Shinohara, M.; Iwata, Y.; Goto, T.;
Oyama, M.; Suzuki, S.; Yamamoto, W.; Yagihara, S.;
Inoue, T.; Oyaizu, S. The Glass Transition and
Dielectric Secondary Relaxation of Fructose− Water
Mixtures. J. Phys. Chem. B. 2008, 112, 15470–15477.
[57] Tominaga, Y.; Asai, S.; Sumita, M.; Panero, S.;
Scrosati, B. A Novel Composite Polymer Electrolyte:
Effect of Mesoporous SiO2 on Ionic Conduction in
Poly (Ethylene oxide)–LiCF3SO3 Complex. J. Power
Sources. 2005, 146, 402–406. DOI: 10.1016/j.
jpowsour.2005.03.035.
[58] Pitawala, H. M. J. C.; Dissanayake, M. A. K. L.;
Seneviratne, V. A.; Mellander, B. E.; Albinson, I.
Effect of Plasticizers (EC or PC) on the Ionic
Conductivity and Thermal Properties of the (PEO) 9
LiTf: Al 2 O 3 Nanocomposite Polymer Electrolyte
System. J. Solid State Electrochem. 2008, 12(7–8),
783–789. DOI: 10.1007/s10008-008-0505-7.
[59] Leo, C. J.; Rao, G. S.; Chowdari, B. V. R. Studies on
Plasticized PEO–Lithium Triflate–Ceramic Filler
Composite Electrolyte System. Solid State Ion. 2002,
148, 159–171. DOI: 10.1016/S0167-2738(02)00107-8.
[60] Pradhan, D. K.; Samantaray, B. K.;
Choudhary, R. N. P.; Thakur, A. K. Effect of
Plasticizer on Structure—Property Relationship in
Composite Polymer Electrolytes. J. Power Sources.
2005, 139, 384–393. DOI: 10.1016/j.jpowso
ur.2004.05.050.
[61] Angell, C. Strong and Fragile Liquids. Relax. Complex
Syst. 1985, 3-12.
[62] Bӧhmer, R.; Ngai, K.; Angell, C. A.; Plazek, D.
Nonexponential Relaxations in Strong and Fragile
Glass Formers. J. Chem. Phys. 1993, 99, 4201–4209.
DOI: 10.1063/1.466117.
[63] Sengwa, R. J.; Choudhary, S.; Sankhla, S. Dielectric
Spectroscopy of Hydrophilic Polymers–
Montmorillonite Clay Nanocomposite Aqueous
Colloidal Suspension. Colloids Surf A Physicochem. Eng.
Asp. 2009, 336(1–3), 79–87. DOI: 10.1016/j.
colsurfa.2008.11.015.
[64] Ramesh, S.; Liew, C. W.; Arof, A. Ion Conducting Corn
Starch Biopolymer Electrolytes Doped with Ionic Liquid
1-Butyl-3-Methylimidazolium Hexafluorophosphate.
J. Non Cryst. Solids. 2011, 357, 3654–3660. DOI:
10.1016/j.jnoncrysol.2011.06.030.