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Materials Science and Engineering B 178 (2013) 167173

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Materials Science and Engineering B
j our nal homepage: www. el sevi er . com/ l ocat e/ mseb
Characterization and temperature-dependent conductivity of polyaniline
nanocomposites encapsulating gold nanoparticles on the surface of
carboxymethyl cellulose
C. Basavaraja, Jin Kyung Kim, Do Sung Huh

Department of Chemistry and Institute of Basic Science, Inje University, Kimhae, Kyungnam621-749, South Korea
a r t i c l e i n f o
Article history:
Received 4 May 2012
Received in revised form17 October 2012
Accepted 2 November 2012
Available online 15 November 2012
Conducting polymer
Gold nanoparticles
Carboxymethyl cellulose
a b s t r a c t
Polyaniline nanocomposites encapsulating gold nanoparticles on carboxymethyl cellulose surface were
prepared via the polymerization of aniline hydrochloride with different carboxymethyl cellulose (CMC)
concentrations (wt.%) using HAuCl
as oxidant. The synthesized composites were characterized byFourier
transform infrared (FTIR) spectroscopy. Surface morphology was studied by electron diffraction scanning
electron microscopy (SEM) and transmission electron microscopy (TEM). The embedded crystallinity
of the composites was investigated by X-ray diffraction (XRD) analyses. The electrical property of the
composites was examined by temperature-dependent DC conductivity in the range of 300500 K. The
composites exhibited higher electrical conductivities with increased CMC concentration under equivalent
conditions. Activation energy for electron transport was also calculated based on the conductivity data.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Micro/nanostructured polyaniline (PANI) has received consid-
erable attention because of its unique characteristics, including
controllable chemical and electrical properties, simple prepara-
tion, low cost, and excellent environmental stability [1]. These
characteristics have led to the application of PANI in various
micro/nanomaterials and devices [2]. The optical, microwave
absorption, and magnetic functions of PANI micro/nanostructures
have also drawn signicant research interest because of their
potential to meet the needs of various technological applications.
Polymer modication by surfactants is an attractive and interest-
ing method of preparing polymer composites. Polymers have been
widely studied in solution and in solid states because of their inter-
esting physical properties, including easy solubility, mesomorphic
behavior, nanostructured morphology, and reversible fusibility
Organic/inorganic nanostructure composites have recently
drawn attention because of their excellent physical, mechanical,
and electrical features, including elevated conductivity, catalytic
activity, gas sensitivity, and optoelectronic properties. Compared
with their bulk counterparts, one-dimensional nanostructures,
suchas wires, rods, belts, andtubes, havebecomethefocus of inten-
sive research because of their unique applications in mesoscopic

Corresponding author. Tel.: +82 55 320 3225.

E-mail address: (D.S. Huh).
physics and in the fabrication of nanoscale devices. Gold nanopar-
ticles (AuNPs) have beenwidely studiedas a component of polymer
composites because of their unique, size-related electronic and
optical properties. AuNPs dispersed in polymeric networks are
currently used in sensors, catalytic materials, conductive inks,
and electron or energy storage. Due to the small surface area of
the above polymer composites, close contact between the metal
nanoparticles and the PANI matrix is inadequate [7,8]. Therefore,
several of these composites are not suitable for industrial appli-
cations. Close contact between metal particles and the polymer is
crucial for the performance of molecular electronic devices because
the charge transfer at the contact point has an important role in its
functionality [911].
Recent advancements in the nanoscale-binding technique have
provided an innovative route for preparing PANI-based composites
with better performance as electrode materials [12,13]. A previous
study has demonstrated that PANI composites with metal oxides
have improved super-capacitor performance. AuNPs have been
widely studied as a component of metal nanoparticles because of
their unique optical and catalytic properties [14]. However, several
of these composites have small surface area; thus, effective inti-
mate contact between the AuNPs and the PANI matrix cannot be
realized [15,16].
Surfactants, such as camphor suphonic, dodecyl benzene sul-
phonic (DBSA), and naphthalene sulfonic acids (NSA), are used as
templates for PANI. However, DBSA and NSA are relatively large
dopants that reduce the interchain interactions among PANI chains
0921-5107/$ see front matter 2012 Elsevier B.V. All rights reserved.
168 C. Basavaraja et al. / Materials Science and Engineering B 178 (2013) 167173
This problem has motivated several researchers to investigate
the compatibility of PANI with water-soluble biopolymers, such
as polyvinyl alcohol and alginate [2123]. The chemical modica-
tion of PANI with carbohydrate polymers is preferable in preparing
multifunctional PANI-metal oxide composites via oxidative-radical
polymerization. Polymer cross-linking reinforces the mechanical
stability of bio-coating against temperature and convection. The
resulting materials are interesting because of their compatibility
with environmental and biological systems.
Cellulose, along with other natural biopolymers, has gained
considerable research interest in materials science due to its envi-
ronmentally attractive origin and properties. These advantageous
properties include renewability, biodegradability, biocompatibil-
ity, abundance, highspecic strength, andnon-abrasiveness during
processing. Consequently, innovations have focused on under-
standing the structureproperty relationships and adaptation of
cellulose-derived products for newspecic applications that result
in decreased use of chemicals. Among the cellulosic ethers, car-
boxymethyl cellulose (CMC) is a very important derivative of
cellulose. CMCs have good solubility, high chemical stability, and
are toxicologically innocuous. They are processed in dissolved
or highly swollen state [24], and are the dominant polymers in
numerous industrial applications, especially where consistency in
the quality of aqueous media and water-containing systems is
required. CMC is the anionic carboxymethyl ether of cellulose pro-
ducedbythealkali-catalyzedreactionof cellulosewithchloroacetic
acid, which is widely used in industries as a thickening and sta-
bilizing agent. Introduced polar carboxyl groups render cellulose
soluble, chemically reactive, and strongly hydrophilic while retain-
ing its connatural odorless, tasteless, nontoxic, and biodegradable
characteristics. CMC is advantageous in fabricating eco-friendly
polymer materials through grafting modication [25,26]. Thus, its
application in superabsorbent elds is promising.
In this study, polymer composites containing PANICMC were
synthesized. The composites were prepared through the polymer-
ization of aniline hydrochloride with different weight percentages
of sodium CMC using gold chloride (HAuCl
) as oxidant. The syn-
thesized composites were characterized by FTIR spectroscopy and
XRD analyses. Surface morphology was analyzed by SEMand TEM.
The atomic and weight percentages of the elements present in the
polymer composites were analyzed by an energy-dispersive X-ray
(EDX) analyzer equipped to the SEM. The temperature-dependent
DC conductivity of the synthesized composites was measured in
the range of 300500K to examine their electrical properties.
2. Experimental
2.1. Materials
AR-grade aniline hydrochloride, gold (III) chloride trihy-
drate (HAuCl
O, 99.0%), and sodium CMC (with average
molecular weight of 90,000, 7781% moisture content, and 0.7
carboxymethyl groups per anhydroglucose) were purchased from
SigmaAldrich Co. (St. Louice, USA). N-Methyl-2-pyrrolidinone
(NMP) was obtained from Junsei Chemical Co. (Tokyo, Japan). N-
Methyl-2-pyrrolidinone was obtained fromJunsei Chemical Co. All
solutions were prepared in aqueous media using deionized water.
2.2. Syntheses of PANIAu polymer and PANIAuCMC
An aqueous solution of 0.5M aniline hydrochloride monomer
oxidant wereusedtopreparePANIAupolymer.
The monomer solution was slowly added to the HAuCl
tion. The mixture was initially sonicated for 30min to initiate
polymerization. A green solution was eventually obtained. The
mixture was sonicated continuously for 56h at room tempera-
ture to obtain a dark green precipitate. The precipitated powder
was ltered by lter paper and washed with hot deionized water
and acetone many times to remove the unreacted monomer and
oxidant. The washed PANIAu composite was dried under vac-
uumat 60

C for 24h to achieve a constant weight. After then, the

dried composite was washed once more with water to ensure the
removal of monomer as well as the oxidant. And it was nally dried
under vacuumat 60

C for 24h.
PANIAuCMC composites were also prepared with the simi-
lar process for the synthesis of PANIAu composite. However, it
was prepared by rst dispersing varied amounts (wt.%) of CMC in
the aqueous solution containing the oxidant (HAuCl
). The amount
(wt.%) of CMC regarded in this study was 10, 20, 30, 40, and 60wt.%.
But for the sake of convenience, we have focused on the prop-
erties of composites using 20, 40 and 60wt.%. The mixture was
then sonicated for 30min. A certain amount of monomer (aniline
hydrochloride) solution was added to the reaction mixture with
continuous sonication when a uniformdispersion of CMCAu was
obtained. Sonicationwas performedfor another 30min, andfurther
continuous sonication was performed for 5h6h at roomtemper-
ature to obtain a dark green precipitate. The precipitated powder
was ltered by lter paper and washed with hot deionized water
and acetone many times to remove the unreacted monomer and
oxidant. The washed PANICMCAu composite was dried under
vacuum at 60

C for 24h to achieve a constant weight. After then,

the dried composite was washed once more with water to ensure
the removal of monomer as well as the oxidant. And it was nally
dried under vacuumat 60

C for 24h.
The PANIAuCMC composites with 20wt.%, 40wt.%, and
60wt.% CMC are hereafter denoted as PANIAuCMC-20, -40, and
-60, respectively.
2.3. Preparation of PANIAu and PANIAuCMC composite lms
The powder was treated with a solution of sodium ethoxide
ONa) and ethanol, and was magnetically stirred at room
temperature for 12h. The precipitate was ltered and washed
repeatedly with ethanol and stored in a desiccator for 4h at room
temperature. Later 12g of nely ground powder was added to
30ml of NMP solution and magnetically stirred for 24h at room
temperature. The concentrated solution was placed into a Petri
dish, and the NMP solvent was allowed to evaporate at 45

C for
48h. The obtained lms with thickness of ca. 30m were placed
in distilled water and rinsed with ethanol, and dried at roomtem-
perature for 24h. To obtain solvent-free lms, the residual NMP
was removed by three cycles of dopingdedoping process using
1M HCl solution and 0.1M NH
OH, respectively for 18h at room
temperature. The resulting NMP-free composite lms were cleaned
in deionized water and were dried at roomtemperature for 24h.
Fig. 1 shows the schematic diagram for the formation of the
PANIAuCMC composite lms. After adding CMC to the aqueous
solution containing HAuCl
, a uniform solution that appeared to
be a complex was formed. Part of the solution was pipetted out
and centrifuged before adding aniline hydrochloride to determine
whether the complex was formed between Au and CMC. The pow-
der sample was analyzedby TEM, whichwill be discussedfurther in
the succeeding sections. A certain amount of aniline hydrochloride
was added into the mixture after obtaining the AuCMC com-
plex. The mixture was sonicated for 30min at room temperature,
and then for another 4h5h to obtain the PANIAuCMC com-
posites. The biopolymer CMC formed a micellar structure when
dispersed in aqueous media, which served as a soft template to
which the formed AuNPs appeared to be attached to in the aqueous
C. Basavaraja et al. / Materials Science and Engineering B 178 (2013) 167173 169
Fig. 1. Overall scheme for the formation of anilineAuCMC complex, PANIAuCMC composite, and PANIAuCMC composite lm.
dispersion. Polymerization occurred after the addition of aniline
hydrochloride, and PANIAuCMC composites were formed.
2.4. Characterization
The characterization techniques used and preparation proce-
dure for thin lms of the synthesized PANICMC composites have
been described in our earlier research [27,28]. The FTIR spectra
of the samples were obtained using the IR spectrometer (Perkin
Elmer, Model No. 783, USA) with a KBr medium at room tem-
perature. Thermal properties were obtained by thermogravimetric
analysis (PerkinElmer Thermogravimetric Analyzer 7) from 20

to 800

C at a rate of 2

C/min in a nitrogen atmosphere. The mor-

phology of the synthesized composite lms was investigated by a
SEM(COXEM-CX100s) and a TEMsystem(JEM-2000, JEOL, Japan).
The atomic and weight percentages of the elements present in
the polymer composites were analyzed by an energy-dispersive
X-ray (EDX) analyzer equipped to the SEM. The XRD patterns
were obtained using a Philips diffractometer (PW 1710) with
CuK (=1.5406

A) radiation. The diffractograms were recorded
at 2

/min. DC electrical measurements of the obtained composite

lms were performed from 300K to 500K using the four-probe
technique. A Keithly 224 constant current source and a Keithly 617
digital electrometer were used.
3. Results and discussion
3.1. Characterization and surface morphology analysis of the
PANIAu and PANIAuCMC composites
Fig. 2 shows the FTIR spectra of the powder samples of CMCAu,
PANIAu, PANIAuCMC-40, and PANIAuCMC-60 composites.
CMC showed its characteristic absorption at 1115 and 1165cm
representing the stretching vibration of the C OH groups. The
strong broad band at 3425cm
in the CMC spectrumcorresponds
to the stretching vibrations of the intramolecular hydrogen bond
). The band at 2927cm
showed the stretching vibrations
of the C H bonds (
). The strong peak at 1616cm
to the stretching vibration of the carboxylic group (

). The
broad medium peak at 1056cm
showed the bending vibrations
of the ether (glycosidic) linkage (
) [2931]. The band regions
shifted slightly lower than the neat CMC, conrming the presence
of AuNPs in the CMC polymer. The PANIAu FTIR spectra were sim-
ilar to those reported in our earlier study [32,33]. The IR bands
for quinine and benzene rings appeared at 1566 and 1755cm
respectively. The C Nstretching near the quinoid ring and that of
the aromatic amine were observed at 1388 and 1311cm
, respec-
tively. The C Hout-of-plane deformationinthe 1,4-disubstituted
benzene ring appeared at 890cm
. The aromatic in the C Hplane
bending modes appeared within the 991cm
Fig. 2. FTIR spectra of CMCAu, PANIAu, PANIAuCMC-40, and PANIAuCMC-
170 C. Basavaraja et al. / Materials Science and Engineering B 178 (2013) 167173
Fig. 3. SEMimages of (a) PANIAu, (b) PANIAuCMC-20, (c) PANIAuCMC-40, and (d) PANIAuCMC-60.
For PANIAuCMC-40 and -60, the stretching vibration of C OH
appeared at 1145 and 1165cm
and at 1125 and 1157cm
respectively. The stretching vibrations of the intramolecular
hydrogen bonds of CMC at 3425cm
disappeared in both
PANIAuCMC-40 and 60. Thus, the shift in the FTIR bands (lower
or higher) of the PANIAuCMC composites suggested the forma-
tion of the composites. The FTIR spectrum of CMCAu, PANIAu,
PANIAuCMC-40, and PANIAuCMC-60 composites shows Au
absorption peaks distinctly at 1591,1485,1382,1178 and 768cm
which are assignable to the presence of Au in the composite
[34]. However, this formation was not sufcient to suggest the
presence of AuNPs in the composites through the FTIR spectra
alone. Therefore, either SEM or TEM data were required to prove
the incorporation of AuNPs into the CMCAu and PANIAuCMC
Fig. 3 shows the SEMimages of (a) PANIAu, (b) PANIAuCMC-
20, (c) PANIAuCMC-40, and (d) PANIAuCMC-60 obtained at
different magnications. By the images it is not easy to see
the difference between PANIAu and PANIAuCMC compos-
ites. However, PANIAu showed nger-like structures similar to
that reported in our earlier research [32,33]. The appearance of
nger-like structures may be due to the incorporation of AuNPs
Fig. 4. TEMimages of (a) PANIAu, (b) PANIAuCMC-20, (c) PANIAuCMC-40, and (d) PANIAuCMC-60.
C. Basavaraja et al. / Materials Science and Engineering B 178 (2013) 167173 171
in the PANI polymer matrix with particle sizes ranging from
25nmto 45nmwhich were approximately calculated by the SEM
Fig. 4 shows the TEMimages of (a) CMCAu, (b) PANIAuCMC-
20, (c) PANIAuCMC-40, and (d) PANIAuCMC-60. The image
of CMCAu shows two types of phase in which one is like as
amorphous phase and the other is amorphous one but small black
particles were dispersed in the phase. The amorphous phase was
probably due to the CMC polymer while the black particles were
originated by the AuNPs. When the PANI polymer was introduced,
the image of composite appeared relatively dark as shown in the
image of PANIAuCMC-20 (Fig. 4b) compared to the image of
CMCAu (Fig. 4a). The surface images of PANIAuCMC-40 (Fig. 4c)
and PANIAuCMC-60 (Fig. 4d) wherein the concentration of CMC
has been further increased were almost similar with the image
of PANIAuCMC-20. However, the images of the two composites
show bigger particles (black) and a polymer chain-like structure.
In the two images it was very difcult to identify PANI, CMC, and
AuNPs separately. Therefore, we can suggest that the increase of
CMC concentration might cause the agglomeration of Au nanopar-
ticles in the composite.
With increased CMC concentration, the polymer caused the
encapsulation of the AuNPs. Consequently, nearly spherically
shaped larger particles were observed for PANIAuCMC-40 and
The surface morphology revealed that increased CMC con-
centration in the PANIAuCMC composites formed a lump-
like structure, which may have been caused by the encap-
sulation of CMC over the AuNPs in the aqueous disper-
sion, followed by the polymerization of PANI. The above
results indicate the successful formation of PANIAuCMC
Fig. 5ad shows the EDXspectra of PANIAu, PANIAuCMC-20,
PANIAuCMC-40, andPANIAuCMC-60, respectively. Thesignals
obtained in the EDX spectra of PANIAu showed the presence of
C, N, and Au elements. Similarly, the signals of the PANIAuCMC
composites indicated the presence of C, N, Au, and O. Table 1
shows the atomic and weight percentages of the elements in
PANIAu and PANIAuCMC. The decreased C, O, and Au percent-
ages in PANIAuCMC were due to the partial oxidation of the
PANI chains in the composites. The reaction scheme illustrated in
Fig. 1 suggests the successful involvement of C, O, and Au dur-
ing the formation of composites. Comparing the signals obtained
in the EDX spectra of PANIAu and PANIAuCMC composites,
the peaks obtained in the spectra of the latter showed the pres-
ence of Au, C, N, and O, conrming the formation of PANIAuCMC
3.2. XRD analysis of PANIAu and PANIAuCMC
Fig. 6 displays the XRD patterns of PANIAu, PANIAuCMC-40,
and PANIAuCMC-60. A slightly broad peak appeared at around

, which is attributed to PANI. The peak was broadened

with the increase of CMC concentration in PANIAuCMC. The
XRD pattern of AuNPs indicates the major Bragg reection peaks
at 2 =35

, 43

, 65

, and 76

, which are (111), (200), (220),

and (311), respectively, as the face-centered cubic structure of
the AuNPs [35,36]. The XRD peaks of PANIAu, PANIAuCMC-
40, and PANIAuCMC-60 composites had similar patterns with
those of AuNPs. The peaks centered at 2 =20

and 25

ascribed to the periodicity of the PANI chain [37,38] in PANIAu
and PANIAuCMC. The diffraction patterns of the PANIAuCMC
composites combined the diffraction peaks from PANIAu and
PANIAuCMC, further proving the existence of AuNPs in the
Fig. 5. EDX spectra of (a) PANIAu, (b) PANIAuCMC-20, (c) PANIAuCMC-40,
and (d) PANIAuCMC-60.
Fig. 6. XRD spectra of PANIAu, PANIAuCMC-40, and PANIAuCMC-60.
3.3. Temperature-dependent DC conductivity of PANIAu and
PANIAuCMC composites
The temperature-dependent DC conductivity of the PANIAu
and PANIAuCMC composite lms were measured in the range
of 300500K. Fig. 7 represents the DC electrical conductivity
172 C. Basavaraja et al. / Materials Science and Engineering B 178 (2013) 167173
Table 1
Atomic and weight percentage data obtained fromthe EDX spectra of PANIAu and PANIAuCMC composites.
Element Atomic%
C N Au O C N Au O
PANIAu 76.08 11.97 4.41 41.23 7.57 39.2
PANIAuCMC-20 64.28 11.19 7.53 8.98 27.22 5.52 52.29 5.06
PANIAuCMC-40 66.79 13.05 2.33 10.83 43.02 9.80 24.63 9.29
PANIAuCMC-60 68.59 16.10 0.63 6.98 53.02 14.51 8.02 7.19
The standard deviation is about 5.
as a function of temperature for PANIAu, PANIAuCMC-20,
PANIAuCMC-40, andPANIAuCMC-60, withdifferent CMC con-
centrations. The DC electrical conductivity varied, similar to a
semiconducting behavior. The conductivity linearly for PANIAu
[39,40] and the PANIAuCMC composites varied with temper-
ature. Therefore, the conduction process is linear and occurs
without percolation. The room-temperature electrical conduc-
tivities of PANIAu, PANIAuCMC-20, PANIAuCMC-40, and
PANIAuCMC-60 were 2.610
, 0.00434, 0.123, and 0.206
S/cm, respectively. Similarly, the electrical conductivities at
503K for PANIAu, PANIAuCMC-20, PANIAuCMC-40, and
PANIAuCMC-60 composites were 0.465, 1.04, 2.65, and 6.63
S/cm, respectively. The activation energy for both PANIAu and
PANIAuCMC composites were also calculated. Activation energy
is the mean value obtained at 323K. The mean values were
calculated and the plot was constructed. Fig. 8 shows the vari-
ation in activation energy with the CMC (wt.%) concentration.
Based on the conductivity and activation energy for PANIAu and
PANIAuCMC composites, the conductivity process was almost
linear (Figs. 7 and 8). The conductivities of the PANIAuCMC com-
posites increased with increased temperature. This conductivity
may be facilitated by the transport of electronic charges between
PANIAu and CMC polymer particles, as well as the inclusion of
CMC polymer.
The presence of AuNPs in neat polymer PANI causes enhanced
conductivity. In addition, the incorporation of CMC further
enhanced the conductivity of the composites. Enhancement
in temperature-dependent DC electrical conductivity can be
attributed to the owof electrons/charge carriers through the PANI
polymer chains, which is assisted by the presence of the CMC poly-
mer. The temperature increase further assists the ow of charge
carriers, causing enhanced conductivity. CMC formed a brillar
structure that encapsulates the AuNPs, and the polymerization of
PANI formed a core-like structure, as described in Fig. 1. Therefore,
Fig. 7. Temperature-dependent DC conductivity of PANIAu, PANIAuCMC-20,
PANIAuCMC-40, and PANIAuCMC-60 composite lms.
Fig. 8. Activation energy (kJ/mol) versus CMC concentration.
the formation of a core-like structure may be responsible for the
enhanced electrical conductivity.
The characterization, surface morphology, and XRD stud-
ies suggest that the presence of CMC in an aqueous solution
containing AuNPs caused the encapsulation of AuNPs in the
synthesized PANIAuCMC composites. The addition of aniline
hydrochloride also caused the polymerization to form a compos-
ite. The incorporation of CMC biopolymer was assumed to assist
in improving the interaction between PANI and AuNPs. The con-
ductivity also increased with increased wt.% of the PANIAuCMC
composites. Increased conductivity was also suggested to be due to
the increased mobility of the charge carriers, which in turn, caused
by increased CMC concentration in the composites. Increased tem-
perature facilitates the mobility of the charge carriers, further
enhancing conductivity.
4. Conclusion
In the present study, new polymer composites containing
polyanilinecarboxymethyl cellulose were prepared via the poly-
merization of aniline hydrochloride with different concentrations
(wt.%) of the biopolymer carboxymethyl cellulose using HAuCl
as an oxidant. The incorporation of the biopolymer enhanced the
electrical conductivity as well as the surface morphology of the
composites. The presence of AuNPs inneat polymer PANI enhanced
the conductivity. The incorporation of CMC further enhanced the
conductivity of the composites. Enhancement in temperature-
dependent DC electrical conductivity can be attributed to the ow
of electrons/charge carriers through the PANI polymer chains,
which is assisted by the presence of the CMC polymer. There-
fore, the incorporation process of CMC in the PANI composite
can make the PANI conductive polymer biodegradable and cost
effective. The concentration of CMC (wt.%) used in this study was
relatively larger than that of PANI. Therefore, this PANIAuCMC
composite host matrix has attractive potential uses in biosensors
C. Basavaraja et al. / Materials Science and Engineering B 178 (2013) 167173 173
for studying microorganisms. The newcomposites may also benet
the development of newapplications for biomaterials in molecular
electronics and other elds.
The present research was supported by the National Research
Foundation of Korea (NRF) (2012-0007192).
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