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Structure and properties of conducting bacterial cellulose-polyaniline


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DOI: 10.1007/s10570-011-9565-4

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Cellulose (2011) 18:1285–1294
DOI 10.1007/s10570-011-9565-4

Structure and properties of conducting bacterial


cellulose-polyaniline nanocomposites
Jessica A. Marins • Bluma G. Soares •
Karim Dahmouche • Sidney J. L. Ribeiro •

Hernane Barud • Denise Bonemer

Received: 8 February 2011 / Accepted: 6 June 2011 / Published online: 15 June 2011
Ó Springer Science+Business Media B.V. 2011

Abstract Conducting composite membranes of cellulose-polyaniline conducting membranes which


bacterial cellulose (BC) and polyaniline doped with find potential applications as electronic devices,
dodecylbenzene sulfonic acid (PAni.DBSA) were sensors, intelligent clothes, etc.
successfully prepared by the in situ chemical poly-
merization of aniline in the presence of hydrated BC Keywords Bacterial cellulose  Polyaniline 
sheets. The polymerization was performed with Nano-composite  SAXS  Impedance spectroscopy
ammonium peroxydisulfate as the oxidant agent and
different amounts of DBSA. The composites were
characterized by X-ray diffraction, attenuation reflec-
tance Fourier transform infrared spectroscopy, scan-
ning electron microscopy (SEM), impedance Introduction
spectroscopy and small angle X ray scattering
(SAXS). The highest electrical conductivity value Conducting nanomaterials have been attracted great
was achieved by using a DBSA/aniline molar ratio of scientific interest due to the increasing demand of
1.5 because this condition provided a better penetra- new technologies for the development of electronic
tion of PAni.DBSA chains inside the hydrated BC devices, sensors, intelligent clothes, to be employed
sheet, as observed by SEM. The in situ polymeriza- in several fields including biology, medicine, defense,
tion gives rise to conducting membranes with the agriculture, etc. In this context, cellulose nanofibers
surface constituted by different degree roughness as appear as very promising support materials for
indicated by Nyquist plots obtained from impedance conductive additives due to their high strength and
spectroscopy and confirmed by SAXS measurements. stiffness associated to renewability, biocompatibility
This preliminary work provides a new way to prepare and biodegradability, among other important proper-
ties (Dufresne and Belgacem 2010; Kamel 2007;
Klemm et al. 2006a; Siro and Plackett 2010).
J. A. Marins  B. G. Soares (&)  K. Dahmouche
Nanocellulose can be mainly obtained from plant
Centro de Tecnologia, Instituto de Macromoléculas—
UFRJ, Bl. J, Ilha do Fundão, Rio de Janeiro, sources in the form of microfibrils, microfibrillated
RJ 21945-970, Brazil cellulose and cellulose whiskers, (Holt et al. 2010),
e-mail: bluma@ima.ufrj.br from green algae (Stromme et al. 2002) and also
directly from extracellular secretion of certain bacte-
S. J. L. Ribeiro  H. Barud  D. Bonemer
Instituto de Quı́mica—UNESP, Araraquara, ria, being Gluconacetobacter Xylinus one of the most
SP 14801-970, Brazil productive (Klemm et al. 2006b). Both bacterial (BC)

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1286 Cellulose (2011) 18:1285–1294

and plant cellulose are constituted by b-D-glucopyr- Maria et al. 2009, 2010). Few months ago, when we
anose units linked by 1-4glycosidic bonds. However, were preparing this paper, it appeared in the open
the nanostructure of BC is obtained directly from the literature an interesting paper, and perhaps the first
bacteria, without treatment. BC is secreted as a one, dealing with the chemical ‘‘in situ’’ polymeriza-
ribbon-shaped fibril, less than 100 nm wide. These tion of pyrrole on BC nanofiber (Müller et al. 2011).
fibers are composed of bundles of much fine micro- The present work presents for the first time the
fibrils of nanometric size (Brown and Laborie 2007; preparation and characterization of conducting nano-
Iguchi et al. 2000; Klemm et al. 2001, 2005). This material by in situ chemical polymerization of aniline
microbiological procedure gives rise to cellulose in the presence of hydrated BC pellicle, aiming future
nanofibers of high purity (free of lignin and hemi- technological applications in electronics and optics.
celluloses), high degree of polymerization, high The influence of the content of dodecylbenzenyl-
crystallinity, high water content and high mechanical sulfonic acid used in the polyaniline synthesis on
stability. All these unique physical and mechanical structure and properties of the composites has been
properties determine its wide range of applications, investigated by Fourier transform infrared (FTIR)
including high quality audio membranes (Cannon and spectroscopy, scanning electron microscopy and
Anderson 1991), temporary skin substitution (Farah conductivity. The nanostructure was also evaluated
1990), electronic paper (Shah and Brown 2005) etc. by small angle X-ray scattering.
For all these reasons, it appears us interesting to
develop new conducting nanofiber-based materials
constituted by polyaniline coated on BC nanofiber Experimental
surface.
Several papers deal with the preparation of cellu- Materials
lose-based conducting materials. Some of them
involve the ‘‘in situ’’ polymerization of pyrrole (Py) Aniline (Ani) (analytical grade, Merck) was distilled
or aniline (Ani) in the presence of cellulose pulp twice under vacuum and stored under nitrogen in a
suspension (Johnston et al. 2006; Kelly et al. 2007; refrigerator. Ammonium peroxydisulfate (APS) (ana-
Qian et al. 2010), pulp fibers and papers (Johnston et al. lytical grade, Isofar), dodecylbenzenylsulfonic acid
2005; Stejskal et al. 2008; Goto 2011), wood or (DBSA) (Fluka, 90%) and ethanol (92.8%, Vetec)
sawdust (Ansari and Pornahad 2010; Sapurina et al. were used without purification. Hydrated Bacterial
2005; Stejskal et al. 2007) microfibrillated cellulose cellulose (BC) samples were provided by FibrocelÒ
(Nystrom et al. 2010) or individual cellulose fibers Products Bio- technological LTDA, (Ibiporã, Paraná-
extracted from Cladofora green algae (Mihranyan et al. Brazil). Bacterium G. xylinus cultivation was con-
2008). Also a chemical polymerization—induced ducted for 96 h at 28 °C in trays of 30 9 50 cm
adsorption process was employed for obtaining con- dimension, containing a sterile medium with the
ducting polymers uniformly coated on cellulose fiber following basic composition: glucose 2% (w/v),
from commercial filter paper (Huang et al. 2005). bactopeptone 0.5% (w/v), yeast extracts 0.5%, anhy-
Other systems consist of a mixture of cellulose drous disodium phosphate 0.27% (w/v) and citric
whiskers suspension with polyaniline (PAni) solution acid monohydrate 0.115% (w/v). After 69 h, highly
(van den Berg et al. 2007) or a dipping of microfibr- hydrated BC blankets with an average thickness of
illated cellulose aerogel in a PAni solution (Paakko 4 mm were produced. The obtained BC hydrogels
et al. 2008). were washed in water, immersed in 1 wt% aqueous
The use of BC on the development of conducting NaOH at 70 °C to remove the bacteria and their
materials is not common. There are few publications, residues, and thoroughly washed in distilled water
most of them focused on the combination of BC with until neutral pH.
carbon nanotubes (Chen et al. 2010; Yan et al. 2008;
Yoon et al. 2006). Silver nanoparticles were also Synthesis of BC-polyaniline composites
impregnated into BC through the in situ Ag? reduc-
tion aiming to develop antimicrobial membranes BC-Pani.DBSA nanocomposites were prepared in
(Barud et al. 2008; Maneerung et al. 2008; Santa ethanol/water (40:60 vol%) medium. Pre-established

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Cellulose (2011) 18:1285–1294 1287

Table 1 Recipes for the Pani.DBSA and their BC-based the diffractogram through the Ruland’s method
composites syntheses (Ruland 1961).
Code BC Ani APS DBSA Electrical conductivity measurements and NyQuist
(cm3) (mmol) (mmol) (mmol) plots were carried out using a Potentiostat galvanostat
analyzer AutoLAB in the frequency range of 10 to
PAni1 – 2.50 2.50 10.00
1 MHz and 10 mA at room temperature. The samples
PAni2 – 2.50 2.50 3.75
in the form of discs of 1 mm diameter were used.
PAni3 – 2.50 2.50 2.50
The microstructure of the composites was charac-
PAniBC1 30 2.50 2.50 10.00
terized by scanning electron microscopy (SEM). The
PAniBC2 30 2.50 2.50 3.75
films surfaces were analyzed by field emission SEM
PAniBC3 30 2.50 2.50 2.50
(FEG-SEM, JEOL—7500F) operating at at 2 kV. The
fracture surface was observed in a JEOL JSM 5600
Scanning electron microscope, operating at 15 kV. In
amounts of DBSA (Table 1) were mixed with 100 mL both cases, the surfaces were sputtered with carbon
ethanol/water solution. Then, 0.23 g (2.5 mmol) of and analyzed with the help of a secondary electron
aniline was added and the resulting solution was (SEI) detector.
stirred at room temperature for homogenization. Thermogravimetric analysis (TGA) was performed
Hydrated BC membrane with 5 9 6 9 1 cm3 dimen- on a Q50 thermobalance from TA Instruments Inc.
sion was immersed into the Ani/DBSA solution for The samples were heated from 30 to 700 °C, at a
15 min under magnetic stirring, in order to promote heating rate of 20 °C/min, under nitrogen flow.
the penetration of the reagents (Ani and DBSA) inside The small angle X ray scattering (SAXS) exper-
the BC hydrogel. The polymerization was carried out iments were carried out at the SAXS beam line of the
at 25 °C by slowly adding 10 mL of aqueous solution Brazilian Synchrotron Light Laboratory (LNLS),
containing 0.55 g (2.5 mmol) of APS to the solution Campinas (Brazil) with a fixed wavelength of 1.608
containing the swollen BC membrane. The total Å under vacuum at room temperature. The scattering
polymerization time was 24 h. After this time, the intensity I(q) was plotted as a function of the wave
BC/Pani.DBSA membrane was washed with ethanol vector q = 4psinh/k, where h is the scattering angle.
and vacuum dried at room temperature, obtaining The scattering intensity was normalized by subtract-
films with 0.05 ± 0.02 mm thickness. The dried BC ing the background scattering and taking account the
film presented a thickness of 0.03 ± 0.01 mm. Pure sample thickness.
Pani.DBSA samples were also prepared using similar
procedure. In these cases, the samples were precipi-
tated from water to the resulting powder was vacuum Results and discussion
dried at room temperature. Table 1 summarizes the
experiment recipes. BC samples used in this work consisted of hydrated
sheets with thickness around 1 mm. After drying, the
Characterization thickness of the BC sheet decreased to as low as
0.03 mm. The in situ polymerization of aniline was
Attenuation reflectance Fourier transformed Infrared performed in the presence of the hydrated (swollen)
spectra (ATR-FTIR) were recorded in a Bruker BC sheet. The polymerization started at the surface of
Spectrometer in the range of 4,000 to 800 cm-1 with the BC sheet, as indicated by the formation of several
64 scans. green points. After a certain period, the sheet became
X-ray diffraction (XRD) measurements were completely dark green and presented a thickness
obtained using a Rigaku Ultima IV difractometer, around 0.05 mm after drying. These sheets were also
equipped with a Cu Ka radiation source (k = self-supporting but very brittle when compared to the
1.45 nm), operating at 40 kV and 100 mA. The pure and dry BC sheet. These results suggest that
scanning rate was 0.058 s-1 and the corresponding PAni.DBSA is formed at the surface of the BC
intensities were measured over a 2h interval from 10 to nanofibers, destroying the original interactions
708. The degree of crystallinity (vc) was estimated from between the BC fibers.

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1288 Cellulose (2011) 18:1285–1294

Fig. 1 FTIR spectra of bacterial cellulose (A), PAniBC1 (B),


PAniBC2 (C), PaniBC3 (D) and pure PAni (E)

The impregnation of the BC nanofibers with


PAni.DBSA was confirmed by ATR-FTIR and
XRD. Figure 1 compares the ATR-FTIR spectra of
BC, PAni.DBSA and the BC/PAni.DBSA composites
prepared with different DBSA concentrations. The
spectrum of BC displays the main characteristic
bands at 3,345 cm-1 (due to stretching vibration of
OH groups), at 2,905 cm-1 (assigned to stretching
vibration of C–H bond in pyranoid ring) and at
1,050 cm-1 (attributed to the stretching vibration of
C–O bonds. (Grande et al. 2009) The spectrum of
PAni.DBSA presents typical peaks at around 1,585
and 1,485 cm-1 due to the stretching vibration of
quinoid and benzenoid structure, respectively. The Fig. 2 TGA curves of (a) PAni.DBSA, (b) their corresponding
BC/PAni.DBSA composites as a function of the DBSA
peak at 1,317 cm-1 is attributed to the stretching concentration and (c) pure BC
vibration of O=S=O groups and another one at
1,030 cm-1 is related to NH?SO3- interactions obtained with Pani-cellulose composites with those
(Babazadeh 2007). The spectra of the composites corresponding to the pure components, cellulose and
display the main characteristic absorptions of BC and PAni.DBSA prepared at the same conditions.
PAni.DBSA components. However, some particular- Figure 2 illustrates the TGA profiles of the samples
ities can be observed, such as: the absorption related prepared with different amount of DBSA. The main
to the OH group (peak a) presents a red shift, degradation parameters are also summarized in
suggesting some interactions between BC and PAni. Table 2. Both cellulose and polyaniline produce
Moreover, all composites display a new band at significant amount of residue. PAni.DBSA prepared
2,100 cm-1 (peak b), which is not present in the with higher amount of DBSA (PAni1) displayed
spectra of both components, indicating the formation lower amount of residue because of the presence of
of new chemical bonds, probably originated from DBSA in large extent.
grafting reactions of PAni.DBSA on the BC chains. To estimate the proportion of polyaniline in each
The amount of polyaniline in the composite was sample, it was assumed that both components in the
estimated from TGA, by comparing the residue composite (cellulose and PAni.DBSA) produce an

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Cellulose (2011) 18:1285–1294 1289

Table 2 TGA parameters of BC, PAni.DBSA and their cor- peaks at 2h = 14.5° and 23°, which are assigned to
responding BC/PAni.DBSA composites as a function of the the (110) and (220) diffraction planes (Watanabe
DBSA concentration
et al. 1998). PAni.DBSA exhibits two main charac-
Code BC DBSA/Ani Onset Residue teristic reflections at 12.6° and 22°. These peaks are
(cm3) (molar ratio) degradation (%) broad and overlap with other reflection peaks sug-
temperature
( °C)
gesting the presence of disordered structures. The
XRD patterns of the composites also present the
Pure BC 30 – 294 14 characteristic peaks related to the both components
PAni1 – 4 240 39 but that one at 2h = 14.5° related to the cellulose
PAni2 – 1.5 239 69 component is shifted towards higher 2h values and
PAni3 – 1.0 239 66 decreases in intensity as the amount of DBSA in the
PAniBC1 30 4 223 27 sample decreases. Additionally, some other reflec-
PAniBC2 30 1.5 223 33 tions are present, indicating the presence of new
PAniBC3 30 1.0 223 33 crystal forms, probably due to the interactions
between the components. The crystallinity degree of
PAni.DBSA in the pure form is similar to that found
amount of residue proportional to the amount of each
for the composite prepared at the same conditions,
component. Therefore, a theoretical relationship for
that is, with similar amount of DBSA. However, this
each composite was built taking into account the
property was strongly influenced by the DBSA
amount of residue of the pure components and
content. As observed in Table 3, the crystallinity
simulating their proportion in the composite. Based
degree is higher in the PAni1 and PAniBC1, which
on this calculation, it was possible to estimate the
was prepared with higher amount of DBSA. This
proportion of PAni in PAniBC1, PAniBC2 and
behavior suggests that the bulky DBSA dopant and
PAniBC3 as around 50, 35 and 35%, respectively.
the free DBSA molecules with the alkyl side chains
Figure 3 compares the XRD patterns of BC,
cause some self organization to form layer-type
PAni.DBSA and their corresponding BC/PAni.DBSA
ordering. (Tsotcheva et al. 2001; Ray et al. 2009).
composites as a function of the DBSA concentration.
Bulk conductivity of PAni.DBSA and their BC-
The spectrum of BC displays two main reflection
based nanocomposites was determined by impedance
analysis, whose dielectric response is described by
the complex impedance or Nyquist plot as Eq. 1:
Z ¼ Z0  jZ00 ð1Þ
where Z0 and Z00 are the real and imaginary parts of
the complex impedance, respectively (Soares et al.
2006). The Nyquist plots of the complex impedance
for PAni.DBSA and BC/PAni.DBSA composites are

Table 3 Crystallinity degree of cellulose, Pani.DBSA and the


composites
Sample Crystallinity (%)

Cellulose 58 ± 1
PAniBC1 48 ± 4
PAniBC2 42 ± 2
PAniBC3 38 ± 2
PAni1 47 ± 4
PAni2 42 ± 2
Fig. 3 WAXS patterns of bacterial cellulose (a), PAniBC1 PAni3 39 ± 2
(b), PAniBC2 (c), PaniBC3 (d) and pure PAni (e)

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1290 Cellulose (2011) 18:1285–1294

Fig. 4 Complex impedance plane (NyQuist plots) of Pani samples as a function of the DBSA concentration

illustrated in Figs. 4 and 5, respectively. From these than in the other systems, indicating a better homo-
plots, the resistance of the samples was determined geneity of this system.
by the intersection of the low frequency end of the The Nyquist plot can be related to an electrical
semicircle arc with the real axis, since R = Z0 when circuit constituted by a resistor connected to a
Z00 = 0 at low frequency. The conductivity (r) values constant phase element (CPE). The impedance value
of the samples, presented in Table 4, were calculated of a CPE is expressed by the following equation:
from the Eq. 2, where ‘ is thickness, and A is the area
1
of sample. ZCPE ¼ ð3Þ
QðjxÞn
l
r¼ ð2Þ where Q is a frequency-independent constant, x is
RA
the angular frequency and n values are the correlation
coefficients for the CPE. (Kobayashi et al. 1984;
Pure PAni.DBSA samples presented Nyquist plots Castagno et al. 2010) The CPE may be related to a
with one semi circle, as expected for one phase capacitor if n = 1, or a resistor if n = 0. When
material. PAni1 prepared with higher DBSA concen- n = 0.5, the charge transport may be associated with
tration showed higher bulk electrical conductivity a diffusion process. The CPE factor (n) is determined
value than the PAni2 and PAni3. This rise of the by Eq. 4, where H is the angle of initial semi-circle
conductivity with the increase the DBSA concentra- (Skale et al. 2007; Yuan et al. 2010).
tion has been already related in the literature (Ohlan
et al. 2009), and is related to the increase of the H
n¼ ð4Þ
doping degree. Bacterial cellulose presented conduc- 90
tivity around 10-6 times smaller than pure polyan- The CPE factor values of PAni1, PAni2 and PAni3
iline, as shown in Table 4. (Fig. 4) corresponded to 0.65, 0.67 and 0.69, respec-
The BC/PAni.DBSA composites presented tively, suggesting a diffusion process of the charge in
Nyquist plots with two semi-circles, indicating the a heterogeneous or porous matrix. This information is
presence of two phases (Fig. 5). The first semi circle consistent with the polyaniline morphology. The CPE
(represented in the insert Figures) was attributed to factor determined for the PAniBC1, PAniBC2 and
the pure polyaniline or regions with great amount of PAniBC3 composites corresponded to 0.61, 0.44 and
polyaniline and the second semi-circle was attributed 0.47, respectively. These values also indicate a
to the composites. The conductivity values of the two diffusion process of the charge in a porous medium.
phases are different, as expected for the heteroge- The lower values of the n exponent for the compos-
neous systems. In both phases, the highest conduc- ites when compared to those found for pure
tivity values were observed for PAniBC2 composite, PAni.DBSA samples suggest a diffusion process
synthesized with a DBSA/aniline molar ratio of 1.5. towards higher porous medium. In this sense,
Regarding the PAniBC3, the difference of the PAniBC1, prepared with higher amount of DBSA
conductivity values between the two phases is lower presented lower porosity.

123
Cellulose (2011) 18:1285–1294 1291

cross-sectional SEM micrographs are illustrated in


the corresponding inserted pictures. BC presents a
typical structure of cellulose produced by bacteria,
constituted by a 3-D network of nanofibers with
thickness of about 50 nm (Fig. 6a) (Gardner and
Blackwell 1975; Klemm et al. 2006a). This unique
nanostructure with large surface area, not found in
vascular plant cellulose, is responsible for its high
ability to absorb a great amount of water (up to 200
times of its dry mass) and its great elasticity, high wet
strength, and conformability (Czaja et al. 2006). Such
nanofibers are difficult to distinguish in the surface
morphology of the BC/PAni.DBSA composites,
especially those prepared with lower amounts of
DBSA (PAniBC2 and PAniBC3—Fig. 6c, d). These
surface morphologies also present different degrees
of roughness indicating that the PAni.DBSA are
formed at the surface of the BC sheets inducing some
compaction of the polymeric structure. The cross-
sectional micrographs give better information regard-
ing the distribution of the PAni.DBSA in the BC
sheet. PAniBC1 composite (Fig. 6b) shows a thin
layer of PAni.DBSA coated on the surface of the BC
sheet and very few amounts of PAni diffused into the
interior of the sheet. This composite presents the
highest amount of PAni.DBSA and the good con-
ductivity value of phase 1 (related to the PAni). This
morphology explains the lower bulk electrical con-
ductivity of this sample (conductivity value of Phase
2). It is believed that the high amounts of DBSA used
to prepare this sample interact with the BC nanofibers
located at the surface of the sheet and form a layer,
which hinder the penetration of the polyaniline grown
chain inside the BC sheet. Such self-organized layer
may be also responsible for the higher crystallinity
degree of this sample, discussed previously.
In the case of PAniBC2 (Fig. 6c) and PAniBC3
(Fig 6d), which were prepared with lower amounts of
DBSA, the PAni.DBSA chains were able to penetrate
inside the BC sheet, giving rise to more homogeneous
composites.
Fig. 5 Complex impedance plane (NyQuist plots) of BC/ The arrangement of the PAni.DBSA in the differ-
Pani.DBSA composites as a function of the DBSA ent BC-based nanocomposites was also evaluated by
concentration
small angle X-ray scattering experiments. Figure 7
illustrates the SAXS patterns of these composites as a
The modification of the BC structure by impreg- function of the amount of DBSA. The SAXS results
nation of PAni.DBSA was confirmed by SEM of PAniBC3 prepared with low amount of DBSA
analysis. Figure 6 presents the FEG–SEM micro- suggest a nanostructure consisted of spatially corre-
graphs of the surfaces of the composites, whose lated PAni nano-domains in the cellulose, forming

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1292 Cellulose (2011) 18:1285–1294

Table 4 A.C Bulk


Sample Conductivity (S/cm) CPE factor (n)
conductivity of bacterial
cellulose, PAniBC1, a b
Phase 1 Phase 2
PAniBC2, PAniBC3 and
polyanilines PAni1 2.09 9 10-2 *** 0.65
PAni2 1.93 9 10-3 *** 0.67
PAni3 4.04 9 10-5 *** 0.69
PAniBC1 1.61 9 10-4 7.78 9 10-6 0.61
a
Phase 1 refers to pure PAniBC2 1.88 9 10-4 8.13 9 10-5 0.44
PAni; b Phase 2 refers to PAniBC3 5.78 9 10 -6
6.72 9 10-7 0.47
composite; c Conductive of
Cellulosec 6.50 9 10-8 0.55
pure cellulose

larger secondary aggregates which present a rough with both the existence of local chemical interaction
surface (slope of the Porod0 s region of the aggregates between PAni and cellulose and with the observed
around 3.7). By increasing the DBSA content (PA- increase of conductivity for this sample (Table 4). In
niBC2) the shoulder observed at high q-values due to the spectrum of the composite containing the highest
spatial correlation between domains is more pro- DBSA content (PAniBC1) the spatial correlation
nounced. This feature occurs probably because the between PAni domains disappears and the slope at
more efficient polymerization and crystallization of low q-values decreases up to around 3, indicating an
PAni promoted by DBSA causes shrinkage of the increase of the roughness degree of the surface,
cellulose chains located around and between the PAni which is in agreement with the PAni.DBSA prefer-
primary domains. This interpretation is consistent entially located at the surface of the BC sheets.

Fig. 6 SEM micrographs of bacterial cellulose (a), PAniBC1 (b), PAniBC2 (c) and PAniBC3 (d)

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Cellulose (2011) 18:1285–1294 1293

Fig. 7 SAXS patterns of PAniBC1(a), PAniBC2(b) and PaniBC3(c)

Conclusions Babazadeh M (2007) A direct one-pot method for synthesis of


polyaniline doped with dodecyl benzene sulphonic acid in
aqueous medium and study of its thermal properties. Iran
Conducting composites were successfully prepared Polym J 16:389–396
by the in situ polymerization of aniline in the Barud HS, Barrios C, Regiani T, Marques RFC, Verelst M,
presence of hydrated bacterial cellulose. The crystal- Dexpert-Ghys J, Messaddeq Y, Ribeiro SJL (2008) Self-
linity degree of the pure PAni.DBSA and the supported silver nanoparticles containing bacterial cellu-
lose membranes. Mater Sci Eng C-Biomimetic Supramol
corresponding BC—based nanocomposites increased Syst 28:515–518
with the DBSA concentration. The optimum DBSA/ Brown EE, Laborie MPG (2007) Bloengineering bacterial
aniline molar ratio to produce BC/PAni.DBSA with cellulose/poly(ethylene oxide) nanocomposites. Biomac-
higher bulk conductivity corresponded to 1.5. Higher romolecules 8:3074–3081
Cannon RE, Anderson SM (1991) Biogenesis of bacterial
amount of DBSA resulted in a DBSA layer at the BC cellulose. Crit Rev Microbiol 17:435–447
sheet surface, which avoid the penetration of the Castagno KRL, Dalmoro V, Mauler RS, Azambuja DS (2010)
polyaniline chains inside the bulk material. This Characterization and corrosion protection properties of
behavior resulted in a decrease of the bulk electrical polypirrole/montmorillonite electropolymerized onto
aluminium alloy 1100. J Polym Res 17:647–655
conductivity. From SAXS experiments, one can Chen P, Yun YS, Bak H, Cho SY, Jin HJ (2010) Multiwalled
suggest the formation of surface with different carbon nanotubes-embedded electrospun bacterial cellu-
degrees of roughness, which is confirmed by SEM lose nanofibers. Mol Cryst Liq Cryst 519:169–178
micrographs. This preliminary study is very promis- Czaja W, Krystynowicz A, Bielecki S, Brown RM (2006)
Microbial cellulose—the natural power to heal wounds.
ing, in the sense that these new BC—based nano- Biomaterials 27:145–151
composites may be found important applications as Dufresne A, Belgacem MN (2010) Cellulose-reinforced com-
optical and electrical displays. Additional experi- posites: from micro-to nanoscale. Polı́meros: Ciência e
ments involving different reaction conditions are in Tecnologia 20:1–10
Farah LFX (1990) Process for the preparation of cellulose film,
progress aiming to achieve a better combination of cellulose film produced thereby, artificial skin graft and its
electrical conductivity and mechanical properties, use. Bio Fill Produtos Biotechnologicos S.A. (Parana,
and will be published sooner. BR), US patent no. 4,912,049
Gardner KH, Blackwell J (1975) Refinement of structure of
Acknowledgments The authors thank CNPq, FINEP and beta-chitin. Biopolymer 14:1581–1595
FAPERJ for the financial support and scholarships. The authors Goto H (2011) Electrically conducting paper from a polyani-
also acknowledge the Brazilian Synchrotron Laboratory line/pulp composite and paper folding art work for a 3D
(LNLS) for the support on SAXS experiments. object. Text Res J 81:122–127
Grande CJ, Torres FG, Gomez CM, Bano MC (2009) Nano-
composites of bacterial cellulose/hydroxyapatite for bio-
medical applications. Acta Biomater 5:1605–1615
Holt BL, Stoyanov SD, Pelan E, Paunov VN (2010) Novel
References anisotropic materials from functionalised colloidal cellu-
lose and cellulose derivatives. J Mater Chem 20:10058–
Ansari R, Pornahad A (2010) Removal of Ce(IV) Ions from 10070
aqueous solutions using sawdust coated by electroactive Huang JG, Ichinose I, Kunitake T (2005) Nanocoating of
polymers. Sep Sci Technol 45:2376–2382 natural cellulose fibers with conjugated polymer:

123
1294 Cellulose (2011) 18:1285–1294

hierarchical polypyrrole composite materials. Chem Ray S, Easteal AJ, Cooney RP, Edmonds NR (2009) Structure
Commun, 1717–1719 and properties of melt-processed PVDF/PMMA/polyani-
Iguchi M, Yamanaka S, Budhiono A (2000) Bacterial cellu- line blends. Mat Chem Phys 113:829–838
lose—a masterpiece of nature’s arts. J Mater Sci 35: Ruland W (1961) X-ray determination of crystallinity and
261–270 diffuse disorder scattering. Acta Crystallogr A 14:1180
Johnston JH, Moraes J, Borrmann T (2005) Conducting poly- Santa Maria LC, Santos ALC, Oliveira PC, Barud HS, Mess-
mers on paper fibres. Synth Met 153:65–68 addeq Y, Ribeiro SJL (2009) Synthesis and characteriza-
Johnston JH, Kelly FM, Moraes J, Borrmann T, Flynn D tion of silver nanoparticles impregnated into bacterial
(2006) Conducting polymer composites with cellulose and cellulose. Mater Lett 63:797–799
protein fibres. Curr Appl Phys 6:587–590 Santa Maria LC, Santos ALC, Oliveira PC, Valle ASS, Barud
Kamel S (2007) Nanotechnology and its applications in lig- HS, Messaddeq Y, Ribeiro SJL (2010) Preparation and
nocellulosic composites, a mini review. Express Polym antibacterial activity of silver nanoparticles impregnated
Lett 1:546–575 in bacterial cellulose. Polimeros-Ciencia E Tecnologia
Kelly FM, Johnston JH, Borrmann T, Richardson MJ (2007) 20:72–77
Functionalised hybrid materials of conducting polymers Sapurina I, Kazantseva NE, Ryvkina NG, Prokes J, Saha P,
with individual fibres of cellulose. Eur J Inorg Chem, Stejskal J (2005) Electromagnetic radiation shielding by
5571–5577 composites of conducting polymers and wood. J Appl
Klemm D Kramer F Kamitakahara H (2006) Materials and Polym Sci 95:807–814
composites from cellulose with well-defined molecular Shah J, Brown RM (2005) Towards electronic paper displays
and supramolecular order. Abstracts of papers of the Am made from microbial cellulose. Appl Microbiol Biotech-
Chem Soc 231, 67-CELL nol 66:352–355
Klemm D, Schumann D, Udhardt U, Marsch S (2001) Bacterial Siro I, Plackett D (2010) Microfibrillated cellulose and new
synthesized cellulose—artificial blood vessels for micro- nanocomposite materials: a review. Cellulose 17:459–494
surgery. Prog Polym Sci 26:1561–1603 Skale S, Dolecek V, Slemnik M (2007) Substitution of the
Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: constant phase element by Warburg impedance for pro-
Fascinating biopolymer and sustainable raw material. tective coatings. Corros Sci 49:1045–1055
Angew Chem Int Ed 44:3358–3393 Soares BG, Leyva ME, Barra GMO, Khastgir D (2006)
Klemm D, Schumann D, Kramer F, Hessler N, Hornung M, Dielectric behavior of polyaniline synthesized by different
Schmauder HP, Marsch S (2006) Nanocelluloses as techniques. Eur Polym J 42:676–686
innovative polymers in research and application. Poly- Stejskal J, Trchova M, Brodinova J, Sapurina I (2007) Flame
saccharides Ii 205:49–96 retardancy afforded by polyaniline deposited on wood.
Kobayashi T, Yoneyama H, Tamura H (1984) Oxidative-deg- J Appl Polym Sci 103:24–30
radation pathway of polyaniline film electrodes. J Elec- Stejskal J, Trchova M, Kovarova J, Prokes J, Omastova M
troanal Chem 177:293–297 (2008) Polyaniline-coated cellulose fibers decorated with
Maneerung T, Tokura S, Rujiravanit R (2008) Impregnation of silver nanoparticles. Chem Pap 62:181–186
silver nanoparticles into bacterial cellulose for antimi- Stromme M, Mihranyan A, Ek R (2002) What to do with all
crobial wound dressing. Carbohydr Polym 72:43–51 these algae? Mater Lett 57:569–572
Mihranyan A, Nyholm L, Bennett AEG, Stromme M (2008) Tsotcheva D, Tsanov T, Terlemezyan L, Vassilev S (2001)
Novel high specific surface area conducting paper mate- Structural investigations of polyaniline prepared in the
rial composed of polypyrrole and Cladophora cellulose. presence of dodecylbenzenesulfonic acid. J Therm Anal
J Phys Chem B 112:12249–12255 Calorim 63:133–141
Müller D, Rambo C, Recouvreux D, Porto L, Barra G (2011) van den Berg O, Schroeter M, Capadona JR, Weder C (2007)
Chemical in situ polymerization of polypyrrole on bac- Nanocomposites based on cellulose whiskers and
terial cellulose nanofibers. Synth Met 161:106–111 (semi)conducting conjugated polymers. J Mater Chem
Nystrom G, Mihranyan A, Razaq A, Lindstrom T, Nyholm L, 17:2746–2753
Stromme M (2010) A nanocellulose polypyrrole com- Watanabe K, Tabuchi M, Morinaga Y, Yoshinaga F (1998)
posite based on microfibrillated cellulose from wood. Structural features and properties of bacterial cellulose
J Phys Chem B 114:4178–4182 produced in agitated culture. Cellulose 5:187–200
Ohlan A, Singh K, Chandra A, Singh VN, Dhawan SK (2009) Yan ZY, Chen SY, Wang HP, Wang B, Wang CS, Jiang JM
Conjugated polymer nanocomposites: synthesis, dielec- (2008) Cellulose synthesized by Acetobacter xylinum in
tric, and microwave absorption studies. J Appl Phys the presence of multi-walled carbon nanotubes. Carbo-
106:044305 hydr Res 343:73–80
Paakko M, Vapaavuori J, Silvennoinen R, Kosonen H, Yoon SH, Jin HJ, Kook MC, Pyun YR (2006) Electrically
Ankerfors M, Lindstrom T, Berglund LA, Ikkala O (2008) conductive bacterial cellulose by incorporation of carbon
Long and entangled native cellulose I nanofibers allow nanotubes. Biomacromolecules 7:1280–1284
flexible aerogels and hierarchically porous templates for Yuan X-Z, Song C, Wang H, Zhang J (2010) Electrochemical
functionalities. Soft Matter 4:2492–2499 impedance spectroscopy in PEM fuel cells, fundamentals
Qian XR, Shen J, Yu G, An XH (2010) Influence of pulp fiber and applications. Springer, London
substrate on conductivity of polyaniline-coated conduc-
tive paper prepared by in situ polymerization. Biore-
sources 5:899–907

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