Article pubs.acs.org/IECR
New Bacterial Cellulose/Polyaniline Nanocomposite Film with One Conductive Side through Constrained Interfacial Polymerization Zhidan Lin,* Zixian Guan, and Zhuoyao Huang College of Science and Engineering, Jinan University, Guangzhou 510632, P.R. China ABSTRACT: Multilayer composites of electrode/electrolyte septum materials can be used as ideal electrode materials for supercapacitors. In this work, bacterial cellulose (BC) was used as a septum to separate the toluene/aniline solution with an aqueous oxidant acidic solution, and the aniline was polymerized in situ on the surface of the BC. Because toluene disperses aniline and controls the migration rate of aniline toward the aqueous oxidant acidic solution through BC, it can limit the oxidative polymerization to a single side of interface between the aqueous oxidant acidic solution and BC. A bacterial cellulose/polyaniline (PANI) composite with a single conductive surface and a surface resistivity of 40.1 Ω cm was successfully produced. The BC component in the new BC/PANI composite can absorb the electrolyte solution and change to a multilayer composite of electrode/electrolyte septum material that could be used in supercapacitors.
1. INTRODUCTION Polyaniline (PANI)/cellulose nanocomposites have recently received much attention because of their ability to conduct electricity and be used as flexible electrode materials.1−3 The most common types of cellulose for the preparation of these conducting nanocomposites include cellulose pulp, cellulose derivatives, cotton cellulose, microcrystalline cellulose, and bacterial cellulose (BC) membranes.4−8 Bacterial cellulose is a special type of cellulose produced through the fermentation of bacteria in a static or agitated culture.9 Although exhibiting a molecular structure similar to that of natural cellulose, BC has a specific ultrafine network structure and desirable properties, such as sufficient porosity, high purity and crystallinity, good mechanical properties, great water holding capability, excellent biodegradability, and biocompatibility.10,11 Recently, some research groups explored the preparation of BC/PANI conducting nanocomposites through the in situ polymerization of aniline (An) nanoparticles on a BC membrane.12−20 In these studies, the amounts of PANI loaded on the BC film and the rate of utilization of the reaction materials remained low.15,17 Moreover, both sides or the bulk of the composite membranes of the BC/PANI films were conductive. When making supercapacitors, such conductive films must be used in conjunction with an electrolyte membrane, such as a porous polytetrafluoroethylene film.21 To make a multilayer composite of electrode/electrolyte septum materials, our research group used permselecivity of materials through the nanofiber network in wet BC and designed a new synthetic route of limited interfacial polymerization by which aniline can be polymerized in situ on the BC surface. Toluene disperses aniline and controls its migration rate toward the aqueous oxidant acidic solution through BC, which can limit the oxidative polymerization to a single side of the interface between the aqueous oxidant acidic solution and the BC. Thus, the nanocomposite BC/PANI membrane can be used as a flexible electrode in a supercapacitor without an electrolyte membrane. In this work, using various concentrations of ammonium persulfate as the oxidant, we produced single-sided conductive BC/PANI nanocomposite membranes. © 2013 American Chemical Society
Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and surface resistance characterizations were used to study the molecular structure, microstructure, and basic electrical properties of composite membranes to verify the assumption.
2. EXPERIMENTAL SECTION 2.1. Materials. Aniline monomer and ammonium persulfate (APS) initiator were purchased from Tianjin Damao Chemical Reagent Company, Tianjin, China. Hydrochloric acid (HCl) and toluene were supplied by Shantou Guanghua Chemical Reagent Company, Shanghai, China. All starting materials were of analytical grade. Bacterial cellulose films with dry thicknesses of 0.014 mm (denoted pure BC-a) and 0.021 mm (denoted pure BC-b) were kindly provided by Hainan Yeguo Foods Company, Haikou City, China. 2.2. Preparation of BC/PANI Nanocomposite Films. Acidic solutions of APS were prepared with 1 mol L−1 HCl solution and various concentrations of APS (0.0125, 0.025, 0.050, and 0.075 mol L−1). The toluene solution of aniline was prepared with a concentration of 0.1 mol L−1 aniline. The bacterial cellulose wet film was washed with deionized water and wrapped on a plastic pipe to form a cup. The aniline solution in toluene was poured into the cup, and then the cup was immersed in an acidic solution of APS for 10 min. After the sample had been allowed to stand at 0 °C for 24 h, PANI polymer formed at the bottom of the cup. The cup was removed from the acidic solution of APS, and the aniline solution was removed by suction. Afterward, the cup was placed on a vacuum filtration device to remove the remaining reagents and washed successively with acetone and deionized water. Next, the cup was dried in a vacuum oven at 60 °C for 24 h. Finally, the planar dry BC/PANI nanocomposite film was Received: Revised: Accepted: Published: 2869
November 30, 2012 January 28, 2013 January 28, 2013 January 28, 2013 dx.doi.org/10.1021/ie303297b | Ind. Eng. Chem. Res. 2013, 52, 2869−2874
Industrial & Engineering Chemistry Research
Article
Figure 1. Schematic diagram of the formation of a BC/PANI nanocomposite film.
carefully removed from the cup. Various BC/PANI nanocomposite films were prepared using different concentration of APS solution. A schematic diagram of the process is shown in Figure 1. Five different samples were prepared with various concentrations of APS ratio for characterization. 2.3. Characterization. Both sides of the BC/PANI nanocomposite films were investigated using an Equinox 55 Fourier transform infrared (FTIR) spectrometer (Bruker). FTIR spectra were recorded using an attenuated total reflectance (ATR) accessory. The samples were analyzed over the range of 4000−600 cm−1 with a spectrum resolution of 4 cm−1. All spectra were averaged over 30 scans. The various BC/PANI nanocomposite films prepared using different concentrations of APS solution were dried under a vacuum to constant weight. The samples were fixed on the sample stage with the green sides facing up, and then the samples were sputter-coated with gold before scanning electron microscopy (SEM) examinations were performed. The surface morphologies of the BC/PANI nanocomposite films were observed on a Philips XL-30 environmental scanning electron microscope at an acceleration voltage of 15 kV. The PANI content on each BC film was calculated using the equation17
thickness instrument with the precision of 0.001 mm. Again, all data were averaged over five different samples.
3. RESULTS AND DISCUSSION 3.1. Optical Observations. Figure 2 shows images of the original BC membrane and BC/PANI composite membrane
Figure 2. Optical images of (a) pure BC film and (b) BC/PANI nanocomposite film containing 60.6 wt % PANI.
containing 60.6 wt % PANI. The original BC membrane was white and semitransparent, and its surface was quite smooth. One side of the BC/PANI composite membrane had the same character as the original BC membrane, and the other side showed an obvious dark green color, confirming the the incorporation of PANI was successfully limited to a single side of the BC membrane. In addition, the BC/PANI nanocomposites were rather flexible and could be curled, the same as the original BC membranes. The experimental hypothesis in this work was verified by optical images: The toluene and hydrophilic nanofiber network of the BC played a special role during membrane preparation. In the reaction stage, the toluene solution of aniline could not penetrate the hydrophilic BC membrane, whereas the water solution of APS could, and the two solutions reacted on the inner surface of the reactor to produce PANI. In the filtering
PANI content = (weight of dried BC/PANI film − weight of dried BC) /weight of dried BC/PANI film
(1)
All data were averaged over five different samples. The samples of BC and BC/PANI were vacuum-dried for 24 h at 60 °C before measurements. The surface resistivities of the two sides of the BC/PANI nanocomposite films were measured using a Bakon 485 surface resistance tester (HAKKO, Guanzhou, China). All data were averaged over five different samples. The thicknesses of the BC/PANI nanocomposite films were measured on a film 2870
dx.doi.org/10.1021/ie303297b | Ind. Eng. Chem. Res. 2013, 52, 2869−2874
Industrial & Engineering Chemistry Research
Article
Figure 3. FTIR-ATR spectra of (a) pure BC film and PANI powder and (b) two sides of a BC/PANI nanocomposite film containing 60.6 wt % PANI.
3.3. SEM Observations. The microstructures of the two sides of the BC/PANI nanocomposite membrane were observed directly by SEM. Figure 4 presents SEM micrographs of the BC/PANI nanocomposite membranes containing various oxidant concentrations. In the SEM image of the original BC membrane (Figure 4a), nanofibers with diameters of 100 nm overlap each other. With the addition of 0.0125 mol L−1 ammonium persulfate as the oxidant to limit the interfacial polymerization reaction, the polymerization side of the BC membrane (Figure 4b) shows overlapping fibers of between 300 and 400 nm on which many particles of 30 nm are dispersed, indicating the successful polymerization reaction of PANI particles on the surface of the nanofibers of the BC membrane with an interconnected electrically conductive network. For the addition of 0.025 mol L−1 APS, the SEM image of the polymerization side of the BC membrane (Figure 4c) shows a similar fiber structure, but the PANI particles have increased to 50 nm in diameter, dispersing the concentration, which could further increase the conductive network. This observation can be attributed to the increase in the oxidant concentration and, thus, in the amount of molecular PANI formed instantly on the interface between the BC membrane and the added toluene, which led to the formation of larger particles on the fiber surface. When 0.050 mol L−1 APS was used (Figure 4d), the PANI particles on the interface reached 1 μm in size, and they were not attached to the nanofiber surface of the BC membrane but rather were suspended on the surface, resulting in weak conductivity. This observation might be due to the high concentration of oxidant at the interface between the BC membrane and toluene, resulting in the formation of too much PANI, which agglomerated as large particles that were much larger than the holes of the BC nanofibers before attaching to the surface of the fibers (see Figure 5). Increasing the APS concentration to 0.075 mol L−1 (Figure 4e) confirmed this hypothesis. In this case, the formation of large PANI particles suspended on the BC membrane prevented the production of a continuous membrane structure. Huge cracks of the membrane could be observed even at low magnification (Figure 4e). 3.4. Properties of BC/PANI Nanocomposite Films. The basic properties of the BC/PANI composite membranes with various concentrations of oxidant are listed in Table 1. With increasing oxidant concentration, the thicknesses of the
stage, the PANI particles could not penetrate the nanofiber network of the BC membrane and thus remained on the inner surface of the reactor. During the drying stage, the nanofiber network was closed, and the BC membrane was changed to a flexible insulating film because of dehydration. 3.2. FTIR Characterization. Infrared spectra of vacuumdried samples of pure BC, PANI powder, and the two sides of a BC/PANI composite membrane containing 60.6 wt % PANI are displayed in Figure 3. All of the characteristic peaks of BC22 are shown in the FTIR spectrum of the white smooth side of the BC/PANI composite membrane (see Figure 3b). The absorption band at 3347 cm−1 can be assigned to the hydroxyl groups of cellulose and water. The absorption bands at 2899 cm−1 can be assigned to C−H stretching of CH2. Absorption bands at 1428 cm−1 can be assigned to CH2 symmetric bending. Absorption band at 1363 cm−1 can be assigned to the stretching and bending modes of hydrocarbons in the cellulose backbone. The absorption peak at 1161 cm−1 can be assigned to the asymmetric stretching of bridge C−O groups. The absorption peaks at 1109 and 1055 cm−1 can be assigned to the skeletal vibrations involving C−O stretching.23 The FTIR spectra demonstrate that, after the reaction, one side still retained the molecular structure of the original BC on which the interfacial polymerization reaction did not occur. In the FTIR spectrum of the dark green side of the composite film, the hydroxyl peak of the BC membrane at 3347 cm−1 disappeared, and the characteristic peaks of PANI were observed instead.24 The absorption peak at 3227 cm−1 can be assigned to N−H stretching. The absorption peaks at 1558 and 1491 cm−1 can be assigned to the stretching of quinone and benzene rings, respectively, in PANI.25 The absorption band at 1291 cm−1 can be assigned to the stretching of the C−N band of the benzene ring.16 The absorption band at 819 cm−1 can be assigned to the out-of-plane bending vibration of the C−H band of the para-substituted benzene ring. These assignments indicate that, after the reaction, PANI was successfully produced on one side of the film on which the interfacial polymerization reaction took place. In the FTIR spectra of the two sides of the film, the characteristic peaks did not coincide, indicating that the PANI produced through interfacial polymerization reaction could not pass through the BC membrane and that the polymerization reaction was limited to only one side of the BC film. 2871
dx.doi.org/10.1021/ie303297b | Ind. Eng. Chem. Res. 2013, 52, 2869−2874
Industrial & Engineering Chemistry Research
Article
Figure 4. SEM micrographs of (a) a pure BC dry film and (b−e) the conductive sides of BC/PANI nanocomposite films prepared at oxidant concentrations of (b) 0.0125, (c) 0.025, (d) 0.050, and (e) 0.075 mol L−1.
Figure 5. Schematic diagram of the formation of PANI particles on the BC surface at two conditions of low and high concentrations of oxidants.
nanocomposite membrane and the PANI layer and the content of PANI increased. It is worth noting that the rate of increase in
the thickness of PANI was much faster than the rate of increase in the PANI content. In conjunction with Figure 5, these results 2872
dx.doi.org/10.1021/ie303297b | Ind. Eng. Chem. Res. 2013, 52, 2869−2874
Industrial & Engineering Chemistry Research
Article
Table 1. Properties of BC/PANI Nanocomposite Films concentration (mol L−1)
surface resistivity (Ω cm)
film thickness (mm)
monomer
total
PANI layer
0.014
(1.77 ± 0.11) × 108
0.0125 0.025 0.050 0.075
0.1 0.1 0.1 0.1
0.039 0.048 0.078 0.118 0.021
0.025 0.034 0.064 0.104
54.3 60.6 63.8 81.3
64.3 ± 0.4 40.1 ± 0.4 177.6 ± 1.3 (1.84 ± 0.10) ×
(1.46 (1.65 (1.78 (1.81 108
0.025
0.1
0.044
0.023
48.8
89.1 ± 0.7
(1.86 ± 0.09) × 108
sample
oxidant
pure BC-a 1 2 3 4 pure BC-b 5
PANI content (%)
PANI side
tensile strength (MPa)
maximum stress (N)
elongation at break (%)
60.2 ± 2.3
9.20 ± 0.14
1.39 ± 0.03
24.7 ± 1.4 19.4 ± 1.0 11.1 ± 0.43 8.1 ± 0.37 57.7 ± 2.1
9.67 ± 0.17 9.32 ± 0.13 8.72 ± 0.19 8.19 ± 0.14 10.98 ± 0.09
1.58 1.91 1.77 1.57 1.47
22.3 ± 1.7
10.11 ± 0.14
1.88 ± 0.07
BC side
± ± ± ±
0.09) 0.09) 0.08) 0.08)
× × × ×
108 108 108 108
± ± ± ± ±
0.03 0.06 0.04 0.01 0.03
nanofibers, and as a result, the surface resistance was found to be very large. Moreover, the thickness of the original BC membrane affected the surface resistance. Sample 5 was prepared from the BC membrane with a dry film thickness of 0.021 mm (pure BC-b; Table 1). The increase in the thickness of the BC membrane led to a decrease in the surface resistance of the conductive network. This behavior was due to the fact that the increase in the thickness of the BC membrane decreased the amount of APS that penetrated under the water pressure, so that the amount of PANI particles decreased. These results show that the network of the BC nanofibers played a significant role in the promotion of electricity conduction. Single-sided BC/PANI nanocomposite membranes with the ability to conduct electricity could be used as ideal flexible electrode materials.
indicate that, with increasing concentration of oxidant (less than 0.050 mol L−1), the content of PANI did not increase significantly, but the size of the PANI particles increased, even outside the network of the BC membrane, sharply increasing the membrane thickness. The concentration of oxidant had no obvious effect on the maximum tensile stress, but the thickness of the loaded membrane had a large decreasing effect on the tensile strength (Figure 6) and enhanced the elongation at break. These
4. CONCLUSIONS In this study, using limited interfacial polymerization, flexible BC/PANI nanocomposite membranes with one conductive side and one electrode resistant side were successfully synthesized. Optical observations revealed that the microstructures of the nanocomposite membranes were affected by the concentration of the oxidant, which affected the surface resistance of the nanofiber network. In this work, at low concentrations of oxidant (less than 0.025 mol L−1 APS), the PANI nanoparticles were attached to the nanofiber network of the BC membrane, and the network exhibited good conductivity. The surface resistance of the nanocomposite membrane reached a magnitude of 101 Ω cm. At higher concentrations of oxidant (greater than 0.025 mol L−1 APS), the PANI particles were agglomerated into larger particles suspended outside the nanofiber network, and the network revealed weak conductivity with a surface of high conductive resistance. The new BC/PANI composite material produced in this project, through the adsorption of the electrolyte solution, could be used as a layered composite of electrode/electrolyte septum material with potential battery applications.
Figure 6. Stress−strain curves of pure BC with (pure BC-a) 0.014and (pure BC-b) 0.021-mm thicknesses; (1−4) BC-a/PANI nanocomposite films containing (1) 0.0125, (2) 0.025, (3) 0.05, and (4) 0.075 mol L−1 oxidant; and (5) a BC-b/PANI nanocomposite film containing 0.025 mol L−1 oxidant. Note that the curve labels correspond to the sample names in Table 1.
observations might be due to the PANI particles being inserted into the BC nanofiber network, decreasing the hydrogen bonding among the fibers, and increasing the deformability of the BC membrane. The surface resistivity of the BC side of the BC/PANI nanocomposite membranes was above 108 Ω cm, reflecting a fully insulating state. With increasing oxidant concentration, the surface resistivity of the PANI side of the BC/PANI membranes initially decreased and then increased. The surface resistance values of samples 1 and 2 were 64.3 and 40.1 Ω cm, respectively, and both reached a magnitude of 101 Ω cm. In combination with the SEM micrographs, these results suggest that the conductive network of sample 2 was prepared under optimal conditions, so that the surface resistance was at the minimum value. Although the PANI layers in samples 3 and 4 were thicker, a conductive network could not form on the BC
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Fax: +86 20 85223271. Notes
The authors declare no competing financial interest. 2873
dx.doi.org/10.1021/ie303297b | Ind. Eng. Chem. Res. 2013, 52, 2869−2874
Industrial & Engineering Chemistry Research
■
Article
Bacterial Cellulose−Polyaniline Nanocomposites. Cellulose 2011, 18, 1285. (19) Shariki, S.; Liew, S. Y.; Thielemans, W.; Walsh, D. A.; Cummings, C. Y.; Rassaei, L.; Wasbrough, M. J.; Edler, K. J.; Bonné, M. J.; Marken, F. Tuning Percolation Speed in Layer-by-Layer Assembled Polyaniline−Nanocellulose Composite Films. J. Solid State Electrochem. 2011, 15, 2675. (20) Auad, M. L.; Richardson, T.; Orts, W. J.; Medeiros, E.; Mattoso, L. H.; Mosiewicki, M. A.; Marcovich, N. E.; Aranguren, M. I. Polyaniline-Modified Cellulose Nanofibrils as Reinforcement of a Smart Polyurethane. Polym. Int. 2011, 60, 743. (21) Liu, F.; Yi, B.; Xing, D.; Yu, J.; Zhang, H. Nafion/PTFE Composite Membranes for Fuel Cell Applications. J. Membr. Sci. 2003, 212, 213. (22) Cai, Z.; Yang, G.; Kim, J. Biocompatible Nanocomposites Prepared by Impregnating Bacterial Cellulose Nanofibrils into Poly(3hydroxybutyrate). Curr. Appl. Phys. 2011, 11, 247. (23) Ferrero, F.; Testore, F.; Malucelli, G.; Tonin, C. Thermal Degradation of Linen Textiles: The Effects of Ageing and Cleaning. J. Text. Inst. 1998, 89, 562. (24) Rosa, M. F.; Medeiros, E. S.; Malmonge, J. A.; Gregorski, K. S.; Wood, D. F.; Mattoso, L. H. C.; Glenn, G.; Orts, W. J.; Imam, S. H. Cellulose Nanowhiskers from Coconut Husk Fibers: Effect of Preparation Conditions on Their Thermal and Morphological Behavior. Carbohydr. Polym. 2010, 81, 83. (25) Zhang, Z.; Wei, Z.; Wan, M. Nanostructures of Polyaniline Doped with Inorganic Acids. Macromolecules 2002, 35, 5937.
ACKNOWLEDGMENTS This project was supported by the Natural Science Foundation of China and Project of Science (Grants 21101076 and 21176100).
■
REFERENCES
(1) Qaiser, A. A.; Hyland, M. M.; Patterson, D. A. Surface and Charge Transport Characterization of Polyaniline−Cellulose Acetate Composite Membranes. J. Phys. Chem. B 2011, 115, 1652. (2) Ebrahim, S. M.; Kashyout, A. B.; Soliman, M. M. Electrical and Structural Properties of Polyaniline/Cellulose Triacetate Blend Films. J. Polym. Res. 2007, 14, 423. (3) Mattoso, L. H. C.; Medeiros, E. S.; Baker, D. A.; Avloni, J.; Wood, D. F.; Orts, W. J. Electrically Conductive Nanocomposites Made from Cellulose Nanofibrils and Polyaniline. J. Nanosci. Nanotechnol. 2009, 9, 2917. (4) Qian, X.; Shen, J.; Yu, G.; An, X. Influence of Pulp Fiber Substrate on Conductivity of Polyaniline-Coated Conductive Paper Prepared by In-situ Polymerization. BioResources 2010, 5, 899. (5) Yin, W.; Li, J.; Li, Y.; Wu, Y.; Gu, T.; Liu, C. Conducting IPN Based on Polyaniline and Crosslinked Cellulose. Polym. Int. 1997, 42, 276. (6) Onar, N.; Aksit, A. C.; Ebeoglugil, M. F.; Birlik, I.; Celik, E.; Ozdemir, I. Structural, Electrical, and Electromagnetic Properties of Cotton Fabrics Coated with Polyaniline and Polypyrrole. J. Appl. Polym. Sci. 2009, 114, 2003. (7) Auad, M. L.; Richardson, T.; Orts, W. J.; Medeiros, E. S.; Mattoso, L. H.; Mosiewicki, M. A.; Marcovich, N. E.; Aranguren, M. I. Polyaniline-Modified Cellulose Nanofibrils as Reinforcement of a Smart Polyurethane. Polym. Int. 2011, 60, 743. (8) Müller, D.; Mandelli, J. S.; Marins, J. A.; Soares, B. G.; Porto, L. M.; Rambo, C. R.; Barra, G. M. O. Electrically Conducting Nanocomposites: Preparation and Properties of Polyaniline (PAni)Coated Bacterial Cellulose Nanofibers (BC). Cellulose 2012, 19, 1645. (9) Czaja, W.; Romanovicz, D.; Brown, R. M. J. Structural Investigations of Microbial Cellulose Produced in Stationary and Agitated Culture. Cellulose 2004, 11, 403. (10) Zhou, P.; Wang, H.; Yang, J.; Tang, J.; Sun, D.; Tang, W. Bacteria Cellulose Nanofibers Supported Palladium(0) Nanocomposite and Its Catalysis Evaluation in Heck Reaction. Ind. Eng. Chem. Res. 2012, 51, 5743. (11) Cai, Z.; Kim, J. Bacterial Cellulose/Poly(ethylene glycol) Composite: Characterization and First Evaluation of Biocompatibility. Cellulose 2010, 17, 83. (12) Wang, H.; Zhu, E.; Yang, J.; Zhou, P.; Sun, D.; Tang, W. Bacterial Cellulose Nanofiber-Supported Polyaniline Nanocomposites with Flake-Shaped Morphology as Supercapacitor Electrodes. J. Phys. Chem. C 2012, 116, 13013. (13) Silva, M. J.; Sanches, A. O.; Malmonge, L. F.; Medeiros, E. S.; Rosa, M. F.; McMahan, C. M.; Malmonge, J. A. Conductive Nanocomposites Based on Cellulose Nanofibrils Coated with Polyaniline-DBSA via In Situ Polymerization. Macromol. Symp. 2012, 319, 196. (14) Qaiser, A. A.; Hyland, M. M.; Patterson, D. A. Control of Polyaniline Deposition on Microporous Cellulose Ester Membranes by in Situ Chemical Polymerization. J. Phys. Chem. B 2009, 113, 14986. (15) Lee, H. J.; Chung, T. J.; Kwon, H. J.; Kim, H. J.; Tze, W. T. Y. Fabrication and Evaluation of Bacterial Cellulose−Polyaniline Composites by Interfacial Polymerization. Cellulose 2012, 19, 1251. (16) Hu, W.; Chen, S.; Yang, Z.; Liu, L.; Wang, H. Flexible Electrically Conductive Nanocomposite Membrane Based on Bacterial Cellulose and Polyaniline. J. Phys. Chem. B 2011, 115, 8453. (17) Lee, B. H.; Kim, H. J.; Yang, H. S. Polymerization of Aniline on Bacterial Cellulose and Characterization of Bacterial Cellulose/ Polyaniline Nanocomposite Films. Curr. Appl. Phys. 2012, 12, 75. (18) Marins, J. A.; Soares, B. G.; Dahmouche, K.; Ribeiro, S. J. L.; Barud, H.; Bonemer, D. Structure and Properties of Conducting 2874
dx.doi.org/10.1021/ie303297b | Ind. Eng. Chem. Res. 2013, 52, 2869−2874
