Carbohydrate Polymers 168 (2017) 182–190

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Conducting cellulose/TiO2 composites by in situ polymerization

of pyrrole
Amany M. ElNahrawy a , Ahmed A. Haroun b , Imad Hamadneh c , Ammar H. Al-Dujaili d ,
Samir kamel e,∗
a
Department of Solid State, Physics Division, National Research Centre, 33 El Bohouth st. (former El tahrir st.), P.O. 12622, Dokki, Giza, Egypt
b
Chemical Industrial Research Division, National Research Centre, 33 El Bohouth st. (former El tahrir st.), P.O. 12622, Dokki, Giza, Egypt
c
Chemistry Department, Faculty of Science, University of Jordan, 11942 Amman, Jordan
d
Hamdi Mango Center for Scientific Research, University of Jordan, 11942 Amman, Jordan
e
Cellulose and Paper Department, National Research Centre, 33 El Bohouth st. (former El tahrir st.), P.O. 12622, Dokki, Giza, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Cellulose/polypyrrole and cellulose/polypyrrole-TiO2 composites were prepared via in situ oxidative
Received 29 November 2016 chemical polymerization of pyrrole using FeCl3 as oxidant. The concentration effect of pyrrole on the
Received in revised form 19 March 2017 structure and properties of prepared matrix has been investigated. Furthermore, the structure of the
Accepted 20 March 2017
prepared materials was characterized using Fourier transform infrared spectroscopy (FTIR), Scanning
Available online 21 March 2017
electron microscopy (SEM), X-ray Diffraction (XRD), and Thermal gravimetrical analysis (TGA). The results
exhibited that the addition of cellulose and TiO2 increase the thermal stability of the polypyrrole sys-
Keywords:
tem. Moreover, dielectric properties of the obtained composites were studied over frequency range from
Cellulose
Polypyrrole
42 Hz to 5 MHz. The electrical measurements including dielectric constant, ␧ (␻), dielectric loss, ␧ (␻),
Nano-composite loss tangent, tan ␦ and ac conductivity, ␴ac were carried.
TiO2 -nanoparticles © 2017 Elsevier Ltd. All rights reserved.
Dielectric properties

1. Introduction ing the doping degree (Ferenets & Harlin, 2007). So it has been
performed in a number of applications, such as sensors, superca-
Conducting polymers are promising materials that possess pacitors, batteries, microwave shielding and corrosion protection;
unique properties which allow them to be used in a wide vari- because it has good environmental stability, ease in synthesis, and
ety of applications (Mihranyan, Garcia, & Stromme, 2008). In characteristic surface charge (Cho et al., 2005). Also, it can be used as
recent years, chemical oxidative polymerization has been success- conducting filler in insulating polymer matrices during preparation
fully developed to produce several interesting conducting-polymer of electrically conducting composites (Amparat, Artita, Walaiporn,
composite based on cellulosic materials and conducting poly- & Sirisart, 2008).
mers (Youssef, Kamel, El-Sakhawy, & El Samahy, 2012; Youssef Building on to the extensive work directed for the development
et al., 2016). The combination of natural materials like cellulose of polymeric composites modified with spherical nanoparticles,
with electronic elements to form multifunctional devices has been the assembly of shape-controlled nanostructure has recently been
the subject of intense scientific research. Significant efforts have gaining importance, both for fundamental scientific research and
been carried out to design cellulose-based flexible supercapaci- technological applications (Skotheim & Reynolds, 2007). Organic-
tor electrodes through the chemical polymerization of conductive inorganic composites are multiphase materials obtained through
polymers on a cellulose pulp suspension. Polypyrrole, which is one the combination of various materials in order to attain new proper-
of the most prominent types of conjugated polymers, is a promis- ties (Amany, Yong, & Ahmed, 2016). So, composites of conducting
ing conducting polymer in electronics, biological, and medical areas polymers with noble metals have beneficial properties, like ionic
due to its straightforward polymerization, environmental stability, and electrical conductivity, optical activity, flexibility, and capac-
and high electrical conductivity that can be controlled by chang- itive properties which make them useful in many technological
applications. In most cases the poor processability due to the insol-
ubility and infusibility of the conducting polymers limits their use
in practical applications (Skotheim & Reynolds, 2007). To overcome
∗ Corresponding author. this problem, the conducting polymers can be incorporated by
E-mail address: [email protected] (S. kamel).

http://dx.doi.org/10.1016/j.carbpol.2017.03.066
0144-8617/© 2017 Elsevier Ltd. All rights reserved.
 A.M. ElNahrawy et al. / Carbohydrate Polymers 168 (2017) 182–190 183

chemical polymerization in electrically nonconducting materials pyrrole/cellulose dispersion was washed with 0.5 M HCl, using a
like cellulosic and solution processable host materials resulting in Büchner funnel, to remove iron residues originating from the FeCl3
the formation of electroconductive composites (Ferenets & Harlin, salt used as the oxidant. The dispersion was then transferred back
2006). to the funnel and dried on a filter paper at 40 ◦ C. The filter paper
TiO2 is common additive with improved applications at the was easily removed from the films when they were dry and kept
nanoscale (Youssef, Kamel, & El-Samahy, 2013). TiO2 nanoparticles for further investigation.
have attracted considerable attention owing to their large surface
area, low density, superior delivering ability, low price, mechanical 2.2. Characterization
resistance, electric and photocatalytic systems (Ahmed & Ahmed,
2011; Sawanta et al., 2011; Ponnusamy, Sakthivel, Subramanian, & 2.2.1. Fourier transfer infrared spectroscopy (FTIR)
Nagarathinam, 2014, Chalal et al., 2014). FTIR spectra polypyrrole, cellulose/polypyrrole, and cellulose/
To enhance the physicochemical properties of cellulose com- polypyrrole-TiO2 composites were recorded with a FT-IR spectrom-
posite, modification has been introduced to the cellulose matrix by eter (Nicolet Impact-400 FT-IR spectrophotometer) under certain
selective doping level of foreign metal ions and others polymers condition such as: scan resolution: 4 cm−1 , scan rate: 2 mm s−1 ,
(Fern, James, Thomas, & Michael, 2007; Ortiz-Serna et al., 2011). number of scan: 32, range: 200–4000 cm−1 , and mode: transmis-
Patrycja et al. prepared composite films of nanofibrillated cel- sion.
lulose/polypyrrole and nanofibrillated cellulose/polypyrrole-silver
nanoparticles for the first time via in situ one-step chemical 2.2.2. XRD
polymerizationt. They found that; composite contaning silver The XRD patterns of cellulose, polypyrrole, cellulose/
nanoparticles exhibited electrical conductivity and strong antimi- polypyrrole, and cellulose/polypyrrole-TiO2 composites were
crobial activity (Patrycja et al., 2014). carried out on a Diano X-ray diffractometer using Cu (K␣1 /K␣2 )
Oxidant agent such as ferric chloride or ammonium persul- radiation source energized at 45 kV and a Philips X-ray diffrac-
fate have been used for oxidation polymerization of pyrrole in tometer (PW 1930 generator, PW 1820 goniometer). The XRD
the presence of cellulosic materials in the last few years due to patterns were recorded in a diffraction angle range from 10 to 80
its importance in emerging technologies as previously reported 2␪.
by Dawei, Qing, Xin, and Guangzhe (2013), Sasso, Zeno, and Petit-
Conil (2010), Beneventi, Alila, Boufi, Chaussy, and Nortier (2006),
2.2.3. Scanning electron microscopy (SEM)
Dall’Acqua et al. (2006). To the best of our knowledge, conducting
The surface morphology of cellulose, polypyrrole, cellu-
composites of cellulose/polypyrrole and TiO2 nanoparticles have
lose/polypyrrole, and cellulose/polypyrrole-TiO2 composites were
been synthesized for the first time via in situ polymerization of
analyzed using scanning electron microscopy(SEM), (JSM 6360LV,
pyrrole.
JEOL/Noran). The microscope was attached to a dispersive energy
So in this work, conductive cellulose composites were prepared
spectrometer (EDS). The images were obtained using an accelerat-
by the in situ polymerization of pyrrole in the cellulose fiber in
ing voltage of 10–15 kV.
the presence of TiO2 nanoparticles. TiO2 helps to elevate ease the
energy crisis through effective utilization of solar energy based
on photovoltaic devise. The described manufacturing process was 2.2.4. Thermogravimetric (TGA)
water-based and did not include any consuming solvent. The choice The thermal stability of polypyrrole, cellulose/polypyrrole, and
of polypyrrole for this study is due to its high conductivity, ease cellulose/polypyrrole-TiO2 composites was tested by thermogravi-
of synthesis, good environmental stability, low toxicity as well as metric analysis (TGA, Shimadzu DTG-60, Japan) at a heating rate of
commercial availability of the monomer. FeCl3 as oxidizing agent 10 ◦ C/min from 25 to 800 ◦ C under a nitrogen atmosphere.
was selected due to its abundant availability and the great poten-
tial for chemical recovery from the reaction medium through the 2.2.5. Dielectric measurements
simple redox cycle Fe+3 ↔ Fe+2 (Huang, Kang, & Ni, 2006). The relative permittivity and conductivity of the prepared sam-
ples were measured using Hioki 3532-50 LCR Hi Tester, frequency
range from 42 Hz–5 MHz.
2. Materials A dielectric measurement, which defines of the measure of a
composite materials respond to an applied field, provides an excel-
Bleached Kraft pulp was kindly provided by IDFO Company, lent means of characterizing the electrical properties of polymeric
Egypt. The ␣-Cellulose, Klason lignin, Hemicelluloses, and Ash con- materials. Dielectric relaxation spectroscopy allows one to study
tents of the pulp are; 77.60 ± 0.65, 0.87 ± 0.23, 21.40 ± 0.76, and the capacitance (C), and the conductance (G), as a function of
1.30 ± 0.41, respectively. TiO2 -nanoparticles were provided from temperature and frequency. The complex dielectric permittivity is
Sigma-Aldich as titanium (IV) oxide CAS 13463-67-7, Mwt. 79.87, given by the following equation:
nanopowder 21 nm, and particle size 99.5%.
␧∗ = ␧ -i␧ (1)

2.1. Preparation of cellulose/polypyrole composite The real part of permittivity, Dielectric constant (␧ ), depicts the
storage of energy in the nanocomposite system (amount of polar-
3 g of cellulose powder was dispersed in 100 mL of water using ization occurring in the material) whereas, the imaginary part of
high-energy ultrasonication for 30 min. 0.03 g TiO2 nanoparticle permittivity, Dielectric loss (␧ ), specifies the dissipation of energy
was added and sonication was continued for another 30 min. Differ- in the system.
ent amount of pyrrole (1, 1.5, 2, and 2.5 mL) was dissolved in 50 mL
aqueous 0.5 M HCl solution, mixed with the cellulose dispersion, Dielectricconstant(␧ ) = dC/␧o A (2)
and stirred for 5 min. A defiant amount of FeCl3 was dissolved in Dielectricloss(␧ ) = Gd/␧o A␻ (3)
100 mL aqueous 0.5 M HCl solution and added to the cellulose pyr-
role dispersion to initiate oxidative polymerization. The oxidant where A is the area of the electrodes, d the thickness of sample, ␧0
(FeCl3 ) to pyrrole was fixed at 3.5 mol ratio. The polymerization the permittivity of the empty space and ␻ the angular frequency
reaction was allowed to proceed for 30 min, after which the Poly (Silva, Valente, Graça, Góes, & Sombra, 2006).
184 A.M. ElNahrawy et al. / Carbohydrate Polymers 168 (2017) 182–190

Fig. 1. FT-IR transmission spectra of; (a) polypyrrole, (b) cellulose/polypyrrol, and (c) cellulose/polypyrrol-TiO2 composites.

Fig. 2. XRD patterns of; (a) cellulose, (b) polypyrrole, (c) cellulose/polypyrrol, and
(d) cellulose/polypyrrol-TiO2 composite.

In ordered to measure dielectric properties the samples were

compressed into plates and connected to the LCR through sam-
ple holder with two platinum parallel electrodes. Each sample was Fig. 3. TGA of; (A) Polypyrrole, (B) Cellulose/Polyrrole, and (C) Cellulose/Polyrrole-
TiO2 composite.
measured as triplicate.

3. Results and discussion Frontana-Uribe, & Ludwigs, 2010). The peak appears at 1030 cm−1
is attributed to C H and N H deformation vibrations (Dawei et al.,
3.1. Fourier transfer infrared spectroscopy 2013).
From Fig. 1b, It was observed that the peak corresponds to OH
The FT-IR spectra of polypyrrole, cellulose/polypyrrole, and of cellulose was shifted to 3614 cm−1 , this may be due to chemi-
cellulose/polypyrrole-TiO2 composites are shown in Fig. 1. Fig. 1(a) cal bonding between N H in the polypyrrole ring and the OH
is the spectrum of the prepared polypyrrole, the peaks at 3737 cm−1 of cellulose (Muller, Rambo, Recouvreux, Porto, & Barra, 2011).
could be attributed to N H stretching vibrations. The peaks at ≈ The absorption peak at about 1200 cm−1 may be related to linkage
1500 and 1450 cm−1 could be attributed to C N, C C and C C between polypyrrole and cellulose chain (Fig. 1(b, c) (Yan, Ying, &
asymmetric and symmetric ring stretching, respectively (Heinze, Juan, 2014)).
 A.M. ElNahrawy et al. / Carbohydrate Polymers 168 (2017) 182–190 185

Fig. 4. SEM of; (A) cellulose, (B) polypyrrole, (C) cellulose/polypyrrole, and cellulose/polypyrrole-TiO2 composite and elemental content in cellulose/polypyrrole-TiO2
composite.

These results indicate that the in situ polymerization of polypyr- 3.3. Thermogravimetric analysis
role onto cellulose still retains its chemical structures well.
However, the addition of TiO2 dramatically decreased the peak Fig. 3 displays the thermal gravimetric analysis of polypyrrole,
intensity at 1030, 1430 and 3400 cm−1 (Fig. 1c), indicating the for- cellulose/polypyrrole, and cellulose/polypyrrole-TiO2 composites
mation cellulose/polypyrrole-TiO2 composite. under N2 atmosphere. It demonstrates that the thermal stability of
the prepared composites is much higher than that of polypyrrole in
the temperature range of 25–800 ◦ C. As polypyrrole is hygroscopic,
nearly 8 wt% weight losses has occurred at 100 ◦ C, due to the evapo-
3.2. Crystallographic structures ration of residual water compared to only 3 wt% weight loss for the
prepared composites. In case of polypyrrole, the weight decrease
The crystallographic structures of cellulose, polypyrrole, cel-
largely however, a considerable enhancement in thermal stability
lulose/polypyrrol, and cellulose/polypyrrol-TiO2 composites are
has been seen for the prepared composites.
characterized using XRD measurements. The X-ray pattern of cellu-
As the temperature increases, the main mass loss of polypyr-
lose (Fig. 2a) clearly exhibits the typical diffraction peaks at 2␪◦ = 9
role and prepared composites starts at about 250 ◦ C corresponding
and 22◦ that belong to crystalline structure of cellulose II (Ericka,
to cellulose and polypyrrole degradation. Finally, weight loss for
Johnson, Sharathkumar, Shelby, & James, 2010). As shown in Fig. 2,
polypyrrole is much more than that for prepared composite. All
polypyrrole only exhibited a broad characteristic peak in the region
the results show that introducing of cellulose and TiO2 into the
15◦ < 2␪ < 30◦ revealing that the resulting polypyrrole powders are
polypyrrole system can enhance the thermal stability of polypyr-
amorphous in nature (Luo et al., 2010).
role.
Also, Fig. 2 displays the XRD peaks of various cellulose/TiO2
nano-composites. The prepared samples give the well-resolved
peak that is indexed as (222), associated with tetragonal phase for 3.4. SEM analysis
TiO2 according to the standard diffraction pattern data of TiO2 in the
JCPDS card (No, 89-4203), indicating that TiO2 crystals are present The morphology of cellulose, polypyrrole, cellulose/polypyrrole,
in these samples. and cellulose/polypyrrole-TiO2 composites was studied using scan-
186 A.M. ElNahrawy et al. / Carbohydrate Polymers 168 (2017) 182–190

Fig. 5. Variation of dielectric constant (␧ ) with frequency at different temperature; (A) room temperature, (B) 50 ◦ C and (C) 75 ◦ C.

ning electron micrographs (Fig. 4). From Fig. 4A it can be seen quency and then decreased to small values at high frequency. The
that, the cellulose fiber is fluffy, similar to raw cotton, with lus- relaxation behavior of the dielectric constant, over the frequency
trous. These millimeter-long fibers also exhibited a very straight range, results from different polarization mechanism in samples
and smooth surface. Fig. 4B shows that PPy has clusters of globular such as interfacial polarization, space charge polarization, orien-
structure due to the formation of aggregates like broken eggshell. tational polarization, electrode polarization, atomic polarization,
Fig. 4C shows the settlement of PPy on the cellulosic fibers in the ionic polarization and electronic polarization. At low frequency
form of clusters. SEM micrographs of cellulose/polypyrrole-TiO2 range the dominant polarization mechanisms are interfacial polar-
composite (Fig. 4D) confirmed the distribution of TiO2 at the surface ization, space charge polarization, orientational polarization and
of the cellulose/polypyrrole. electrode polarization, where it can follow the applied field and
hence samples attains high values of dielectric constant (␧ ) at
low frequency range. Interfacial polarization can be attributed to
3.5. Dielectric properties the presence of electrically heterogeneous materials, such as TiO2 ,
polypyrrole and cellulose, and it contributes to motion of virtual
It is well known that structural properties and dielectric prop- charge that trapped at the interface of the components, whereas the
erties of polymer composites can be affected by the polymer type, electrode polarization arises from the accumulation of free charge
dopant type and temperature as seen in the present work. on electrodes under the effect of applying electric field and leading
The prepared samples take the code number a, b, c, d, and to an apparent large macroscopic polarization of the material, high
e according to pyrrole content as following; 100% pyrrole, 3 g dielectric permittivity (Ladhar et al., 2015).
cellulose/2 mL pyrrole, 3 g cellulose/1 mL pyrrole/0.03 g TiO2 , 3 g The relaxation behavior can be explained by the fact that the
cellulose/1.5 mL pyrrole/0.03 g TiO2 , and 3 g cellulose/2 mL pyr- dipole structure of the system couldn’t be able to respond, alter-
role/0.03 g TiO2 respectively. The variation of dielectric constant nate, to the applied electric field at high frequency which leads to
(permittivity) (␧ ) and dielectric loss as a function of frequency for decreasing the total polarization and hence decreasing the dielec-
the prepared samples with different composition of cellulose, pyr- tric constant with frequency ␧ (␻) (Aly, Haroun, & Ibraheim, 2011).
role and TiO2 nanoparticles, at different temperatures is shown in The dielectric permittivity ␧ (␻) of the conducting polypyrrole (a),
Figs. 5 and 6. Fig. 5 is higher than that of all other samples, this increment may be
Fig. 5 shows a relaxation behavior for the dielectric constant, attributed to the fact that more charge carriers (proton, electron. . .)
where the dielectric constant (␧ ) has high values at low fre-
 A.M. ElNahrawy et al. / Carbohydrate Polymers 168 (2017) 182–190 187

Fig. 6. Variation of dielectric constant loss (␧ ) with frequency at different temperatures; (A) room temperature, (B) 50 ◦ C and (C) 75 ◦ C.

in polypyrrole become localized resulting in increasing number (cellulose/polypyrrole-TiO2 ) has high values of dielectric permit-
of dipolemoment which leads to higher dipole polarization and tivity due to the existence of different polarization mechanism in
hence increasing dielectric permittivity. The high values of (␧ )), the composite (Marija et al., 2015).
Fig. 6, observed at lower frequency were attributed to the dif- The frequency dependent on of dielectric loss (tan(␦)) shown in
ferent polarization processes such as orientational polarization, Fig. 7 shows a distinct peak at low frequency region. The presence of
space charge polarization and interfacial polarization. Interfacial low frequency peak of tan(␦) may be attributed to the existence of
polarization may arise from the presence of electrically hetero- ␤-relaxation. The low frequency ␤-relaxation may be attributed the
geneous materials, such as TiO2 , polypyrrole and cellulose, and orientation polarization of the different polar groups inside sam-
it contributes to motion of virtual charge which is trapped at ples such as polar OH group in cellulose chain and space charge. The
the interface of the components. The charges circulating in the high values of dielectric loss for (a & e) sample is attributed to DC
prepared nan-ocomposites are blocked at the interface sample- conductivity contribution due to the high concentration of the con-
electrode, resulting in the increase of (␧ )) under the effect of the ducting polypyrrole that yields high concentration of charge carrier
electric field as shown in Fig. 6. (Vijayalakshmi, Ashokan, & Shridhar, 2000; El-Sayed, Mahmoud,
From Figs. 5 and 6(a) the ␧ and ␧ ) of the cellulose-polypyrrole Fatah, & Hassen, 2011).
(b) is lower than that of polypyrrole, it can be explained on the It is known that materials with higher values of tan (␦) can be
basis that charge carriers (proton, electron.) trapped in the poly- considered as lossy materials with strong ability to absorb electro-
mer chains lead to decreasing number of localized charge and hence magnetic waves (EM). In such materials the loss in electromagnetic
decreasing number of dipolemoment in the system that decrease waves can be attributed to the interaction of electromagnetic waves
the dielectric permittivity. Also the decreasing in dielectric per- with mobile electrons and different polarization mechanism such
mittivity and dielectric loss in (b) sample can be attributed to the as space charge polarization, orientational polarization and inter-
formation of a bond between polypyrrole and cellulose through OH facial polarization (Marija et al., 2015). Also, in most polymeric
intermolecular bond of cellulose and hence decreasing the polarity materials dielectric losses may be attributed to the perturbation of
of cellulose which leads to decreasing dielectric permittivity (Nada, phonons that caused by electric field and the energy loss appears
Dawy, & Salama, 2004; Ladhar et al., 2015). in heat form.
In nano-composite system, there are different types of polar- The thermal gravimetric analysis of the prepared samples
ization that affect the dielectric permittivity such as dipole demonstrates that samples are stable in temperature range up to
orientational and interfacial polarization. Also, TiO2 has a char- 100 ◦ C. So the electrical conductivity was carried out at three dif-
acteristic polarity that contributes to the total polarization ferent temperatures below 100 ◦ C.
through orientational polarization. So, the nano-composite system
188 A.M. ElNahrawy et al. / Carbohydrate Polymers 168 (2017) 182–190

Fig. 7. Variation of dielectric loss (tan (␦)) with frequency at different temperatures; (A) room temperature, (B) 50 ◦ C and (C), 75 ◦ C.

It is known that the total conductivity of materials is consistent sharp increase with frequency, it can be attributed to charge carri-
from DC conductivity and AC conductivity. The total conductivity ers, polarons and electrons, which are transported by the hopping
is given by: process through defect sites along the chains of the polymer.
As seen from Fig. 8, the AC conductivity increases with the
T = DC + ac (ω) (4) increase of Polypyrrole; this behavior can be attributed to the fact
that polypyrrole supports the composite by more favorable sites
The first term is frequency independent and represents the DC
that facilitate the hopping of polarons between them due to the
conductivity due to the band conduction. The second term rep-
extension of polypyrrole chain length (Kumar and Sarmah, 2011).
resents the AC conductivity due to the hopping processes of the
Fig. 8 shows that the AC conductivity of the samples at 3 different
charge carrier and it given by:
temperatures increased slightly with increasing temperature and

ac (ω) = ε0 ε ω (5) this can be attributed to the thermal stability up to 100 ◦ C.

The experimental electrical conductivity ␴ () of the composites

in the frequency range of 42 Hz–5 MHz was calculated from the AC 4. Conclusion
resistance R() measurements using the following equation:
In this study, pulp fibers were functionalized with polypyrrole
1 d
 (␯) = . (6) in the presence of TiO2 nanoparticles via in-situ chemical oxidative
R (␯) A
polymerization of pyrrole. The formed polypyrrole deposited on
where A is the cross-section area of the electrode and d is the the cellulosic fibres.
thickness of the sample. Increasing polypyrrole content in the composite enhanced the
The frequency dependence of AC conductivity at three different dielectric properties of cellulose, where dielectric properties such
temperatures is shown in Fig. 8. The AC conductivity curves show as AC conductivity and dielectric permittivity were increased
two trends of electrical conductivity over the frequency range from with increasing polypyrrole content in the nano-composite. The
42 Hz to 5 MHz. At frequency range from 42 Hz to 104 the AC con- dielectric permittivity (ε ) with frequency revealed that dielectric
ductivity shows a slow increase in conductivity with frequency, relaxation at low frequency was due to the electrode polarization
nearly frequency independent. This slow increase can be attributed effects at low frequency. The linear behavior of dielectric loss (ε )
to the DC conductivity (␴dc ) contribution to the total conductivity with decreasing frequency at low frequency range suggested that
which results from the migration of free charges in the compos- the DC conductivity effect more dominant than that of the electrode
ites. While at frequency higher than 104 the conductivity shows a polarization.
 A.M. ElNahrawy et al. / Carbohydrate Polymers 168 (2017) 182–190 189

Fig. 8. Variation of AC conductivity (␴ ()) with frequency at different temperature (A, room temperature, B, 50 ◦ C and C, 75 ◦ C).

Conflict of interests Dall’Acqua, L., Tonin, C., Varesano, A., Canetti, M., Porzio, W., & Catellani, M. (2006).
Vapour phase polymerisation of pyrrole on cellulose-based textile substrates.
Synthetic Metals, 156(5–6), 379–386.
The authors declare that they have no conflict to interests. Dawei, Z., Qing, Z., Xin, G., & Guangzhe, P. (2013). A nanocellulose polypyrrole
composite based on tunicate cellulose. International Journal of Polymer Science,
2013. Hindawi Publishing Corporation [Article ID 175609, 6 pages].
El-Sayed, S., Mahmoud, K. H., Fatah, A. A., & Hassen, A. (2011). DSC, TGA and
Acknowledgements dielectric properties of carboxymethyl cellulose/polyvinyl alcohol blends.
Physica B, 406, 4068–4076.
The authors acknowledge the Science and Technology Devel- Ericka, N., Johnson, F., Sharathkumar, K. M., Shelby, F. T., & James, W. R. (2010).
X-ray diffraction of cotton treated with neutralized vegetable oil-based
opment Fund (STDF), Egypt and Scientific Research Support Fund macromolecular crosslinkers? Journal of Engineered Fibers and Fabrics, 5(1),
(SRSF), Jordan for financial support of the research activities related 10–20.
to project; Project ID 22929. Ferenets, M., & Harlin, A. (2007). Chemical in situ polymerization of polypyrrole on
poly(methyl metacrylate) substrate. Thin Solid Films, 515, 5324–5328.
Fern, M. K., James, H. J., Thomas, B., & Michael, J. R. (2007). Functionalised hybrid
materials of conducting polymers with individual fibres of cellulose. European
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