Cellulose (2012) 19:16451654 DOI 10.

1007/s10570-012-9754-9

ORIGINAL PAPER

Electrically conducting nanocomposites: preparation and properties of polyaniline (PAni)-coated bacterial cellulose nanobers (BC)
D. Muller J. S. Mandelli J. A. Marins B. G. Soares L. M. Porto C. R. Rambo G. M. O. Barra

Received: 8 February 2012 / Accepted: 23 July 2012 / Published online: 1 August 2012 Springer Science+Business Media B.V. 2012

Abstract Free-standing lms of bacterial cellulose (BC) and polyaniline (PAni) (BC/PAni) composites with high electrical conductivity values (0.9 S cm-1) and good mechanical properties (40 MPa) were prepared through in situ oxidative chemical polymerization of aniline (Ani) on the surface of synthesized BC nanobers by using FeCl36H2O, as oxidant. The inuence of polymerization conditions such as oxidant content, protonic acid, and reaction time on electrical conductivity, morphological, tensile properties and thermal stability of the BC/PAni composites was investigated. Electrical conductivities of BC/PAni composites increased with increasing reaction time due to the formation of a continuous layer that completely coated the nanober surface. FTIR spectra of BC/PAni composites produced with and without
D. Muller J. S. Mandelli G. M. O. Barra (&) Polymer and Composites Laboratory, Mechanical Engineering Department, Federal University of Santa Catarina (UFSC), Florianopolis, SC, Brazil e-mail: guiga@emc.ufsc.br J. A. Marins B. G. Soares Centro de Tecnologia, Federal University of Rio de Janeiro, Rio de Janeiro, RJ, Brazil L. M. Porto Chemical and Food Engineering Department, UFSC, Florianopolis, SC, Brazil C. R. Rambo Electrical Engineering Department, UFSC, Florianopolis, SC, Brazil

protonic acid exhibited overlapped absorption bands of both BC and PAni, except for quinoid and benzoid bending modes of PAni. The in situ oxidative chemical polymerization gives rise to conducting membranes with the surface constituted by different PAni content, as indicated through CHN elemental analysis. The crystalline structure of BC was not affected by the incorporation of PAni. Scanning electron microscopy analysis of the composites revealed that PAni consisted of nanoparticles around 70 nm in mean size to form a continuous coating that encapsulates the BC nanobers. The BC/PAni composites obtained by the method described in this work have interesting properties that may nd important technological applications such as sensors, electronic devices, intelligent clothes, exible electrodes and tissue engineering scaffolds. Keywords Bacterial cellulose Polyaniline Conducting composites

Introduction There is a growing interest in developing nanober based conducting composites containing intrinsically conducting polymers (ICP), such as polyaniline (PAni) and polypyrrole (PPy) for a number of technological applications, including electronic devices, sensors, and intelligent clothes. These materials are generally obtained through in situ oxidative polymerization of

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pyrrole (Py) or aniline (Ani) in the presence of industrial textiles (Lee and Hong 2000; Cucchi et al. 2009; Johnston et al. 2005; Beneventi et al. 2006) or electrospun nanobrous templates (Li et al. 2006; Liu et al. 2008; Chronakis et al. 2006; Picciani et al. 2009). Among several nanoberbased materials, bacterial cellulose (BC) can be an attractive insulating polymer matrix for the preparation of conducting nanocomposites. BC is a versatile biopolymer with a wide range of properties that can be used for several applications, including biomedical devices and scaffolds for tissue and organ engineering (Rambo et al. 2008; Recouvreux et al. 2011). This polymer is produced through cellulose biosynthesis in aqueous solution and exhibits a nanobrous network similar to that those found in electrospun polymer scaffolds. Moreover, these materials can maintain their structure and mechanical stability even in hydrogel form. In this context, conducting nanocomposites comprised of BC coated with conducting polymers emerge as new promising polymer platform that present a unique combination of the tensile strength, toughness, biocompatibility, high surface areas with the non cytotoxy (Li et al. 2006; Kamalesh et al. 2000), electronic, optical, magnetic and chemical properties of conduct ing polymers (Muller et al. 2011) . Although several papers deal with the preparation of cellulosebased conducting materials (Sasso et al. 2010a, b) only very recently was BC employed for this purpose (Muller et al. 2011; Marins et al. 2011; Hu et al. 2011; Lee et al. 2012). Some studies dealing with carbon nanotubes (Yoon et al. 2006; Yan et al. 2008; Chen et al. 2010) or silver nanoparticles (Barud et al. 2008; Maneerung et al. 2008; Santa Maria et al. 2009) lled BC composites were reported in the literature. However, the rst BC/ICP conductive nanocomposite with electrical conductivity value as high as 1 S cm-1 was recently reported by Muller et al. (2011). In this work, dried BC nanobers were coated with polypyrrole through in situ oxidative polymerization of pyrrole aqueous solution by using iron III chloride (FeCl36H2O), as oxidizing agent. BC/PAni composites, on the other hand, have been developed by different groups. Marins et al. performed the in situ polymerization of aniline in the presence of BC hydrogel sheets (Marins et al. 2011). The polymerization occurred in the presence of dodecylbenzene sulfonic acid (DBSA) and ammonium persulfate (APS). According to the authors, the morphology,

crystallinity degree and electrical conductivity were affected by DBSA concentration. Hu et al. used wet BC membranes and studied the inuence of reaction time and different types of protonic acids on the electrical conductivity of BC/PAni composites (Hu et al. 2011). As expected, the amount of PAni deposited on the BC nanobers and electrical conductivity values of BC/ PAni blends enhanced with increasing the reaction time reaching a maximum of 5 9 10-2 S cm-1 after 90 min. Lee et al. (2012) obtained BC/PAni composites through direct in situ polymerization of aniline on BC bers by using HCl and p-toluene sulfonic acid (PTSA) solutions as protonic acid and APS, as the oxidant. Electrical conductivity values of BC/PAni doped with and without PTSA were 1.3 and 0.8 S cm-1, respectively. All BC/PAni reported in the literature employed APS as the oxidant. The FeCl3 should be a good approach for preparing these conducting nanocomposites because in aqueous solutions, iron III forms aquo-hydroxyl complexes (Hosny et al. 1997; Sasso et al. 2010a, b) and some of them (mainly Fe3? and Fe(OH)2?) are adsorbed on acellulose surface (Beneventi et al. 2006). When an appropriated amount of iron III is adsorbed on the cellulose bers, the polymerization takes place preferentially on the ber surface to form a continuous conducting coating that fully encapsulates the bers without altering signicantly their morphology and physicalchemical properties (Beneventi et al. 2006; Johnston et al. 2005; Kelly et al. 2007). Considering the reported advantages of FeCl3 as the oxidant, the aim of this work is the preparation and characterization of conducting nanomaterial through in situ chemical polymerization of aniline in the presence of hydrated BC by using iron (III) chloride hexahydrate.

Experimental Materials Aniline (analytical grade, Merck) was distilled under vacuum and stored in a refrigerator. Iron (III) chloride hexahydrate (FeCl36H2O) was purchased from Vetec and used without any further purication. Gluconacetobacter hansenii, strain ATCC 23769, acquired from the Collection of Tropical Culture (CCT) (Andre Tosello Foundation, Brazil) was used for the cellulose production.

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Synthesis of bacterial cellulose The bacterial cellulose (BC) membrane synthesis was carried out by cultivating the bacterium for 3 days, under static conditions, according to the procedure described elsewhere (Rambo et al. 2008). Briey, G. hansenii pre-cultivation was carried out overnight in conical asks, containing sterile aqueous medium with mannitol, yeast extract, and bactopeptone, adjusted to an initial pH of 6.6 with NaOH aqueous solution (1 mol L-1). To produce the BC membranes, sterile medium with the same composition as the sterilized pre-inoculum was inoculated with 10 % of the pre-inoculum that was previously, vigorously stirred to release cells from the cellulosic mass, and added to a 24-well culture plate (TPP Techno Plastic Products AG, Switzerland) and left for 3 days at room temperature. At the end of the batch culture the bacteria and their residues were removed with a solution of 0.1 mol L-1 NaOH at 90 C for 20 min and thoroughly washed in distilled water until neutral pH. BC/PAni composite preparation Bacterial cellulose/PAni nanocomposites were prepared through the in situ aniline oxidative polymerization by using iron (III) chloride hexahydrate (FeCl36H2O) as oxidant. The reactions were performed in the presence of HCl aqueous solution (namely BC/PAni.HCl) or in the absence of mineral acid (series BC/PAni.W). In the rst series, BC hydrogel membranes with diameter of 10 mm were immersed in an HCl aqueous solution (0.5 mol L-1) containing 0.1 mol L-1 of aniline. After 10 min under magnetic stirring, an appropriate amount of FeCl3 aqueous solution was added and the polymerization was carried out at 5 C during different time intervals, under magnetic stirring. Similar procedure was employed for the reactions performed without the addition of HCl. After polymerization the BC/PAni membranes were thoroughly washed with HCl aqueous solution (0.1 mol L-1) in order to extract the byproducts and residues of the reaction and vacuum dried at room temperature. The thickness of the dried conducting polymer composites was in the range of 0.010.02 mm. For comparison, pure PAni samples were also synthesized using a similar procedure. PAni samples

obtained in the presence of HCl (PAni.HCl) and in absence of HCl (PAni.W) as conducting powder were ltered, washed with HCl aqueous solution (0.1 mol L-1) and distilled water, respectively, and dried at room temperature. Physicochemical and electrical characterization The electrical conductivity of the membranes was measured using the four-probe method by a Keithley electrometer 6517A and a Keithley power source 6220. The impregnation of the BC nanobers with PAni was evaluated through Fourier transform infrared spectroscopy (FTIR) in a Shimadzu, model IR PRESTIGE-2, instrument with an ATR (attenuated total reectance) accessory and ZnSe crystal (ATR Smart Performance module). The spectra of dried BC and BC/PAni composites were recorded in the range of 4,000700 cm-1 by accumulating 64 scans at a resolution of 4 cm-1. Thermogravimetric analysis (TGA) was performed on a Q50 thermobalance from TA Instruments Inc. The samples were heated from 30 to 700 C, at a heating rate of 20 C/min, under nitrogen ow. The PAni content in the composites was determined using CHN Elemental Analyzer from PerkinElmer 2400 Series II with accuracy of 0.3 %. The method was based on the combustion of the BC, PAni and composites in an oxygen atmosphere at 925 C. Tensile tests of BC membranes and BC/PAni composites with thicknesses in the range 1030 lm were performed using a Dynamic mechanical analyzer (Q-800, TA Scientic) equipped with clamp for lms. The tests were performed at room temperature and speed of 3 mm min-1. The BC and composites were kept under vacuum conditions before analysis. The modulus of elasticity, tensile strength and elongation at break were calculated from the stressstrain curves considering at least six analyses of each sample. X-ray diffraction (XRD) measurements were obtained at room temperature using a Philips diffractometer model X0 Pert with CuKa radiation (k = 1.54 nm). Dried BC and composite membrane were placed on an aluminum plate and measured over a 2h interval of 550 with steps of 1 min-1. The degree of crystallinity (vc) of the cellulose membrane was estimated from the diffractogram through the ratio between the areas under the 1" and (200) crystalline 10 peaks and the total area, according to the method

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placed over an aluminum support and sputtered with gold.

Results and discussion The in situ polymerization of aniline in the presence of BC hydrogel membranes was performed in water solution (BC/PAni.W) or in HCl aqueous solution (BC/PAni.HCl). During polymerization the BC membranes turned from white to lightly green within 2 h of reaction and after 6 h the membranes became completely green, indicating the coating of the BC nanobers by PAni. The effect of the oxidant/aniline

Fig. 1 Electrical conductivity of BC/PAni composites versus FeCl3/Ani molar ratio

described by Watanabe and Tabuchi (1998). The crystalline domain size (t) or the extent of order of the polymers prepared in water and HCl was estimated using the Scherrers equation: t 0:9k W cos h 1

where k is the x-ray wavelength, W is the line broadening at half the maximum intensity (FWHM) in radians, and h is the Bragg angle. The 1" 10 diffraction plane was used for the calculus of W. The microstructure of the samples was evaluated by Field-Emission Gun Scanning electron microscopy (FEG-SEM, JEOL JSM-670F) operating at 15 kV and 80 A. For the observations, BC and composites membranes with diameters of 5 mm were dried and

Fig. 2 Electrical conductivity as function of reaction time

Fig. 3 FTIR spectra of BC; PAni and BC/PAni composites prepared with 6 and 18 h reaction time

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Cellulose (2012) 19:16451654 Fig. 4 TG curves of BC; PAni and BC/PAni composites prepared with 6 and 18 h reaction time

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(FeCl3/Ani) molar ratio on the electrical conductivity of BC/PAni composites after 6 h of reaction is shown in Fig. 1. In both systems, the electrical conductivity increased as the FeCl3/Ani molar ratio increased, reaching a plateau at a FeCl3/Ani ratio of 2, with electrical conductivity values of around 3.5 9 10-2 and 5 9 10-1 S cm-1 for BC/PAni.W and BC/ PAni.HCl, respectively. For all FeCl3/Ani molar ratios employed, the addition of HCl resulted in higher values of conductivity, suggesting higher protonation degree of PAni. Nevertheless, relatively high conductivities were obtained in systems obtained without the presence of HCl. According Kelly et al. the reduction

process of FeCl3 may provide enough HCl to promote the formation of emeraldine (Kelly et al. 2007). Moreover, for FeCl3/Ani molar ratio higher than 4, BC/PAni samples could be handled but very brittle when compared to the BC/PAni membranes obtained by using FeCl3/Ani ratio of 2 or 1.3 for aniline polymerization on BC nanobers. According Beneventi et al. (2006), under aggressive polymerization conditions cellulose can be subjected to acid hydrolysis and ber degradation. In order to obtain BC/PAni composites with higher electrical conductivity at low FeCl3/Ani ratio, and prevent cellulose degradation, the inuence of the

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1650 Table 1 TGA parameters of BC, PAni and their corresponding BC/PAni composites

Cellulose (2012) 19:16451654 PAni contenta (%)

Code

BC (mm3)

Reaction time (h)

Onset degradation temperature (oC) 276 220 218 224 240 215 214

Residue (%)

Electrical conductivity (S cm-1) 1.7 9 10-13 9.1 9 10-1 7.4 9 10-2 8,2 9 10-4 8,9 9 10-1 2.2 9 10-4 5.5 9 10-2

BC PAni.HCl Pani.W BC/PAni.HCl BC/PAni.HCl BC/PAni.W

a

1 1 1 1 1

18 18 6 18 6 18

2 57 61 29 28 28 40

17.8 38.8 24.0 42.5

Calculated by CHN analysis

BC/PAni.W

Fig. 5 Tensile stressstrain curve of (a) air dried BC, (b) BC/ PAni.W (66/34) and (c) BC/PAni.HCl (49/51) (wt./wt.)

reaction time on the electrical conductivity was investigated for samples prepared at FeCl3/Ani = 1.3/1 (Fig. 2). The electrical conductivity proles are characterized by a sharp initial increase after 5 h of reaction, and tend to a plateau after 18 h. This behavior is probably attributed to the high PAni yield achieved at this time which allows the formation of continuous conducting layers on the BC nanober surface. These results reveal that the adequate reaction time to prepare BC/PAni composites with higher electrical conductivities at 0.1 mol L-1 aniline concentration and molar ratio (FeCl3/Ani) of 1.3/1 is above 18 h. Figure 3 shows the ATR-FTIR spectra of PAni.HCl, PAni.W, BC and BC/PAni composites prepared with aniline concentrations (0.1 mol L-1), oxidant/aniline molar ratio (1.3/1) and reaction times of 6 and 18 h. The characteristic broad band of

Fig. 6 X-ray diffraction patterns of pure cellulose membrane, pure PAni polymerized in water and HCl and PAni/BC blends synthesized in H2O and HCl for 18 h

cellulose OH groups appears at 3,342 cm-1. The bands 2,915 and 1,642 cm-1 are attributed to the asymmetrically stretching vibration of CH and the OH bending of the absorbed water, respectively. The broad absorption band in the range of 1,060 1,030 cm-1 is assigned to the vibration of the CO and COC functional groups of the pyranose ring skeletal (Grande et al. 2009). PAni exhibits an absorption band at 1,556 cm-1 and 1,470 cm-1, assigned to the stretching vibration of quinoid and benzoid structure, respectively. The spectra of the BC/ PAni.HCl and BC/PAni.W composites produced with 6 and 18 h reaction time exhibited overlapped absorption bands of both components, except for the quinoid and benzoid structure. Small peaks in transmittance at around 1,556 and 1,470 cm-1 and the bending modes

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Fig. 7 FEG-SEM micrographs of BC (a), BC/PAni.W and BC/PAni.HCl composite obtained with 0.1 mol L-1 aniline concentration after: 6 h (b and c) and 18 h (d and e) reaction time, respectively

for OH groups of BC were observed for BC/PAni composites obtained for 6 h reaction time, which indicates that the BC was coated with PAni.HCl or PAni-W. Otherwise, with increasing the reaction time (18 h), the stretching vibration of quinoid and benzoid structure of PAni is increased while the OH group band is decreased. As expected, these results indicate that the content of PAni in the coating layer was enhanced with reaction time. Thermogravimetric analysis was employed to determine the thermal stability of BC/PAni samples prepared by different procedures. Figure 4 compares

the TG proles of the BC/PAni samples prepared with different conditions. The main degradation parameters are summarized in Table 1. The TG curves of the BC/ PAni composites display two main degradation stages. The rst one is related to the presence of moisture in the samples. The second stage is attributed to the decomposition of the amorphous BC region (Hu et al. 2011). The onset temperature of the thermo-degradation of BC/PAni is similar for all samples, as shown in Table 1. However, the composites exhibited lower onset degradation temperature than that of pure BC. According to Hu et al. and Marins et al., this behavior

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Fig. 8 FEG-SEM micrographs of BC (a), BC/PAni.W (b) and BC/PAni.HCl (c) obtained with 0.1 mol L-1 aniline concentrations after 18 h fracture surface

can be associated with the weakened intermolecular hydrogen bonding of cellulose chains by the presence of PAni (Hu et al. 2011; Marins et al. 2011). The amount of PAni in the composites was determined by CHN analysis and the results are also presented in Table 1. The composite prepared without the addition of HCl (BC/PAni.W) presented higher incorporation of PAni on BC surfaces than those found for BC/PAni.HCl composites. However, the electrical conductivity values of BC/PAni.W composites were not higher, which indicates that the lower protonation degree of PAni.W should be the cause for the lower conductivity. Figure 5 shows the stressstrain curves for BC and BC/PAni composites. BC sheets and their composites show typical brittle behavior material, i.e., all samples exhibit elongation at break lower than 1.9 %. The tensile strength and Young0 s Modulus of pure BC are about 64 MPa and 4.8 GPa, respectively. For BC/ PAni.W or BC/PAni.HCl, the tensile strength values were 48 and 41 MPa, respectively, which are 25 and 36 % lower than the values for the pure BC. Moreover, the Young0 s modulus of composites were approximately 2.5 GPa, which are 48 % lower than BC. These

results suggest that PAni is formed on BC nanobers, reducing inter and intramolecular hydrogen bonding of BC nanobers. Figure 6 shows the X-ray diffraction spectra of PAni, BC and composites produced in water and in HCl. Diffraction patterns of PAni produced in H2O and HCl exhibit two broad peaks around 20 and 26, which are peaks assigned to PAni (Yun and Kim 2006; Raghavendra et al. 2003). XRD-spectrum of cellulose reveals its nanocrystalline nature, characterized by two main diffraction planes 1" and (200) typical of 10 cellulose I (Watanabe and Tabuchi 1998; Czaja et al. 2006). The estimated crystallite size of the pure cellulose membrane is 7.4 nm, in accordance with Watanabe and Tabuchi (1998). The estimated degree of crystallinity of the cellulose membranes is 55 5 %. The produced blends exhibit a semicrystalline nature. Two main peaks can be identied in the spectra of BC/PAni blends prepared in water and HCl, which are assigned to the 1" and (200) 10 diffraction planes of cellulose, with a superposing halo from PAni. The crystallite size of the blend was 6.1 nm and the blend prepared in H2O exhibits crystallite size of 7.7 nm, which suggests that

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polymerization of PAni in HCl caused a decrease on the extent of order of cellulose, probably due to a weak acidic degradation rather than a direct effect of PAni. The FEG-SEM micrographs of a dried BC and BC/ PAni composite surfaces are shown in Fig. 7. The BC membrane was formed by a network structure of long cellulose nanobers with high aspect ratio (Fig. 7a) as described in Muller et al. (2011). In both BC/PAni composites the presence of PAni particles entangled with cellulose nanobers can be observed (Fig. 7cf). A more detailed morphological analysis of BC/PAni composites produced with 0.1 mol L-1 after 18 h reaction time is shown in high magnication FEGSEM micrographs of Fig. 8. The micrographs revealed that PAni was constituted of particles with mean size of 10 nm merged together to form a uniform layer that completely coated the nanober surface. The polymer coating adhered to the nanober and a continuous conducting network was formed which was responsible for the high electrical conductivity values. For BC/PAni composites the mean diameter was 100 nm, which is approximately 2-fold higher than the values for the uncoated cellulose nanobers.

high surface area with electrical, optical and magnetic properties of PAni.
Acknowledgments The authors gratefully acknowledge the nancial support by Conselho Nacional de Desenvolvimento Cientco e TecnologicoCNPq, Coordenacao de Aperfeicoamento de Pessoal de Ensino SuperiorCAPES, ` and Fundacao de Amparo a Pesquisa e Inovacao do Estado de Santa CatarinaFAPESC. We are sincerely thankful to Central Electronic Microscopy Laboratory, Santa Catarina Federal University (LCME-UFSC).

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Conclusion Flexible and conducting nanobrous membranes composed of BC and PAni were obtained through in situ oxidative chemical polymerization of aniline in the presence of BC membranes by using FeCl36H2O as the oxidant. The electrical conductivity of the composite was dependent on the oxidant concentration and reaction time. BC/PAni.HCl composites prepared with HCl solution exhibited higher electrical conductivity but lower tensile strength than BC/PAni.W. Nevertheless, relatively high conductivity was achieved in systems obtained in absence of HCl. The BC/PAni micrographs revealed that the conducting nanober material was constituted of a continuous conducting material distributed uniformly on the BC nanober surface. The method described in this article reveals that FeCl3 is a promising candidate as oxidant for preparing BC/PAni composites with good mechanical properties and electrical conductivity values higher or similar than those found for BC/PAni composites obtained by using APS and protonic acids. These materials may exploit BC properties, which include good tensile strength, toughness, biocompatibility, and

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