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Received: 8 February 2011 / Accepted: 6 June 2011 / Published online: 15 June 2011
Ó Springer Science+Business Media B.V. 2011
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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
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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
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.
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Cellulose (2011) 18:1285–1294 1291
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1292 Cellulose (2011) 18:1285–1294
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
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