Polyaniline-Based Composites and Nanocomposites

Polyaniline-Based Composites and Nanocomposites

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites Fen Ran, Yongtao Tan Lanzhou University of Technology, Lanzhou, P.R. China Composites or...

2MB Sizes 0 Downloads 72 Views

CHAPTER

7

Polyaniline-Based Composites and Nanocomposites

Fen Ran, Yongtao Tan Lanzhou University of Technology, Lanzhou, P.R. China

Composites or nanocomposites of conducting polymer/inorganic material with unique physical properties have attracted more and more attention in past decades [1,2]. The combination of the components with high level of dispersion in the nanoscale in the composites or nanocomposites is considered to provide better performance and expected to find applications in many fields, such as photoelectrochemical devices, electrochemical devices, nonlinear optical systems, and so on [3e5]. As such, many publications have been reported for synthesis and applications of polyaniline (PANI)eTiO2 nanocomposites, PANIecalcium carbonate composites, natural fiberebased PANI composites, filler-based PANI composites, PANIe silica nanocomposites, PANIeclay nanocomposites, PANIeporous carbon nanocomposites, PANIelayered silicate composites, PANIecopper nanocomposites, PANIemontmorillonite nanocomposites, PANIegraphene nanocomposites, and cellulose whiskersePANI nanocomposites.

7.1 POLYANILINEeTIO2 NANOCOMPOSITES Titanium dioxide (TiO2) is an n-type semiconducting material with very interesting properties, such as chemical stability, high photocatalytic activity, nontoxicity, low cost, availability, good mechanical flexibility, conductivity, and so on [6,7]. It has potential applications in the fields of lightweight battery electrodes, electromagnetic shielding devices, anticorrosion coatings, and sensors [8,9]. To get most of their benefits, nanotubes, nanowires, nanoparticles, and nanorod composites of TiO2 and PANI have been developed [10].

7.1.1 NANOTUBES TiO2 nanotubes are promising substrates for the electrodeposition of conductive polymers such as polyvinyl alcohol, polypyrrole, PANI, poly 3,4-ethylenedioxythiophene, and poly (3-hexylthiophene) in different applications [11e14]. The electrodeposition of PANI onto TiO2 nanotubes increases surface area of the final electrode that is very important for special applications [15]. Mujawar et al. [16] prepared PANIeTiO2 nanotubes by electropolymerization of polymerization onto TiO2 nanotubes by Polyaniline Blends, Composites, and Nanocomposites. http://dx.doi.org/10.1016/B978-0-12-809551-5.00007-2 Copyright © 2018 Elsevier Inc. All rights reserved.

175

176

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

anodizing titanium for supercapacitor application and obtained a high specific capacitance of 740 F/g at a constant current of 3.0 A/g. After 1100 chargeedischarge cycles, the specific capacitance decreases from 740 to 650 F/g. Gobal and Faraji [17,18] first introduced small palladium nanoparticles onto TiO2 nanoparticles by sonochemical reduction of Pdþ2, which affect the ordered growth of PANI, reducing the charge transfer resistance and increasing surface area of PANI. Based on this approach, PANIepalladiumeTiO2 electrodes with highly porous structures can also be prepared by electrodeposition of PANI on palladium nanoparticleeloaded TiO2 nanotubes. The specific capacitance of PANIepalladiumeTiO2 can reach 1060 F/g in 1.0 mol/L H2SO4 electrolyte, which can maintain 94% of initial capacity after 10 days being used in electrochemical experiments, showing good cycle stability. Ordered titania nanotube array (TiO2eTi) can be used as a support for electroactive materials [19]. The high accessible surface area of titania nanoactive array and the chemical stability are beneficial to the enhancement of the adhesion between PANI and the substrate and hence improves the cycle life. A composite electrode of PANI nanowireetitania nanotube array is further synthesized via an electrochemical route by electropolymerizing aniline onto the anodized titania nanotube array (Fig. 7.1). Specific capacitance is as high as 732 F/g at 1 A/g, which remains 543 F/g when the current density is increased by 20 times. The maximum energy density is 36.6 Wh/kg at a high power density of 6000 W/kg, and an excellent long cycle life is obtained with retention of 86% of the initial specific capacitance

FIGURE 7.1 Schematic illustration of the preparation process of disordered polyaniline (PANI) nanowire array on the TiO2eTi substrate [20].

7.1 PolyanilineeTiO2 Nanocomposites

after 2000 cycles [20]. The good electrochemical performance is attributed to the unique microstructure of the disordered PANI nanowire arrays encapsulated inside the TiO2 nanotubes, providing high surface area, fast diffusion path for ions and long-term cycle stability. In addition, the semiconductor nature of TiO2 nanotubes often leads to low electrochemical activity and poor conductivity, thereby restricting its applications. To achieve improved conductivity of TiO2 nanotubes, thermal treatments, hydrogenated processes, chemically and electrochemically self-doped methods have been developed [21e23]. In this case, TiO2 nanotubes can be annealed in H2 to synthesize hydrogenated TiO2 nanotubes (HeTiO2) and PANI/H-TiO2 nanotubes by electrochemical deposition compared with the areal capacitance of air-TiO2 nanotubes (0.42 mF/cm2) due to its improved electrical conductivity [24]. TiO2 nanotube layer can also promote the formation of a concentration gradient of aniline monomer and thus indirectly plays an important role in dynamic template. Because of this unique structure, the specific capacitance of the electrode is around 897.35 F/g at a current density of 0.21 A/g in 0.05 mol/L H2SO4 electrolyte [25]. The highly sensitive and rapid NO gas sensor is prepared with carbon [email protected] PANI with embedding TiO2. The advantages of TiO2 photocatalyst in gas sensing are apparent in the improvement in both sensitivity and response rate [26]. Electrodeposition of PANI onto TiO2 nanoparticles/multiwalled carbon nanotubes also benefits for visible light photoelectrocatalysis [27e30].

7.1.2 NANOPARTICLES The hybridization of PANI and TiO2 leads to unique material, which exhibits the enhancement of many properties, and PANI/TiO2 nanohybrids have been successfully synthesized [31e33]; however, research works on obtaining good dispersion of TiO2 nanoparticles in PANI matrix also have been extensively conducted based on ultrasonification [34,35]. In this case, dispersion of TiO2 nanoparticles in PANI matrix should be an important aspect for any application of TiO2ePANI hybrid composites. To obtain photocatalytic nanofibereTiO2 nanoparticles hybrid, a simple approach has been reported to achieve high dispersion state of the hybrid based on the surface charge by the layer-by-layer self-assembly method. The hybridization of PANI nanofiber and TiO2 nanoparticles results in an enhancement of photocatalytic activity for visible light [2]. Nanoparticles are often used as seeds to grow one-dimensional nanomaterials or as core materials to prepare coreeshell nanostructures. On the other hand, the presynthesized inorganic nanoparticles can also be used as starting building blocks to prepare inorganic polymer nanocomposites. Oleate functional group protected anatase TiO2 plays multifunctional roles in synthesis and construction of highly complex SiO2eTiO2ePANI materials as starting sites for PANI deposition, a secondary material phase for nanocomposites, preinstalled seeds for TiO2 growth, and primary nanobuilding blocks for preparation of TiO2 shell via selfassembly. With the assistance of the TiO2 nanoparticles, a total of six complex

177

178

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

coreeshell and hollow sphere nanoparticles have been developed: SiO2eTiO2, SiO2eTiO2ePANI, SiO2eTiO2ePANIeTiO2, TiO2ePANI, TiO2ePANIeTiO2, and TiO2eTiO2 [36]. When the monomer aniline is immobilized onto the surface of TiO2 nanoparticles by a coupling agent, a hybrid nanoparticle with a range of possible sizes would be synthesized as TiO2ePANI coreeshell nanoparticles. The method is single step and simple (Fig. 7.2). The hybrid nanoparticles are afforded in high yield under mild reaction conditions and simultaneously show improved charge transport and electrochromic behavior compared to either PANI alone or physically blended with TiO2 [37]. In addition, to prepare polymereTiO2 nanoparticles, surface of TiO2 nanoparticles is also modified with the in situ chemical oxidative polymerization of aniline. Modification of TiO2 nanoparticles with PANI would improve the interfacial adhesion between the constituents of nanocomposites, which result in better dispersion of nanoparticles in the polyvinyl chloride (PVC) matrix. PVC/PANI-TiO2 nanoparticles show higher thermal resistance tensile strength and Young’s modulus compared to those of unfilled PVC and PVCeTiO2 nanoparticles [38].

7.1.3 NANOWIRES PANI nanocomposites are always prepared by in situ chemical oxidative polymerization or electrochemical polymerization. First, TiO2 nanoparticles are converted to TiO2 nanowires through a hydrothermal process using 10% NaOH, subsequently the TiO2 nanowires are dispersed in a dodecylbenzene sulfonic acid solution. After that, the aniline monomer is added and the polymerization occurred on the addition of ammonium persulfate as an initiator. The TiO2ePANI nanowires can be obtained, and morphology and crystalline structure can be controlled by varying the TiO2 nanowires ratio. The prepared TiO2ePANI nanowires can be further used as conductive packaging materials [39]. The activated carboneTiO2 nanowires also can be used as the supporting materials for the preparation of ternary nanocomposites of carboneTiO2ePANI nanowires via using an in situ polymerization method. The introduction of TiO2 nanowires could greatly improve the long-term cycle

FIGURE 7.2 Schematic of hybrid coreeshell growth from TiO2eMAA to TiO2ePANIeDBSA [37].

7.1 PolyanilineeTiO2 Nanocomposites

stability of carboneTiO2ePANI composites [40]. TiO2ePANI coreeshell nanofibers with ultraviolet photoresponse can also be designed and fabricated. When the coreeshell nanofibers are tested in oxygen and nonoxygen environment under ultraviolet illumination, a decrease and an increase in photoconduction are observed [41]. TiO2ePANI nanocomposite fiber films can be further fabricated by electrospinning, calcinations, and in situ polymerization. The surface morphology of this hierarchical nano-/microstructure is related to the structure of TiO2 nano-/microfiber film, the time and temperature of in situ polymerization [42]. Heterostructured arrays of TiO2 nanowires/PANI nanoflowers/TiO2 nanowires can also be made by the combination of the hydrothermal and in situ multiple wet chemical deposition methods. In this process, highly oriented n-type TiO2 nanowires are grown on fluorine-doped tin oxide (FTO) glass substrate by the hydrothermal method. Then, p-type PANI is deposited on as-grown TiO2 nanowires array by in situ wet chemical deposition method. The thickness and morphology of PANI layer could be controlled by changing the reaction solution to fresh solution per hour for depositing multiple times (Fig. 7.3). Another as-grown TiO2 nanowire array would cover on TiO2 nanowires/PANI nanoflowers heterostructured arrays face to face to obtain the heterostructured arrays of TiO2 nanowires/PANI nanoflowers/TiO2 nanowires [43].

7.1.4 NANORODS TiO2ePANI nanorods can be prepared by the radiolysis polymerization method [44], and TiO2ePANI nanorods also can be prepared into hybrid electrochromic film [45]. Jian Gong et al. synthesized vertical aligned [email protected] coreeshell nanorods for high-performance supercapacitors. TiO2 nanorods grow on the FTO substrate and then carbon-coated TiO2 nanorods are obtained. Finally, PANI is polymerized onto the carbon-coated TiO2 nanorods and thus [email protected] coreeshell nanorods are obtained (Fig. 7.4) [46].

FIGURE 7.3 Schematic illustration of the fabrication of TiO2 NWs/polyaniline NFs/TiO2 NWs heterostructured arrays [43]. FTO, fluorine-doped tin oxide; PANI, polyaniline; NF, nanoflower; NW, nanowire.

179

180

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

(A)

(C) (E)

(B)

(D)

FIGURE 7.4 SEM images of TiO2 nanorods (A and C) and the [email protected] polyaniline coreeshell nanocomposite (B and D). TEM image of the [email protected] polyaniline coreeshell nanocomposite, and elemental maps of O, Ti, C, and N for [email protected] (E) [46].

The photocatalytical activity of the hierarchical rutile TiO2 nanorod spheres is about twice that of the famous commercial photocatalyst P25; however, hierarchical rutile TiO2 nanorod spheres are lacking of visible light utilization [47]. To get a material with high visible light photocatalytical activity, PANIeTiO2 nanocomposites with bionic nanopopilla structure, synthesized by a facile hydrothermal method, exhibit the superior photocatalytic effects to that of pure TiO2 and P25 samples attributed due to the structural features of PANIeTiO2 microspheres and the synergistic effect between PANI and TiO2 that facilitates a larger amount of surface active sites [48].

7.1.5 NANOSHEETS The nanocomposites of TiO2 nanosheets and PANI is fabricated by deposition of water-dispersible PANI on interdigitated gold electrodes decorated with TiO2 nanosheets via dip coating. Specifically, TiO2 nanosheets is in situ grown on the electrodes by a simple hydrothermal treatment of the electrospun nanofibers of poly(methyl methacrylate) containing a tetrabutyl titanium precursor in the presence

7.3 Natural FibereBased Polyaniline Composites

of only water. The nanosheet materials exhibit highly sensitive, selective, and repeatable electrical responses toward NH3, which is related to the high specific surface area and the p/n heterojunction between TiO2 nanosheets and PANI [49].

7.2 POLYANILINEeCALCIUM CARBONATE COMPOSITES Calcium carbonate (CaCO3) has been widely used in the development of hybrid organiceinorganic materials due to the good properties of CaCO3 compound such as biocompatibility, large specific area, hierarchical structure, and mesoporosity [50,51]. This inorganic material can adsorb or encapsulate compounds and deliver them in areas with an acidic pH, which is found in solid neoplastic tissues [52]. Hybrid materials based on CaCO3 and PANI have been synthesized with interesting results, exhibiting improved or novel characteristics in comparison to those of the base components of PANI or CaCO3 [53,54]. Aimed to generate hybrid CaCO3 microparticles loaded with PANI for photothermal therapy, Neira-Carrilo et al. synthesized hybrid nanomaterials with CaCO3 and PANI in a simple, reproducible manner, which represent a novel type of hybrid biomaterial. In the nanocomposite material, the CaCO3 microparticles are solid and agglomerated with a diameter of about 30 nm. The agglomeration of CaCO3 microparticles could occur due to the direct electrostatic interaction between the carboxylate groups of the carboxymethyl cellulose with the CaCO3 microparticles, where the particles tend to agglomerate strongly. These agglomerates exhibit an elongated morphology, ranging from 1 mm to 500 nm in length and about 100 nm in wide. The resultant CaCO3 microparticlesePANI hybrid nanocomposite could be used as a photothermal therapy agent for cancer ablation, and the development concept used for PANI-based micro- or nanobioparticles could serve as a platform for the next generation of in vivo cancer photothermal therapy agents [55].

7.3 NATURAL FIBEReBASED POLYANILINE COMPOSITES Many natural or artificial microfibers show an ideal starting material for various applications because of their excellent biocompatibility, high surface-to-mass ratio, good mechanical performance, and ability to be shaped in various forms. In the past decade, natural fiber has been the object of an increasing interest as a potential biomaterial forming the core of scaffolds aimed at tissue engineering, regeneration, or repair purposes [56]. The availability of fiber materials able to conduct electrical signals is expected to widen the range of the possible applications in various fields. Conducting kenafePANI biofibers [57,58], natural rubber-PANI/short nylon-6 fibers [59], and natural Brazilian amazonic fibers [60] have been fabricated to prepare the conducting composite fibers without significant loss in the tensile properties. At first, people improved the conductivity of natural fiber by blending conductive inorganic materials into natural fibers. Comparing with the usual method, the construction of conductive conjugated polymers such as PANI, polypyrrole, and

181

182

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

3,4-ethylenedioxythiophene on natural fibers provides a useful tool for producing new natural fiberebased conducting materials. Many works have focused on preparing natural fiberePANI composites by in situ polymerization [61]. For instance, polyanilineesilk fibroin composite fibers is fabricated without any modification of silk fibroin surface and show varied conductivity in the range of 0.9e1.2  102 S/cm. Structural analysis indicates that the interactions including hydrogen bonding and electrostatic attraction existed between silk fibroin macromolecules and PANI. The peptide linkages bearing on silk fibroin conjugated cation radicals. In addition, the composite fibers still possess former fibrillar morphology and strength properties [62]. In recent years, despite some successes accumulated on these conductive composites via various polymerization approaches, it is found that only a few PANI particles are attached on the natural fiber surface, which in large degree restrict the real applications of these composites [63]. To obtain high conductivity of the composites, it is essential to produce a uniform conductive polymer layer on the natural fiber surface to form a coreeshell coaxial structure. Different from some electrospun nanofibers, which are readily coated by PANI layers because of small diameter; however, natural fibers always have large size in diameter of about 15 mm so that constructing PANI/natural fiber with a coaxial structure is difficult [64]. As such, many modification approaches have been developed to face this challenge, the most used of which is modification of the natural fiber with some chemical. It is certified that the initial modified natural fibers yield much more uniform PANI layer compared to the untreated one [65]. Xia et al. first modified natural silk fibroin fibers with methyl orange, which is both a good acid dye for silk and successful template for inducing conductive polymer nanostructure [66], via an in situ oxidation technique, a composite with the coreeshell coaxial-line structure was prepared. Different from the composites prepared by untreated fibers, which have only some conductive polymer particles and clumps formed on the fiber surface due to lack of negative group, the composites prepared with methyl orange show the coree shell coaxial-line structure [Fig. 7.5]. More importantly, by controlling the reaction time, the coating density of PANI on the composite fiber could be effectively adjusted. It is suggested that methyl orange promotes the generation of PANI shell coated on the fibers. Based on the uniformly PANI surface, the composite fibers exhibit good biocompatibility, cell attachment, and proliferation [67].

7.4 FILLER-BASED POLYANILINE COMPOSITES Recent studies have shown that the introduction of multiwalled carbon nanotubes in PANI enhances the electrical properties by facilitating chargeetransfer processes between the two components [68e70]. Nanocomposites of nanotubes with different polymers have been prepared using several methods such as melt mixing, in situ polymerization, grafting, macromolecules to the carbon nanotubes, and electrochemistry [71]. Different acids, viz methane sulfonic acid, camphor sulfonic acid,

7.4 Filler-Based Polyaniline Composites

FIGURE 7.5 The FTIR spectrum (A), SEM images (B and C), and TGA curve (D) of natural silk fibroinepolyaniline (coreeshell) coaxial fiber prepared by in situ polymerization of aniline on the MO-modified SF surface for 24 h [67].

hydrochloric acid, and H2SO4 are used to synthesize PANI by chemical polymerization, and different forms of carbon, viz carbon black, graphite, and carbon nanotube are used to prepare PANIecarbon composites by in situ method [72]. Thus, in essence, PANIecarbon nanotube composites prepared using organic acid dopants are most suitable for conducting fillers. Many materials, especially some polymers, offer outstanding properties, such as mechanical and chemical resistance, adhesion, and durability. These advantages make them a great host for conductive fillers such as PANI and its composites. For instance, to reach high conductivities without damaging the mechanical properties of epoxy resin, the amount of conductive filler has to be as low as possible. Hence, many materials are selected to blend with PANI, such as aluminum, graphite, aluminum nitrides, nickel, zinc sulfide, titanium dioxide, silver particles, barium titanate, clays, montmorillonite, carbon black, single-walled carbon nanotube, magnetite, and hydrochloride [73e76].

183

184

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

When PANI hydrochloride is blended into phenol formaldehyde resin (resole) by mechanical mixing, the mechanical properties (adhesive strength) of the blended resins is improved due to the significant reduction of the accelerating effect of PANI hydrochloride on the curing of the resin and the curing time. It is concluded that the PANI hydrochloride plays an important role as filler in phenolic resin polymer matrices [77]. Epoxy resin composites with anhydride as a hardener are also prepared with different amount of PANI and Fe3O4 fillers for electromagnetic applications. The investigation of effects of PANI and Fe3O4 loading on permittivity, permeability, and microwave absorption properties reveals that the electromagnetic parameters were higher in hybrid PANIemagnetiteeepoxy resin composites than in dielectric PANIeepoxy resin composites, the permittivity and the permeability parameters increase to high values with the rate of fillers in the composite and remain constant with the frequency [78]. In many applications of paints, it is convenient to formulate a composite made up of inorganic particles (a pigment) with a suitable chemical composition and that are coated with a functional layer of a conductive polymer. The reinforcement of coatings with lamellar filler particles leads to improvement of mechanical properties of paint film. The adhesion of coating to the substrate, so as the adhesion of individual layers one to another are tightly connected with phenomena, such as osmotic blistering, peeling, and cracking of the coating films [79]. The surface of lamellar filler particles is covered with PANI layer during chemical oxidative polymerization of aniline, and the combination of lamellar filler and PANI enhanced mechanical resistance [80]. PANI with carbon aerogel as conducting filler synthesized by an in situ chemical oxidative polymerization method indicates that the three-dimensional carbon nanonetwork of carbon is entirely buried inside the PANI matrix and its introduction basically does not change the structure of PANI. The electrochemical performances of the as-prepared PANI materials with carbon filler are notably improved due to the introduction of carbon filler [81,82]. Hybrid electrochromic materials are synthesized via copolymerization of aniline with p-phenylenediamine-functionalized single-walled carbon nanotubes in the presence of poly(styrene sulfonate) dopant in an aqueous medium. PANI-grafted single-walled carbon nanotubes are uniformly dispersed in the PANIepoly(styrene sulfonate) matrix. The chargeetransfer resistances of the hybrid decreased due to the greatly increased redox reactivity leads to much enhanced electrochromic contrast [83]. One-dimensional multiwalled carbon nanotube nanocomposite fibers are fabricated to improve electrical properties using electrospinning. PANI and poly(ethylene oxide) are used as a conducting and nonconducting matrix, respectively, for hybrid nanofibers including multiwalled carbon nanotubes. The hybrid nanofibers fabricated by electrospinning show an enhanced electrical conductance and a stable linear ohmic behavior [84]. Highly uniform composite nanofibers composed of welloriented single-walled carbon nanotubes wrapped in conducting polymer also can be fabricated using electrospinning. Water-soluble PANI is used as a conducting material to improve the processability during electrospinning. The water-soluble PANI

7.5 PolyanilineeSilica Nanocomposites

plays an important role as a conducting polymer matrix to achieve aligned carbon nanotubes in composite nanofibers and to form uniform nanofibers [85]. PANIeclay nanofillers are used to study the impact of filler morphology on the electrical properties of composites. Clay is used as a nanostructured template to increase the PANI aspect ratio. The use of PANIeclay nanofillers reduces the electrical percolation threshold of composites, and the conductivity of composites is improved. A classical alkaline curing accelerator, such as imidazole, exhibits chemical incompatibilities with the PANI conductive form, resulting in less conductive composites [86]. PANIemontmorillonite is also synthesized as nanocomposite filler. The organiceinorganic polymer matrix is formed in two independent steps: inorganic building units are formed in situ by the solegel process, followed by organic polymeric matrix formation by polyaddition reactions of epoxy groups with amines. The filler composition affects both the mechanical and surface properties of the coatings [87]. PANI particles encapsulated into an insulating polymer using miniemulsion polymerization of divinylbenzene can also be used as high dielectric constant fillers. The resulting composites in a polydimethylsiloxane matrix are prepared and the resulting films show a more than threefold increase in dielectric constant, breakdown field strengths above 50 V/mm, and increased strain at break. These novel materials allow tuning the actuation strain or stress output and have potential as materials for energy harvesting [88].

7.5 POLYANILINEeSILICA NANOCOMPOSITES As a classical inorganic material, nanosilica has wide applications due to its high specific surface area, large pores, tuneable porosity, and high chemical stability [89,90]. Therefore, the composites formed by mesoporous silica and PANI may possess many good properties and performance such as good electrochemical performance. The PANIesilica nanocomposites can be easily synthesized by in situ oxidative polymerization of aniline in the presence of different amount of SiO2 nanoparticles. The SiO2 nanoparticles are encapsulated by PANI. Thus, the thermal decomposition temperature of PANI in nanocomposites is lower than that of pristine PANI, although the conductivity decreases [91]. Based on this, silicaePANI nanocomposites with high dielectric permittivity performance are also obtained [92]. When phosphoric acid is used as doping acid, PANI nanocomposites fill with silica nanoparticles synthesized by an initiated polymerization method show a positive giant magnetoresistance performance [93]. Epoxy resin nanocomposites reinforced with silica nanoparticles have been prepared at different nanoparticle loading levels. The surface functionality of the silica nanoparticles is manipulated by the phosphoric-doped conductive PANI via the surface-initiated polymerization. The glass transition temperature is improved and the mechanical properties are enhanced due to the filling of epoxy resin nanocomposites with the functionalized silica nanoparticles [94].

185

186

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

Surface imprinting and adoption of a nanosized physical form are two effective approaches to overcome the template transfer difficulty within molecularly imprinted polymers. By using a nanoreactor as a substrate for the reaction between the monomer and the template to conquer the problem, negatively charged hexagonal nanochannels of SBA-15 can act as a support for attachment of positively charged aniline monomers and the 2,4-dinitrophenol template [95]. When platinum nanoparticles are supported on PANIemesoporous silica film, the mesochannels perpendicular to the underlying electrode surface can confine the electrodeposition of PANI and improve the mechanical strength of PANI. The secondary and tertiary imines on the PANI backbone can readily complex with PtCl6 2 , which can further reduce to generate Pt nanoparticles. The obtained Pt [email protected] mesosilica film hybrid material exhibit a good electrocatalytic activity toward oxidation of H2O2 [96]. The composite electrode formed by mesoporous silica and PANI possesses a good electrochemical activity and relatively large specific surface area to improve the electrochemical performance. However, for a PANIesilica nanocomposite, if the PANI chains are isolated in the channels or pores of mesoporous silica could not form a conductive network, the electrical performance of the composite would be decreased very greatly due to the free movement of electrons being restricted within the PANI chains [97]. Mesoporous PANIesilica nanocomposites with a full interpenetrating structure for pseudocapacitors are synthesized via the vapor phase approach, which possess a uniform particle morphology and full interpenetrating structure, leading to a continuous conductive PANI network with a large specific surface area. With the merits of the large specific surface area and suitable pore size distribution, the nanocomposites show a large specific capacitance of 1702.68 F/g due to its high utilization of the active materials [98]. Besides nanoparticle composites, PANIesilica composites can be selfassembled into nanotube composites. Self-assembled PANI nanotubes are synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in aqueous medium in the presence of colloidal silica particles of an average diameter about 12 nm, without added acid (Fig. 7.6). The electrical conductivity of PANIenanotubesesilica nanocomposites is in the range of 3.3e4.0  103 S/ cm [99].

7.6 POLYANILINEeCLAY NANOCOMPOSITES Clay has always played a major role in human life. Clay raw materials are used, and their value is recognized in many economic branches, agriculture, civil engineering, and environmental studies. This is largely because of their wide-ranging properties, high resistance to atmospheric conditions, geochemical purity, easy access to their deposits near the earth’s surface, and low price. Clay minerals, the essential constituents of argillaceous rocks, can be classified in seven groups according to their crystal structure and crystal chemistry. Clay raw materials are divided in the same way into seven groups. Polymereclay nanocomposites have attracted great interest,

7.6 PolyanilineeClay Nanocomposites

FIGURE 7.6 TEM images of the polyanilineenanotubesesilica nanocomposites [99].

because they exhibit remarkable improvement in material properties such as mechanical, thermal, electrical, and optical properties when compared with pristine polymer or conventional micro- and macrocomposites. The clays are more commonly employed, and when added in quantities below 5% in nanocomposites, they impart a significant increase in material properties, such as mechanical, optical, magnetic, barrier, and especially permeability and flammability resistance [100,101]. A multiassembly of clay plates in presence of conjugate polymer system can be used to regulate the tunneling of charge carriers and the electron transfer properties [102,103]. PANIeclay nanocomposites can be synthesized by intercalation of monomer at elevated temperature followed by oxidation polymerization of aniline in the presence of oxidants such as (NH4)2S2O8 [104,105]. A mechanochemical technique has been proposed for the synthesis of polymereclay nanocomposite in which the monomer intercalation and polymerization can be accomplished by mechanical grinding in mortar and a pestle [106e108]. This technique is considered to be a green chemistry way of production of bulk PANIeclay nanocomposites. A ball mill grinding technique also can be used for the synthesis of polymer nanocomposites [109]. Based on this technique, various PANIeclay nanocomposites derived from aniline and substituted aniline derivatives have been synthesized by mechanochemical intercalation method. The appearance of green color indicates the formation of PANIeclay nanocomposite. Similarly, aniline derivatives such as o-anisidine in the form of HCl salt can form intercalation into the clay lattices. The intercalated aniline derivatives are ground mechanically in the presence of oxidizing agent ammonium peroxysulfate, which leads to formation of substituted PANIeclay nanocomposites [110].

187

188

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

The physical mixture of a polymer and clay may not form a nanocomposite, analogous to polymer blends, and in most cases separation into discrete phases takes place. In immiscible systems, which typically correspond to the more conventionally filled polymers, the poor physical interaction between the organic and the inorganic components leads to poor mechanical and thermal properties. In contrast, strong interactions between the polymer and clay in polymereclay nanocomposites lead to the organic and inorganic phases being dispersed at the nanometer level. As a result, nanocomposites exhibit unique properties not shared by their microcounterparts or conventionally filled polymers [111,112]. Clays are naturally hydrophilic, making it difficult to interact and obtain a homogeneous mixture with the polymer matrices. As such, clays always need to be modified before using it to prepare polymereclay nanocomposites. For example, to prepare PANIeclay nanocomposites, clays are modified to be hydrophobic, making the intercalation of many engineering PANI possible [113]. The melt rheology of PANI-dinonylnaphthalene dissulfonic acid gel nanocomposites with organically modified (modified with cetyl trimethylammonium bromide) montmorillonite clay is studied for three different clay concentrations at the temperature range of 12e160 C [114]. For many applications, PANIeclay nanocomposites are always grafted onto the surface of substrates such as iron, steel, and other metals. Polymereclay nanocomposites can be prepared via chemical grafting of PANI onto a ZneAl layered double hydroxides. Decavanadate anion with anticorrosive activity is intercalated into ZneAleNO3 layered double hydroxides via anion-exchange reaction, and the decavanadate-intercalated layered double hydroxides are treated with raminopropyltriethoxysilane to form a bonding layer on its surface, where PANI is in situ polymerized to form a new kind of polymereclay composite. The PANI-/ clay-based coating offers better protection against corrosion than these of the PANI and decavanadate-intercalated clay nanocomposites [115]. The chemical grafting of PANI/vermiculite is applied to prepare PANIevermiculite clay nanocomposites by in situ chemical oxidative grafting polymerization. The percentage of grafted PANI is 142.7 wt% as a mass ratio of the grafting PANI and charged nanovermiculites. The introduction of vermiculite clay nanosheets has a beneficial effect on the thermal stability of PANI. The electrical conductivity of the nanocomposites is 3.9  103 S/cm, a value typical for semiconductor [116]. PANI-modified clay is also incorporated into the poly(amic acid) solution during a novel double intercalation polymerization procedure and forms 1,4-oxydianiline and pyromellitic dianhydride. PANI-modified clayepolyimide nanocomposite containing highly intercalated montmorillonite is synthesized by in situ double intercalation polymerization followed by thermal imidization. The presence of PANIeclay resulted in a decrease in the poly(amic acid) solution, viscosity attained the maximum value at a shorter reaction time. The thermomechanical properties of the composites increase with increasing filler concentration [117]. Nanocomposites consisting of PANI and clay minerals are also synthesized mechanochemically to intercalate anilinium fluoride. The nanocomposites contain much more PANI in the clay layers than those prepared by a conventional solution method [107].

7.7 PolyanilineeManganese Dioxide Nanocomposites

7.7 POLYANILINEeMANGANESE DIOXIDE NANOCOMPOSITES Manganese oxide has the advantages of low cost, natural abundance, environmental friendship, and interesting electrochemical performance in the application, which make it look more promising in research [118]. Many kind of manganese oxides/ PANI have been synthesized in recent years. Pan and coworkers synthesized nanometer tubular PANI using crystal-oxidative manganese oxides as a template that is dissolved in the reductive environment during synthesis [119]. Manganese oxide is used as the physical template and the chemical oxidative initiator for the aniline polymerization, as shown in Fig. 7.7. The template can be removed after the reaction, as manganese oxide is reduced into soluble Mn2þ ions. Much morphology of PANI structures, such as nanotubes, spherical tube brushes, and double-shell nanotubes can be fabricated using this method. Nano-PANI and manganese oxide nanometer tubular composites can be further fabricated by a surface-initiated polymerization method and used as electrochemical capacitor electrode materials. The microstructure of the nanotubes can be controlled by aniline amount. The electrochemical performance of these nanocomposite materials show high capacitance of 386 F/g in aqueous 1 mol/L NaNO3 electrolyte with the potential range from 0 to 0.6 V (vs. SCE). It should be noted that the pure PANI would be obtained if enough MnO2 is added [120].

FIGURE 7.7 Polyaniline nanotubes synthesized from manganese oxide templates [119].

189

190

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

7.8 POLYANILINE-POROUS CARBON COMPOSITES Carbon materials with the advantages of various nanostructures, good chemical/ physical stability, light weight, large surface areas, and good conductivity have long been considered as ideal substrates for PANI deposition. Many studies have been conducted and achieved good performance by incorporating PANI with different carbon materials including 0-dimensional active carbon [121,122], 1-dimensional carbon nanofiber or carbon nanotube [123,124], 2-dimensional graphene [125], and 3-dimensional porous carbon [126]. The carbon materials as substrate can also facilitate fast transport/collection of electrons from PANI to carbon substrates as well as to the current collectors [127e129]. To date the hierarchically porous carbon materials have been widely prepared through different methods such as directly carbonizing carbon precursors, template-guided methods (zeolites, silica, or AAO template), hydrothermal treatment, ice-templating or freeze-casting, etc. [130]. Phase separation induced by immersion precipitation method is carried to prepare freestanding hierarchically porous carbon materials, which has been demonstrated to be a very effective approach [131]. Herein, three-dimensional freestanding hierarchically porous carbon materials are fabricated, and PANI with high pseudocapacitance is decorated on carbon through in situ chemical polymerization of aniline monomers. Nanocomposites consisting of PANI and multiwalled carbon nanotubes are also prepared by in situ emulsion polymerization of aniline monomer on the surface of multiwalled carbon nanotubes, using sodium dodecyl sulfate as an emulsifier [132]. Benefiting from the synergistic effects between hierarchical porous carbon and PANI, the resulting composites as electrode materials present dramatic electrochemical performance with high specific capacitance up to 290 F/g at 0.5 A/g [133]. The composites of nano-PANI and carbon scaffold prepared via in situ chemical polymerization exhibit a high specific capacitance of 239 F/g and lower resistance compared to pure PANI. The advanced structure of the composites of nano-PANI and carbon scaffold can be shown in Fig. 7.8. Among various carbon materials, carbon quantum dots with exceptional conducting properties that arise from quantum confinement and edge effects can realize the goal of improving the conductivity of PANI-based electrode materials. However, there is limited information concerning the fabrication of carbon quantum dotse PANI hybrid by electrodeposition method and application as electrode materials. Based on this case, composites electrode material of carbon quantum dotsPANIecarbon fibers is fabricated by directly photoelectrodepositing the carbon quantum dots and PANI on the surface of carbon fibers. The carbon quantum dots are interconnected with PANI to promote electron transportation, which could efficiently improve the conductivity of PANI and enhance its Faradic process. The unique hybrid structured composites show high specific capacitance, excellent rate capability, and cycle stability for energy storage application [134]. For energy storage application, nitrogen-doping would play a great role for enhancing the conductivity and the wettability of the electrode. Thus, hierarchically porous nitrogendoped carbonePANI nanowire array nanocomposites are synthesized by a facile

7.9 PolyanilineeCopper Nanocomposites

(A)

(B)

(C)

(D)

FIGURE 7.8 SEM images of (A and B) C-scaffold, and (C and D) nano-polyaniline/C-scaffold composite [133].

in situ polymerization. The specific capacitance of the nanocomposites of hierarchically porous nitrogen-doped carbonePANI nanowire array electrode shows high specific capacitances of 1080 F/g in 1 mol/L H2SO4 [135].

7.9 POLYANILINEeCOPPER NANOCOMPOSITES Although conducting polymer composites have many interesting physical properties and important application potentials, suitable combinations of metal nanoparticles such as copper or nickel nanoparticles with conductive polymers such as PANI or polypyrrole can result in nanocomposite materials having unique physical and chemical properties that can have wide application potential in diverse areas. Conductive PANIecopper nanocomposites can be synthesized by in situ polymerization of aniline in the fabricated copper suspension, which are fabricated by electrical explosion of wire in solution of polyacrylic acid and ethanol. Through this method, pure copper nanoparticles are uniformly dispersed into the polymer matrix, and the conductivity of the nanocomposites is higher than that of pure PANI and increased with increasing content of copper [136]. For the structure of the nanocomposites, the X-ray diffraction result shows that PANI is amorphous and copper is polycrystalline. Two phases of Cu and Cu2O are formed in aqueous solution while

191

192

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

single Cu phase is obtained in ethanol solution [137]. Copper-containing nanocomposites of PANI can also be synthesized by introducing copper (II) chloride (with the reduction of copper cations with sodium borohydride and hydrazine hydrate and without it) in the oxidative polymerization of aniline (ammonium peroxydisulfate oxidant). The more drastic increase in the rate of hydrogenation of p-nitroaniline and its conversion (compared with those of the electrochemical process on the Cu cathode) results from the activation of the cathode with PANI composites with the copper salt, whose cations are reduced to the metal phases in the electrochemical system [138]. PANIecopper and PANIenickel composites can also be synthesized in the presence and absence of surfactants using ammonium persulfate as an initiator. Incorporating surfactants not greatly affects the morphology and physicochemical properties of the composites. As a result, the surfactant-induced surface characteristics also have an effect on the conductivity of the nanocomposites [139].

7.10 POLYANILINEeMONTMORILLONITE NANOCOMPOSITES In spite of excellent electrical conductivity and outstanding thermal stability, PANI exhibits poor mechanical properties. This means that application of PANI alone as the main coating polymer or even as the filler in the other conventional coatings does not show perfect performance for corrosion protection [140]. Introduction of montmorillonite silicate layers into PANI matrix would result in an improvement in mechanical and anticorrosion properties as compared to the pristine polymer or conventional composite [141e143]. The obtained nanocomposites show conspicuously enhanced thermal, optical, and electrochemical properties [141]. The increased interfacial areas and improved bond characteristics between polymer and high modulus silicate layers may be responsible for the mechanical property enhancement of PANIeclay nanocomposites. In addition, the higher corrosion protection could be due to the promoted barrier properties of silicate layers against aggressive species [144]. Table 7.1 shows some of the recent publications focused on the anticorrosion properties of epoxy and/or PANI coatings containing montmorillonite silicate layers. The method is, however, time-consuming sometimes and might be difficult to scale up for practical purposes especially in mass application involving different shape and size of metal surfaces. Thus, alternative methods such as modification of anticorrosive paints or primers with PANIeclay nanoparticles could be considered as excellent candidates for commercial applications. For example, PANI filled with organo-modified montmorillonite is added to the zinc-rich ethyl silicate primer as a barrier pigment. Layer-by-layer films are fabricated with alternating layers of montmorillonite and either PANI emeraldine salt or polyethylenimine. The layerby-layer films deposited onto ITO substrates are used as electrochemical sensors for detecting heavy metal ions simultaneously using electrochemical measurements by square wave anodic stripping voltammetry [156].

Table 7.1 Recent Trends on Anticorrosion Study of Nanocomposite Coatings Containing Montmorillonite [140] Composition of Coating MMT

OMMT

PANI

Epoxy

Surface

Coating Characterization

Additional Remarks

[144]

U

U

U

e

Steel

PANI/clay was used as a primer coating

[145]

e

U

U

e

Steel

FT-IR, XRD, TEM, gas permeability, GPC, UV spectroscopy, Tafel, EIS, electrical conductivity XRD, SEM, electrical conductivity, EIS, OCP

[146]

e

U

U

e

Steel

[147]

U

U

U

e

Iron

[148]

e

e

U

e

Steel

[149]

e

U

U

e

Steel

[150]

e

U

U

e

Steel and aluminum

FT-IR, XRD, TEM, GPC, TGA, DSC, DMA, Tafel FT-IR, electrical conductivity, Tafel, cyclic voltammetry FT-IR, XRD, cyclic voltammetry, UV spectroscopy, EIS, anodic polarization, electrical conductivity FT-IR, XRD, TEM, Tafel, electrical conductivity, UV spectroscopy, GPC XRD, FT-IR, SEM, TEM, UV spectroscopy, DC polarization

The prepared PANIeclay nanocomposites were added to zinc-rich ethyl silicate primer as a barrier pigment PANI/clay was used as a primer coating PANI/clay was used as a primer coating The sodium cation of MMT was replaced with anilinium one and nanocomposite was used as a primer coating PANI/clay was used as a primer coating Poly(amic acid)/clay coating were prepared and effect of PANI addition on anticorrosion properties was observed Continued

7.10 PolyanilineeMontmorillonite Nanocomposites

References

193

194

Composition of Coating References

MMT

OMMT

PANI

Epoxy

Surface

Coating Characterization

Additional Remarks

[151]

e

U

e

U

Steel

FT-IR, XRD, TEM, gas permeability, TGA, DSC, DMA, UV spectroscopy, Tafel

[152]

e

U

e

U

Steel

[153]

e

U

e

U

Steel

[154]

e

U

U

U

Aluminum

FT-IR, XRD, TEM, DMA, DSC, TGA, gas permeability, Tafel, LOI, EIS Optical microscopy, salt fog test, EIS, Tafel, polarization measurement, adhesion and water absorption tests FT-IR, XRD, SEM, EIS

The epoxy was modified by siloxane and its effect on ultimate properties of modified nanocomposite was investigated Epoxy/clay was used as a primer coating

[155]

U

U

e

U

Steel

FT-IR, XRD, TEM, EIS, adhesion, salt spray test

This work

U

U

U

U

Steel

FT-IR, XRD, Tafel, EIS, immersion test, adhesion test

The effect of nanoglass flake and OMMT addition on corrosion performance of epoxy coating was compared PANI/clay was added to the epoxy coating Clay nanolayers were added to the water-based zinc-rich epoxy coating PANIeclay nanocomposites were added to the epoxy coating

DMA, dynamic mechanical analysis; DSC, differential scanning calorimetry; EIS, electrochemical impedance spectroscopy; GPC, gel permeation chromatography; LOI, limiting oxygen index; OCP, open circuit potential; SEM, scanning electron microscopy; TEM, transmission electron microscopy; TGA, thermo-gravimetric analysis.

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

Table 7.1 Recent Trends on Anticorrosion Study of Nanocomposite Coatings Containing Montmorillonite [140]dcont’d

7.11 PolyanilineeGraphene Nanocomposites

7.11 POLYANILINEeGRAPHENE NANOCOMPOSITES Carbon materials exhibit quite efficient regeneration performance due to high electrical conductivity, whereas graphene shows better deionization performance than the other carbon materials such as activated carbon powder, even with a much lower surface area [157]. Graphene is a two-dimensional material with carbon atoms arranged in a regular hexagonal pattern to form one-atom thick sheets. Carbon atoms are sp2-boned in the bond length of 0.144 nm. The electron mobility of graphene can be as high as 200,000 cm2/V$S [158]. This demonstrates that the electrical conductivity of graphene is excellent. More importantly, being a single-atom layer structure, the theoretical surface area of graphene is 2630 m2/g [159]. Most importantly, the interlayered open structure of graphene sheets favors easy ion adsorption and desorption. These properties make the nanocomposites of graphene and PANI an attractive candidate in various applications [160,161]. GrapheneePANI nanocomposites have been chosen, which aim to increase the ion electrosorption capacitance of graphene. Zou et al. synthesized grapheneePANI nanocomposites by chemical polymerization of aniline in the presence of dispersed graphene sheets. The ion removal performance of the nanocomposites is determined by using a membrane capacitive deionization bench-scale system [162]. Electroconductive grapheneePANI nanocomposites based on poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) and partially reduced graphene oxide are synthesized by in situ oxidative polymerization of 3,4-ethylenedioxythiophene using poly(4styrenesulfonate) as a template in the presence of graphene oxide. During polymerization, graphene oxide is partially reduced in which the resulting nanocomposites display a stable aqueous suspension. The obtained nanocomposites show an enhanced electrical conductivity of 9.2 S/cm [163]. By introducing sodium dodecyl sulfate solution, the high conductivity and thermal stability of PANIegraphene nanocomposites can also be prepared by in situ chemical oxidation polymerization. The conductivities of PANIegraphene nanocomposites are strongly dependent on the content of sodium dodecyl sulfate (see Fig. 7.9). Maximum conductivity of PANIe graphene nanocomposites can reach to 90.3 S/cm by adding 250 mg/mL sodium dodecyl sulfate, which is about two times of magnitude higher than that of PANIe graphene nanocomposites without sodium dodecyl sulfate [164]. To prepare a more stable PANI and graphene, covalent bonding of the two components is pretty important. For this novel approach, graphene oxide is functionalized first by introducing amine groups onto the surface with the reduction of graphene oxide in the process and then served as the anchor sites for the growth of PANI via in situ polymerization. After the functionalization process, the grapheneePANI composite electrode exhibits remarkably enhanced electrochemical performance with specific capacitance of 489 F/g at 0.5 A/g, which is superior to those of the composites without covalently bonding or its individual components. The outstanding electrochemical performance of the hybrid can be attributed to its covalently synergistic effect between graphene and PANI, suggesting promising potentials for energy storage [165].

195

196

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

FIGURE 7.9 Conductivity dependence of polyanilineegraphene nanocomposites on sodium dodecyl sulfate [164].

7.12 CELLULOSE WHISKERSePOLYANILINE NANOCOMPOSITES Cellulose fibers have been widely used due to their sustainability and good mechanical properties. Nanocellulose fibrils have recently gained attention from researchers and industry because it has high tensile modulus (138 GPa), which is higher than that of the S-glass (86e90 GPa) and comparable to Kevlar (131 GPa), rendering them good reinforcement for natural and synthetic polymer matrices [166e168]. Cellulose nanowhiskers, with size ranging from a few to tens of nanometers in one dimension, have some unique properties, including renewable resource, excellent mechanical properties, high specific surface area, biodegradability, and biocompatibility [169]. Moreover, cellulose, rich in hydroxyl group, has good affinity with a variety of polymers, including conducting polymers [170,171]. Cellulose nanowhiskers can be prepared from a variety of sources, such as wood pulp, plant fibers (e.g., hemp, sisal, flax, ramie, jute, algae) [172], microbial (Acetobacter xylinum) [173], sea creatures (tunicate) [174], fruits (banana and grape skin) [175], and even agricultural products (e.g., cornhusk, wheat straw) [176], which make them more attractive and applicable. Cellulose fibers have been used to reinforce brittle conducting polymers, such as polypyrrole, PANI, and polythiophene for various applications [177]. Combining cellulose nanowhiskers and PANI is promising for developing green functional polymer nanocomposites [178]. Liu et al. used nanocellulose as the matrix and added PANI as conducting component to produce the nanocellulose-based flexible

7.13. Conclusions

and electrically conducting composite films. The combination of nanocellulose and PANI gives the nanocomposites good conductivity and excellent mechanical properties. The composites, combining good mechanical properties of cellulose nanowhiskers and conductivity of PANI, have great potential in anticorrosion coatings, conducting adhesives, antistatic and electromagnetic interference shielding materials, biodegradable smart sensors/actuators, and batteries [179]. The creation of conducting networks within composite materials is very important to reduce the generally expensive conducting polymer content to create conducting/ nonconducting domains, and to adjust conductivity of the final composites. Cellulose/ poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate)-based polystyrene composites with an extremely low percolation threshold of the conductive polymer is developed and can be applied onto the other conducting composites to reduce the required conducting polymer content and increase the ease of processing as electrical percolation [180]. Nanocomposites of natural rubber reinforced with cellulose nanofibrils and cellulose nanofibrials/PANI can be further obtained by casing/evaporation method. Cellulose nanofibrils are isolated from cotton microfibrils by acid hydrolysis and coated with PANI by in situ polymerization of aniline onto cellulose nanofibrils in the presence of hydrochloride acid and ammonium peroxydisulfate to produce cellulose nanofibrils/PANI. These nanocomposites show better thermal stability compared to the conventional composites. In addition, mechanical properties of natural rubber are significantly improved with nanofibril incorporation, the electrical conductivity of natural rubber increases five orders of magnitude for natural rubber with the addition of 10 wt% cellulose nanofibrilsePANI composites [181].

7.13 CONCLUSIONS In summary, PANI can be used as conducting polymer to fabricate the functionalized nanocomposites such as PANIeTiO2 nanocomposites, PANIecalcium carbonate composites, natural fiberebased PANI composites, filler-based PANI composites, PANIesilica nanocomposites, PANIeclay nanocomposites, PANIeporous carbon nanocomposites, PANIelayered silicate composites, PANIecopper nanocomposites, PANIemontmorillonite nanocomposites, PANIegraphene nanocomposites, and cellulose whiskersePANI nanocomposites. Various morphologies of nanotubes, nanorods, nanowires, nanoparticles, nanosheets, nanoplates, and nanowhiskers have been designed and fabricated by in situ chemical polymerization. The covalent bonding of the components of the composites or nanocomposites make it having more stable properties for various applications such as energy storage, catalyst and other systems. With the fast development of PANI in recent years, one can imagine that more and more composites and nanocomposites with advanced structures and morphologies would be developed in the future years.

197

198

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

REFERENCES [1] M. Biswas, S.S. Raya, Y.P. Liu, Water dispersible conducting nanocomposites of poly(N-vinylcarbazole), polypyrrole and polyaniline with nanodimensional manganese (IV) oxide, Synth. Met. 105 (2) (1999) 99e105. [2] N. Prastomo, M. Ayad, G. Kawamura, A. Matsuda, Synthesis and characterization of polyaniline nanofiber/TiO2 nanoparticles hybrids, J. Ceram. Soc. Jpn. 119 (1389) (2011) 342e345. [3] M.M. Ayad, N. Prastomo, A. Matsuda, J. Stejskal, Sensing of silver ions by nanotubular polyaniline film deposited on quartz-crystal in a microbalance, Synth. Met. 160 (1) (2010) 42e46. [4] S. Xiong, Q. Wang, Y. Chen, Preparation of polyaniline/TiO2 hybrid microwires in the microchannels of a template, Mater. Chem. Phys. 103 (2) (2007) 450e455. [5] R. Shrivastava, S. Saxena, S.P. Satsangee, R. Jain, Graphene/TiO2/polyaniline nanocomposite based sensor for the electrochemical investigation of aripiprazole in pharmaceutical formulation, Ionics 21 (7) (2015) 2039e2049. [6] B. O’regan, M. Grfitzeli, A low-cost, high-efficiency solar cell based on dyesensitized, Nature 353 (6346) (1991) 737e740. [7] S. Deivanayaki, V. Ponnuswamy, S. Ashokan, P. Jayamurugan, R. Mariappan, Synthesis and characterization of TiO2-doped polyaniline nanocomposites by chemical oxidation method, Mater. Sci. Semicond. Process. 16 (2) (2013) 554e559. [8] J. Huang, R.B. Kaner, A general chemical route to polyaniline nanofibers, J. Am. Chem. Soc. 126 (3) (2004) 851e855. [9] X. Zhang, W.J. Goux, S.K. Manohar, Synthesis of polyaniline nanofibers by “nanofiber seeding”, J. Am. Chem. Soc. 126 (14) (2004) 4502e4503. [10] M.R. Karim, J.H. Yeum, M.S. Lee, K.T. Lim, Preparation of conducting polyaniline/ TiO2 composite submicron-rods by the g-radiolysis oxidative polymerization method, React. Funct. Polym. 68 (9) (2008) 1371e1376. [11] C.C. Yang, W.C. Chien, Y.J. Li, Direct methanol fuel cell based on poly (vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO2/PSSA) composite polymer membrane, J. Power Sourc. 195 (11) (2010) 3407e3415. [12] M. Ouyang, R. Bai, Y. Xu, C. Zhang, C.A. Ma, M. Wang, H.Z. Chen, Fabrication of polypyrrole/TiO2 nanocomposite via electrochemical process and its photoconductivity, Trans. Nonferrous Metals Soc. China 19 (6) (2009) 1572e1577. ´ . Ra´cz, C. Visy, Electrochemical grafting of poly(3, 4[13] C. Jana´ky, G. Bencsik, A ethylenedioxythiophene) into a titanium dioxide nanotube host network, Langmuir 26 (16) (2010) 13697e13702. [14] J. Lee, J.Y. Jho, Fabrication of highly ordered and vertically oriented TiO2 nanotube arrays for ordered heterojunction polymer/inorganic hybrid solar cell, Sol. Energy Mater. Sol. Cells 95 (11) (2011) 3152e3156. [15] Y. Xie, H. Du, Electrochemical capacitance performance of polypyrroleetitania nanotube hybrid, J. Solid State Electrochem. 16 (8) (2012) 2683e2689. [16] S.H. Mujawar, S.B. Ambade, T. Battumur, R.B. Ambade, S.H. Lee, Electropolymerization of polyaniline on titanium oxide nanotubes for supercapacitor application, Electrochim. Acta 56 (12) (2011) 4462e4466. [17] F. Gobal, M. Faraji, Electrodeposited polyaniline on Pd-loaded TiO2 nanotubes as active material for electrochemical supercapacitor, J. Electroanal. Chem. 691 (2013) 51e56.

References

[18] Y.B. Xie, C.J. Huang, L.M. Zhou, Y. Liu, H.T. Huang, Supercapacitor application of nickel oxideetitania nanocomposites, Compos. Sci. Technol. 69 (13) (2009) 2108e2114. [19] Y.B. Xie, L.M. Zhou, C.J. Huang, H.T. Huang, J. Lu, Fabrication of nickel oxideembedded titania nanotube array for redox capacitance application, Electrochim. Acta 53 (10) (2008) 3643e3649. [20] K.Y. Xie, J. Li, Y.Q. Lai, Z.A. Zhang, Y.X. Liu, G.G. Zhang, H.T. Huang, Polyaniline nanowire array encapsulated in titania nanotubes as a superior electrode for supercapacitors, Nanoscale 3 (5) (2011) 2202e2207. [21] M. Salari, K. Konstantinov, H.K. Liu, Enhancement of the capacitance in TiO2 nanotubes through controlled introduction of oxygen vacancies, J. Mater. Chem. 21 (13) (2011) 5128e5133. [22] H. Wu, C. Xu, J. Xu, L.F. Lu, Z.Y. Fan, X.Y. Chen, Y. Song, D.D. Li, Enhanced supercapacitance in anodic TiO2 nanotube films by hydrogen plasma treatment, Nanotechnology 24 (45) (2013) 455401. [23] J.M. Macak, B.G. Gong, M. Hueppe, P. Schmuki, Filling of TiO2 nanotubes by selfdoping and electrodeposition, Adv. Mater. 19 (19) (2007) 3027e3031. [24] J.Q. Chen, Z.B. Xia, H. Li, Q. Li, Y.J. Zhang, Preparation of highly capacitive polyaniline/black TiO2 nanotubes as supercapacitor electrode by hydrogenation and electrochemical deposition, Electrochim. Acta 166 (2015) 174e182. [25] Z. Shao, H.J. Li, M.J. Li, C.P. Li, C.Q. Qu, B.H. Yang, Fabrication of polyaniline nanowire/TiO2 nanotube array electrode for supercapacitors, Energy 87 (2015) 578e585. [26] J.M. Yun, S.Y. Jeon, H.I. Kim, Improvement of NO gas sensing properties of polyaniline/MWCNT composite by photocatalytic effect of TiO2, J. Nanomater. 2013 (2013) 3. [27] W.D. Zhang, L.C. Jiang, Y.X. Yu, X.L. Wei, Electrodeposition of polyaniline onto TiO2 nanoparticles/multiwalled carbon nanotubes for visible light photoelectrocatalysis, J. Nanosci. Nanotechnol. 14 (9) (2014) 7032e7037. [28] J. Zhu, X.Q. Liu, X.H. Wang, X.H. Huo, R. Yan, Preparation of polyanilineeTiO2 nanotube composite for the development of electrochemical biosensors, Sensors Actuators B Chem. 221 (2015) 450e457. [29] K. Yang, W.H. Pu, Y.B. Tan, M. Zhang, C.Z. Yang, J.D. Zhang, Enhanced photoelectrocatalytic activity of Cr-doped TiO2 nanotubes modified with polyaniline, Mater. Sci. Semicond. Process. 27 (2014) 777e784. [30] J.C. Xu, W.M. Liu, H.L. Li, Titanium dioxide doped polyaniline, Mater. Sci. Eng. 25 (2005) 444e447. [31] J.B. Zheng, G. Li, X.F. Ma, Y.M. Wang, G. Wu, Y.N. Cheng, PolyanilineeTiO2 nanocomposite-based trimethylamine QCM sensor and its thermal behavior studies, Sens. Actuators 133 (2008) 374e380. [32] G.K.R. Senadeera, T. Kitamura, Y. Wadab, S. Yanagida, Deposition of polyaniline via molecular self-assembly on TiO2 and its uses as a sensitiser in solid-state solar cells, J. Photochem. Photobiol. 164 (2004) 61e66. [33] H. Zhang, R.L. Zong, J.C. Zhao, Y.F. Zhu, Dramatic visible photocatalytic degradation performances due to synergetic effect of TiO2 with PANI, Environ. Sci. Technol. 42 (2008) 3803e3807. [34] H.S. Xia, Q. Wang, Ultrasonic irradiation: a novel approach to prepare conductive polyaniline/nanocrystalline titanium oxide composites, Chem. Mater. 14 (2002) 2158e2165.

199

200

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

[35] D.C. Schnitzler, A.J.G. Zarbin, Organic/inorganic hybrid materials formed from TiO2 nanoparticles and polyaniline, J. Braz. Chem. Soc. 15 (3) (2004) 378e384. [36] D.P. Wang, H.C. Zeng, Multifunctional roles of TiO2 nanoparticles for architecture of complex CoreShells and hollow spheres of SiO2TiO2polyaniline system, Chem. Mater. 21 (20) (2009) 4811e4823. [37] W.J. Bae, A.R. Davis, J. Jung, W.H. Jo, K.R. Carter, E.B. Coughlin, One-pot synthesis of hybrid TiO2epolyaniline nanoparticles by self-catalyzed hydroamination and oxidative polymerization from TiO2emethacrylic acid nanoparticles, Chem. Commun. 47 (38) (2011) 10710e10712. [38] A. Olad, S. Behboudi, A.A. Entezami, Effect of polyaniline as a surface modifier of TiO2 nanoparticles on the properties of polyvinyl chloride/TiO2 nanocomposites, Chin. J. Polym. Sci. 31 (3) (2013) 481e494. [39] A.M. Youssef, Morphological studies of polyaniline nanocomposite based mesostructured TiO2 nanowires as conductive packaging materials, RSC Adv. 4 (2014) 6811e6820. [40] Q.Q. Tan, Y.X. Xu, J. Yang, L.L. Qiu, Y. Chen, X.X. Chen, Preparation and electrochemical properties of the ternary nanocomposite of polyaniline/activated carbon/ TiO2 nanowires for supercapacitors, Electrochim. Acta 88 (2013) 526e529. [41] S.X. Yang, X.J. Cui, J. Gong, Y.L. Deng, Synthesis of TiO2epolyaniline coreeshell nanofibers and their unique UV photoresponse based on different photoconductive mechanisms in oxygen and non-oxygen environments, Chem. Commun. 49 (41) (2013) 4676e4678. [42] Q.Z. Yu, M. Wang, H.Z. Chen, Z.W. Dai, Polyaniline nanowires on TiO2 nano/microfiber hierarchical nano/microstructures: preparation and their photocatalytic properties, Mater. Chem. Phys. 129 (2011) 666e672. [43] X.H. Zu, H. Wang, G.B. Yi, Z. Zhang, X.M. Jiang, J. Gong, H.S. Luo, Self-powered UV photodetector based on heterostructured TiO2 nanowire arrays and polyaniline nanoflower arrays, Synth. Met. 200 (2015) 58e65. [44] M.R. Karim, M.S. Lee, K.T. Lim, Preparation of conducting polyaniline/TiO2 composite nanorods by the radiolysis polymerization method, in: Microprocesses and Nanotechnology, 2007 Digest of Papers, IEEE, 2007, pp. 202e203. [45] X.Q. Fu, C.Y. Jia, Z.Q. Wan, X.L. Weng, J.L. Xie, L.J. Deng, Hybrid electrochromic film based on polyaniline and TiO2 nanorods array, Org. Electron. 15 (11) (2014) 2702e2709. [46] L. Zhang, L. Chen, B. Qi, G.C. Yang, J. Gong, Synthesis of vertical aligned [email protected] coreeshell nanorods for high-performance supercapacitors, RSC Adv. 5 (3) (2015) 1680e1683. [47] H. Xu, F.L. Jia, Z.H. Ai, L.Z. Zhang, A general soft interface platform for the growth and assembly of hierarchical rutile TiO2 nanorods spheres, Cryst. Growth Design 7 (7) (2007) 1216e1219. [48] J.H. Wei, Q. Zhang, Y. Liu, R. Xiong, C.X. Pan, J. Shi, Synthesis and photocatalytic activity of polyanilineeTiO2 composites with bionic nanopapilla structure, J. Nanoparticle Res. 13 (8) (2011) 3157e3165. [49] Y. Li, H.T. Ban, H.J. Zhao, M.J. Yang, Facile preparation of a composite of TiO2 nanosheets and polyaniline and its gas sensing properties, RSC Adv. 5 (129) (2015) 106945e106952. [50] O. Grassmann, G. Mu¨ller, P. Lo¨bmann, Organic-inorganic hybrid structure of calcite crystalline assemblies grown in a gelatin hydrogel matrix: relevance to biomineralization, Chem. Mater. 14 (11) (2002) 4530e4535.

References

[51] S. Mann, G.A. Ozin, Synthesis of inorganic materials with complex form, Nature 382 (6589) (1996) 313e318. [52] M. Mihai, I. Bunia, F. Doroftei, C.D. Varganici, B.C. Simionescu, Highly efficient copper (II) ion sorbents obtained by calcium carbonate mineralization on functionalized cross-linked copolymers, Chem. A Eur. J. 21 (13) (2015) 5220e5230. [53] C. Sanchez, B. Julia´n, P. Belleville, M. Popall, Applications of hybrid organice inorganic nanocomposites, J. Mater. Chem. 15 (35e36) (2005) 3559e3592. [54] A. Neira-Carrillo, D.F. Acevedo, M.C. Miras, C.A. Barbero, D. Gebauer, H. Co¨lfen, J.L. Arias, Influence of conducting polymers based on carboxylated polyaniline on in vitro CaCO3 crystallization, Langmuir 24 (21) (2008) 12496e12507. [55] A. Neira-Carrillo, E. Yslas, Y.A. Marini, P. Va´squez-Quitrala, M. Sa´ncheza, A. Riverosb, D. Ya´n˜eza, P. Cavalloe, M.J. Kogan, D. Acevedo, Hybrid biomaterials based on calcium carbonate and polyaniline nanoparticles for application in photothermal therapy, Colloids Surf B Biointerfaces 145 (2016) 634e642. [56] A.J. Meinel, K.E. Kubow, E. Klotzsch, M. Garcia-Fuentes, M.L. Smith, V. Vogel, H.P. Merkle, L. Meinel, Optimization strategies for electrospun silk fibroin tissue engineering scaffolds, Biomaterials 30 (17) (2009) 3058e3067. [57] S.I.A. Razak, W.A.W.A. Rahman, S. Hashim, M.Y. Yahya, Enhanced interfacial interaction and electronic properties of novel conducting kenaf/polyaniline biofibers, Polym. Plast. Technol. Eng. 52 (1) (2013) 51e57. [58] S.I.A. Razak, W.A.W.A. Rahman, N.F.A. Sharif, M.Y. Yahya, Simultaneous numerical optimization of the mechanical and electrical properties of polyaniline coated kenaf fiber using response surface methodology: nanostructured polyaniline on natural fiber, Compos. Inter. 19 (7) (2012) 411e424. [59] S. Chandran, S.K. Narayanankutty, Polyaniline-coated short nylon fiber/natural rubber conducting composite, Polym. Plast. Technol. Eng. 50 (5) (2011) 443e452. [60] F.G. Souza, G.E. Oliveira, C.H.M. Rodrigues, B.G. Soares, M. Nele, J.C. Pinto, Natural Brazilian amazonic (Curaua´) fibers modified with polyaniline nanoparticles, Macromol. Mater. Eng. 294 (8) (2009) 484e491. [61] A.G. Supri, S.J. Tan, H. Ismail, P.L. The, Properties of (Low-density polyethylene)/ (natural rubber)/(water hyacinth fiber) composites: the effect of polyaniline, J. Vinyl Addit. Technol. 20 (2) (2014) 122e130. [62] Y.Y. Xia, Y. Lu, Fabrication and properties of conductive conjugated polymers/silk fibroin composite fibers, Compos. Sci. Technol. 68 (6) (2008) 1471e1479. [63] I. Cucchi, A. Boschi, C. Arosio, F. Bertini, G. Freddi, M. Catellani, Bio-based conductive composites: preparation and properties of polypyrrole (PPy)-coated silk fabrics, Synth. Met. 159 (3) (2009) 246e253. [64] J.Y. Lee, C.A. Bashur, A.S. Goldstein, C.E. Schmidt, Polypyrrole-coated electrospun PLGA nanofibers for neural tissue applications, Biomaterials 30 (26) (2009) 4325e4335. [65] S.I.A. Razak, W.A.W.A. Rahman, S. Hashim, M.Y. Yahya, In situ surface modification of natural fiber by conducting polyaniline, Compos. Inter. 19 (6) (2012) 365e376. [66] X.M. Yang, Z.X. Zhu, T.Y. Dai, Y. Lu, Facile fabrication of functional polypyrrole nanotubes via a reactive self-degraded template, Macromol. Rapid Commun. 26 (21) (2005) 1736e1740. [67] Y.Y. Xia, X. Lu, H.L. Zhu, Natural silk fibroin/polyaniline (core/shell) coaxial fiber: fabrication and application for cell proliferation, Compos. Sci. Technol. 77 (2013) 37e41.

201

202

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

[68] M. Cochet, W.K. Maser, A.M. Benito, M.A. Callejas, M.T. Martı´nez, J. Benoit, J. Schreiber, O. Chauvet, Synthesis of a new polyaniline/nanotube composite:“insitu” polymerisation and charge transfer through site-selective interaction, Chem. Commun. 16 (2001) 1450e1451. [69] W.K. Maser, A.M. Benito, M.A. Callejas, T. Seeger, M.T. Martınez, J. Schreiber, J. Muszynski, O. Chauvet, Z. Osva´th, A.A. Koo´s, L.P. Biro´, Synthesis and characterization of new polyaniline/nanotube composites, Mater. Sci. Eng. C 23 (1) (2003) 87e91. [70] S. Bhadra, D. Khastgir, N.K. Singha, J.H. Lee, Progress in preparation, processing and applications of polyaniline, Prog. Polym. Sci. 34 (8) (2009) 783e810. [71] P. Gajendran, R. Saraswathi, Polyaniline-carbon nanotube composites, Pure Appl. Chem. 80 (11) (2008) 2377e2395. [72] E.J. Jelmy, S. Ramakrishnan, M. Rangarajan, N.K. Kothurkar, Effect of different carbon fillers and dopant acids on electrical properties of polyaniline nanocomposites, Bull. Mater. Sci. 36 (1) (2013) 37e44. [73] S.M. Abbas, M. Chandra, A. Verma, R. Chatterjee, T.C. Goel, Complex permittivity and microwave absorption properties of a composite dielectric absorber, Compos. A Appl. Sci. Manuf. 37 (11) (2006) 2148e2154. [74] D.A. Makeiff, T. Huber, Microwave absorption by polyanilineecarbon nanotube composites, Synth. Met. 156 (7) (2006) 497e505. [75] S.K. Dhawan, K. Singh, A.K. Bakhshi, A. Ohlan, Conducting polymer embedded with nanoferrite and titanium dioxide nanoparticles for microwave absorption, Synth. Met. 159 (21) (2009) 2259e2262. [76] P. Chandrasekhar, K. Naishadham, Broadband microwave absorption and shielding properties of a poly (aniline), Synth. Met. 105 (2) (1999) 115e120. [77] N.A. Abdelwahab, A.M. Ghoneim, M.A.A. El-Ghaffar, Polyaniline hydrochloride for a novel application: accelerator and filler for phenol-formaldehyde resin, J. Adhesion Sci. Technol. 26 (8e9) (2012) 1093e1108. [78] B. Belaabed, J.L. Wojkiewicz, S. Lamouri, N.E. Kamchib, T. Lasrib, Synthesis and characterization of hybrid conducting composites based on polyaniline/magnetite fillers with improved microwave absorption properties, J. Alloys Comp. 527 (2012) 137e144. [79] A. Kalendova´, I. Sapurina, J. Stejskal, D. Vesely´, Anticorrosion properties of polyaniline-coated pigments in organic coatings, Corros. Sci. 50 (12) (2008) 3549e3560. [80] H. Kukackova´, A. Kalendova´, Investigation of mechanical resistance and corrosione inhibition properties of surface-modified fillers with polyaniline in organic coatings, J. Phys. Chem. Sol. 73 (12) (2012) 1556e1561. [81] F. Xu, G.D. Zheng, D.C. Wu, Y.R. Liang, Z.H. Li, R.W. Fu, Improving electrochemical performance of polyaniline by introducing carbon aerogel as filler, Phys. Chem. Chem. Phys. 12 (13) (2010) 3270e3275. [82] B. Sonerud, S. Josefsson, K.M. Furuheim, L. Boyer, C. Frohen, J. Pelto, Nonlinear electrical properties and mechanical strength of EPDM with polyaniline and carbon black filler, in: 2013 IEEE International Conference on Solid Dielectrics (ICSD), IEEE, 2013, pp. 366e369. [83] S.X. Xiong, J. Wei, P.T. Jia, L.P. Yang, J. Ma, X.H. Lu, Water-processable polyaniline with covalently bonded single-walled carbon nanotubes: enhanced electrochromic properties and impedance analysis, ACS Appl. Mater. Interfaces 3 (3) (2011) 782e788.

References

[84] Y.J. Kim, M.K. Shin, S.J. Kim, S. Kim, H. Lee, J. Park, S.I. Kim, Electrical properties of polyaniline and multi-walled carbon nanotube hybrid fibers, J. Nanosci. Nanotechnol. 7 (11) (2007) 4185e4189. [85] M.S. Kang, M.K. Shin, Y.A. Ismail, S.R. Shin, S.I. Kim, H. Kim, H. Lee, S.J. Kim, The fabrication of polyaniline/single-walled carbon nanotube fibers containing a highlyoriented filler, Nanotechnology 20 (8) (2009) 085701. [86] M. Oyharc¸abal, T. Olinga, M.P. Foulc, V. Vigneras, Polyaniline/clay as nanostructured conductive filler for electrically conductive epoxy composites. Influence of filler morphology, chemical nature of reagents, and curing conditions on composite conductivity, Synth. Met. 162 (7) (2012) 555e562.  ´rkova´, P. Bober, J. Kotek, J. Stejskal, Bi-hybrid coatings: polyaniline[87] M. Spı montmorillonite filler in organic-inorganic polymer matrix, Chem. Pap. 67 (8) (2013) 1020e1027. [88] M. Molberg, D. Crespy, P. Rupper, F. Nu¨esch, J.E. Ma˚nson, C. Lo¨we, D.M. Opris, High breakdown field dielectric elastomer actuators using encapsulated polyaniline as high dielectric constant filler, Adv. Funct. Mater. 20 (19) (2010) 3280e3291. [89] D.P. Xu, Z.H. Huang, L. Han, Y. Yao, S.N. Che, Amphiphilic ABC triblock terpolymer templated large-pore mesoporous silicas, Mater. Lett. 141 (2015) 176e179. [90] H.Q. Shao, H. Zhou, X.Y. Guo, Y.Q. Tao, T. Jiang, M.G. Qin, Chromium catalysts supported on mesoporous silica for ethylene tetramerization: effect of the porous structure of the supports, Catal. Commun. 60 (2015) 14e18. [91] F. Zalloi, A. Olad, Fabrication of conductive polyaniline nanocomposites based on silica nanoparticles via in-situ chemical oxidative polymerization technique, synthesis and reactivity in inorganic, Met. Org. Nano Met. Chem. 45 (1) (2015) 86e91. [92] K. Dutta, S.K. De, High dielectric permittivity in silicaepolyaniline nanocomposites, J. Nanosci. Nanotechnol. 6 (2) (2006) 499e504. [93] H.B. Gu, J. Guo, X. Zhang, Q.L. He, Y.D. Huang, H.A. Colorado, D.P. Young, Giant magnetoresistive phosphoric acid doped polyanilineesilica nanocomposites, J. Phys. Chem. C 117 (12) (2013) 6426e6436. [94] H.B. Gu, J. Guo, X. Zhang, Q.L. He, Y.D. Huang, H.A. Colorado, D.P. Young, Flameretardant epoxy resin nanocomposites reinforced with polyaniline-stabilized silica nanoparticles, Ind. Eng. Chem. Res. 52 (23) (2013) 7718e7728. [95] A. Mehdinia, M. Ahmadifar, M.O. Aziz-Zanjani, A. Jabbarib, M.S. Hashtroudic, Selective adsorption of 2, 4-dinitrophenol on molecularly imprinted nanocomposites of mesoporous silica SBA-15/polyaniline, Analyst 137 (18) (2012) 4368e4374. [96] L.H. Ding, B. Su, A non-enzymatic hydrogen peroxide sensor based on platinum nanoparticleepolyaniline nanocomposites hosted in mesoporous silica film, J. Electroanal. Chem. 736 (2015) 83e87. [97] Y.Q. Don, Y.P. Zhai, F.W. Zeng, X.X. Liu, B. Tu, D.Y. Zhao, Encapsulation of polyaniline in 3-D interconnected mesopores of silica KIT-6, J. Colloid Interface Sci. 341 (2) (2010) 353e358. [98] L. Zu, X.G. Cui, Y.H. Jiang, Z.K. Hu, H.Q. Lian, Y. Liu, Y.S. Jin, Y. Li, X.D. Wang, Preparation and electrochemical characterization of mesoporous polyaniline-silica nanocomposites as an electrode material for pseudocapacitors, Materials 8 (4) (2015) 1369e1383.  c-Marjanovic, L. Dragicevic, M.J. Milojevic, M. Mojovic, S. Mentus, Synthesis [99] G. Ciri and characterization of self-assembled polyaniline nanotubes/silica nanocomposites, J. Phys. Chem. B 113 (20) (2009) 7116e7127.

203

204

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

[100] J. Konta, Clay and man: clay raw materials in the service of man, Appl. Clay Sci. 10 (4) (1995) 275e335. [101] R.A. Vaia, G. Price, P.N. Ruth, H.T. Nguyen, J. Lichtenhan, Polymer/layered silicate nanocomposites as high performance ablative materials, Appl. Clay Sci. 15 (1) (1999) 67e92. [102] C.J. Jing, L.S. Chen, Y. Shi, X.G. Jin, Synthesis and characterization of exfoliated MEH-PPV/clay nanocomposites by in situ polymerization, Eur. Polym. J. 41 (10) (2005) 2388e2394. [103] M. Eckle, G. Decher, Tuning the performance of layer-by-layer assembled organic light emitting diodes by controlling the position of isolating clay barrier sheets, Nano Lett. 1 (1) (2001) 45e49. [104] T.W. Lee, O.O. Park, J. Yoon, J.J. Kim, Polymer-layered silicate nanocomposite lightemitting devices, Adv. Mater. 13 (3) (2001) 211e213. [105] G.M.D. Nascimento, V.R.L. Constantino, M.L.A. Temperini, Spectroscopic characterization of a new type of conducting polymer-clay nanocomposite, Macromolecules 35 (20) (2002) 7535e7537. [106] S. Yoshimoto, F. Ohashi, Y. Ohnishi, T. Nonami, Synthesis of polyanilinee montmorillonite nanocomposites by the mechanochemical intercalation method, Synth. Met. 145 (2) (2004) 265e270. [107] S. Yoshimoto, F. Ohashi, Y. Ohnishi, T. Nonami, Solvent free synthesis of polyanilineeclay nanocomposites from mechanochemically intercalated anilinium fluoride, Chem. Commun. 17 (2004) 1924e1925. [108] S. Yoshimoto, F. Ohashi, T. Kameyama, Characterization and thermal degradation studies on polyaniline-intercalated montmorillonite nanocomposites prepared by a solvent-free mechanochemical route, J. Polym. Sci. B Polym. Phys. 43 (19) (2005) 2705e2714. [109] J. Huang, J.A. Moore, J.H. Acquaye, R.B. Kaner, Mechanochemical route to the conducting polymer polyaniline, Macromolecules 38 (2) (2005) 317e321. [110] N. Kalaivasan, S.S. Shafi, Synthesis of various polyaniline/clay nanocomposites derived from aniline and substituted aniline derivatives by mechanochemical intercalation method, J. Chem. 7 (4) (2010) 1477e1483. [111] P.C. LeBaron, Z. Wang, T.J. Pinnavaia, Polymer-layered silicate nanocomposites: an overview, Appl. Clay Sci. 15 (1) (1999) 11e29. [112] M. Biswas, S.S. Ray, Recent Progress in Synthesis and Evaluation of Polymermontmorillonite Nanocomposites, New Polymerization Techniques and Synthetic Methodologies, Springer Berlin Heidelberg, 2001, pp. 167e221. [113] B. Vijayakumar, K.O. Anjana, G.R. Rao, Polyaniline/clay nanocomposites: preparation, characterization and electrochemical properties, IOP Conf. Ser. Mater. Sci. Eng. 73 (1) (2015) 012112. IOP Publishing. [114] A. Garai, A.K. Nandi, Rheology of polyaniline-dinonylnaphthalene disulfonic acid (DNNDSA) montmorillonite clay nanocomposites in the sol state: shear thinning versus pseudo-solid behaviour, J. Nanosci. Nanotechnol. 8 (4) (2008) 1842e1851. [115] J.L. Hu, M.Y. Gan, L. Ma, Z.T. Li, J. Yan, J. Zhang, Synthesis and anticorrosive properties of polymereclay nanocomposites via chemical grafting of polyaniline onto ZnAl layered double hydroxides, Surf. Coat. Technol. 240 (2014) 55e62. [116] Z. Tang, P. Liu, J. Guo, Z. Su, Preparation of polyaniline/vermiculite clay nanocomposites by in situ chemical oxidative grafting polymerization, Polym. Int. 58 (5) (2009) 552e556.

References

[117] J. Wang, J.O. Iroh, S. Hall, Effect of polyaniline-modified clay on the processing and properties of clay polyimide nanocomposites, Appl. Clay Sci. 99 (2014) 215e219. [118] R.N. Reddy, R.G. Reddy, Solegel MnO2 as an electrode material for electrochemical capacitors, J. Power Sourc. 124 (1) (2003) 330e337. [119] L.J. Pan, L. Pu, Y. Shi, S.Y. Song, Z. Xu, R. Zhang, Synthesis of polyaniline nanotubes with a reactive template of manganese oxide, Adv. Mater. 19 (3) (2007) 461e464. [120] F. Ran, Y.Y. Yang, L. Zhao, X.Q. Niu, D.J. Zhang, L.B. Kong, Y.C. Luo, L. Kang, Preparation of [email protected] by surface initiated polymerization method using as a nano-tubular electrode material: the amount effect of aniline on the microstructure and electrochemical performance, J. Energy Chem. 24 (4) (2015) 388e393. [121] Z.B. Lei, Z.W. Chen, X.S. Zhao, Growth of polyaniline on hollow carbon spheres for enhancing electrocapacitance, J. Phys. Chem. C 114 (46) (2010) 19867e19874. [122] X.T. Ning, W.B. Zhong, L. Wan, Ultrahigh specific surface area porous carbon nanospheres and its composite with polyaniline: preparation and application for supercapacitors, RSC Adv. 6 (30) (2016) 25519e25524. [123] S.J. He, X.W. Hu, S.L. Chen, H. Hu, M. Hanif, H.Q. Hou, Needle-like polyaniline nanowires on graphite nanofibers: hierarchical micro/nano-architecture for high performance supercapacitors, J. Mater. Chem. 22 (11) (2012) 5114e5120. [124] C.Z. Meng, C.H. Liu, L.Z. Chen, C.H. Hu, S.S. Fan, Highly flexible and all-solid-state paperlike polymer supercapacitors, Nano Lett. 10 (10) (2010) 4025e4031. [125] H.L. Wang, Q.L. Hao, X.J. Yang, L.D. Lu, X. Wang, Effect of graphene oxide on the properties of its composite with polyaniline, ACS Appl. Mater. Interfaces 2 (3) (2010) 821e828. [126] P. Yu, X. Zhao, Z. Huang, Free-standing three-dimensional graphene and polyaniline nanowire arrays hybrid foams for high-performance flexible and lightweight supercapacitors, J. Mater. Chem. A 2 (35) (2014) 14413e14420. [127] C.R. Zhu, X.H. Xia, J.L. Liu, Z.N. Fan, D.L. Chao, H. Zhang, H.J. Fan, TiO2 [email protected] nanoflake coreebranch arrays for lithium-ion battery anode, Nano Energy 4 (2014) 105e112. [128] W. Ye, J. Zhu, X.J. Liao, S.H. Jiang, Y.H. Li, H. Fang, H.Q. Hong, Hierarchical threedimensional micro/nano-architecture of polyaniline nanowires wrapped-on polyimide nanofibers for high performance lithium-ion battery separators, J. Power Sourc. 299 (2015) 417e424. [129] S.Y. Wang, M. Li, M.Y. Gan, S.N. Fu, W.Q. Dai, T. Zhou, X.W. Sun, H.H. Wang, H.N. Wang, Free-standing 3D graphene/polyaniline composite film electrodes for high-performance supercapacitors, J. Power Sourc. 299 (2015) 347e355. [130] J. Tang, Y.K. Yamacuchi, Carbon materials: MOF morphologies in control, Nat. Chem. 8 (7) (2016) 638e639. [131] P.V. Witte, P.J. Dijkstra, F.J. Jin, Phase separation processes in polymer solutions in relation to membrane formation, J. Membr. Sci. 117 (1) (1996) 1e31. [132] B.S. Singu, P. Srinivasan, K.R. Yoon, Emulsion polymerization method for polyaniline-multiwalled carbon nanotube nanocomposites as supercapacitor materials, J. Solid State Electrochem. 20 (12) (2016) 3447e3457. [133] K.W. Shen, F. Ran, Y.T. Tan, X.Q. Niu, H.L. Fan, K. Yan, L.B. Kong, L. Kang, Toward interconnected hierarchical porous structure via chemical depositing organic nanopolyaniline on inorganic carbon scaffold for supercapacitor, Synth. Met. 199 (2015) 205e213.

205

206

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

[134] Z.C. Zhao, Y.B. Xie, Enhanced electrochemical performance of carbon quantum dotspolyaniline hybrid, J. Power Sourc. 337 (2017) 54e64. [135] P. Yu, Z. Zhang, L. Zheng, F. Teng, L. Hu, X. Fang, A novel sustainable flour derived hierarchical nitrogen-doped porous carbon/polyaniline electrode for advanced asymmetric supercapacitors, Adv. Energy Mater. 6 (20) (2016). [136] A.J. Liu, L.H. Bac, K. Ji-Soon, K. Byoung-Kee, K. Jin-Chun, Synthesis and characterization of conducting polyaniline-copper composites, J. Nanosci. Nanotechnol. 13 (11) (2013) 7728e7733. [137] A.J. Liu, L.H. Bac, K. Jin-Chun, L.Z. Liu, Preparation and characterization of polyaniline-copper composites by electrical explosion of wire, J. Nanosci. Nanotechnol. 12 (7) (2012) 6031e6035. [138] N.M. Ivanova, E.A. Soboleva, Y.A. Visurkhanova, I.V. Kirilyus, Electrocatalytic activity of polyaniline-copper composites in electrohydrogenation of p-nitroaniline, Russ. J. Electrochem. 51 (2) (2015) 166e173. [139] A. Uygun, E. Aslan, Comparative study of conducting polyaniline/copper and polyaniline/nickel composites in the presence of surfactants, Polym. Int. 59 (8) (2010) 1162e1167. [140] A.H. Navarchian, M. Joulazadeh, F. Karimi, Investigation of corrosion protection performance of epoxy coatings modified by polyaniline/clay nanocomposites on steel surfaces, Prog. Org. Coat. 77 (2) (2014) 347e353. [141] Q.Y. Soundararajah, B.S.B. Karunaratne, R.M.G. Rajapakse, Montmorillonite polyaniline nanocomposites: preparation, characterization and investigation of mechanical properties, Mater. Chem. Phys. 113 (2) (2009) 850e855. [142] K.C. Chang, G.W. Jang, C.W. Peng, C.Y. Lin, J.C. Shieh, J.M. Yeh, J.C. Yang, W.T. Li, Show more comparatively electrochemical studies at different operational temperatures for the effect of nanoclay platelets on the anticorrosion efficiency of DBSAdoped polyaniline/Naþ-MMT clay nanocomposite coatings. Electrochim. Acta 52 (16) (2007) 5191e5200. [143] G.M.D. Nascimento, V.R.L. Constantino, R. Landers, M.L.A. Temperini, Aniline polymerization into montmorillonite clay: a spectroscopic investigation of the intercalated conducting polymer, Macromolecules 37 (25) (2004) 9373e9385. [144] K.C. Chang, M.C. Lai, C.W. Peng, Y.T. Chen, J.M. Yeh, C.L. Lin, J.C. Yang, Comparative studies on the corrosion protection effect of DBSA-doped polyaniline prepared from in situ emulsion polymerization in the presence of hydrophilic Naþ-MMT and organophilic organo-MMT clay platelets, Electrochim. Acta 51 (26) (2006) 5645e5653. [145] E. Akbarinezhad, M. Ebrahimi, F. Sharif, M.M. Attar, H.R. Faridi, Synthesis and evaluating corrosion protection effects of emeraldine base PAni/clay nanocomposite as a barrier pigment in zinc-rich ethyl silicate primer, Prog. Org. Coat. 70 (1) (2011) 39e44. [146] J.M. Yeh, S.J. Liou, C.Y. Lai, P.C. Wu, Enhancement of corrosion protection effect in polyaniline via the formation of polyaniline-clay nanocomposite materials, Chem. Mater. 13 (3) (2001) 1131e1136. [147] A. Olad, A. Rashidzadeh, Preparation and anticorrosive properties of PANI/Na-MMT and PANI/O-MMT nanocomposites, Prog. Org. Coat. 62 (3) (2008) 293e298. [148] H.V. Hoang, Electrochemical Synthesis of Novel Polyaniline-montmorillonite Nanocomposites and Corrosion Protection of Steel, Chemnitz University of Technology, 2006.

References

[149] T.H. Kuo, Y.L. Chen, C.L. Chen, J.H. Chang, I.L. Lin, S.H. Chen, Y.C. Chang, J.M. Yeh, Preparation and anticorrosion property of polyaniliane/organo-clay nanocomposite coatings: comparative studies of different intercalating agent, J. Polym. Eng. 30 (5e7) (2010) 309e328. [150] J. Wang, Synthesis and Properties of Polyimide/organo Clay and Polyimide/ polyaniline-modified Clay Nanocomposites, University of Cincinnati, 2010. [151] J.M. Yeh, H.Y. Huang, C.L. Chen, W.F. Su, Y.H. Yu, Siloxane-modified epoxy resine clay nanocomposite coatings with advanced anticorrosive properties prepared by a solution dispersion approach, Surf. Coat. Technol. 200 (8) (2006) 2753e2763. [152] C.F. Dai, P.R. Li, J.M. Yeh, Comparative studies for the effect of intercalating agent on the physical properties of epoxy resin-clay based nanocomposite materials, Eur. Polym. J. 44 (8) (2008) 2439e2447. [153] M. Nematollahi, M. Heidarian, M. Peikari, S.M. Kassiriha, N. Arianpouya, M. Esmaeilpour, Comparison between the effect of nanoglass flake and montmorillonite organoclay on corrosion performance of epoxy coating, Corros. Sci. 52 (5) (2010) 1809e1817. [154] M.G. Hosseini, M. Jafari, R. Najjar, Effect of polyanilineemontmorillonite nanocomposite powders addition on corrosion performance of epoxy coatings on Al 5000, Surf. Coat. Technol. 206 (2) (2011) 280e286. [155] M.R. Bagherzadeh, T. Mousavinejad, Preparation and investigation of anticorrosion properties of the water-based epoxy-clay nanocoating modified by Naþ-MMT and Cloisite 30B, Prog. Org. Coat. 74 (3) (2012) 589e595. [156] A.D. Barros, M. Ferreira, C.J.L. Constantino, M. Ferreira, Nanocomposites based on LbL films of polyaniline and sodium montmorillonite clay, Synth. Met. 197 (2014) 119e125. [157] H.B. Li, L.D. Zou, L.K. Pan, Z. Sun, Novel graphene-like electrodes for capacitive deionization, Environ. Sci. Technol. 44 (22) (2010) 8692e8697. [158] N. Choudhary, W. Choi, Graphene synthesis and applications, CRC Press 36 (4) (2015) 620e626. [159] A. Peigney, C. Laurent, E. Flahaut, R.R. Bacsa, A. Rousset, Specific surface area of carbon nanotubes and bundles of carbon nanotubes, Carbon 39 (4) (2001) 507e514. [160] Z. Wang, B. Dou, L. Zheng, G. Zhang, Z. Liu, Effective desalination by capacitive deionization with functional graphene nanocomposite as novel electrode material, Desalination 299 (2012) 96e102. [161] L. Lai, H. Yang, L. Wang, B.K. Teh, J. Zhong, Preparation of supercapacitor electrodes through selection of graphene surface functionalities, ACS Nano. 6 (7) (2012) 5941e5951. [162] C. Yan, Y.W. Kanaththage, R. Short, C.T. Gibson, L. Zou, Graphene/Polyaniline nanocomposite as electrode material for membrane capacitive deionization, Desalination 344 (2014) 274e279. [163] S.B. Lee, S.M. Lee, N.I. Park, S. Lee, D.W. Chung, Preparation and characterization of conducting polymer nanocomposite with partially reduced graphene oxide, Synth. Met. 201 (2015) 61e66. [164] Y.C. Lin, F.H. Hsu, T.M. Wu, Enhanced conductivity and thermal stability of conductive polyaniline/graphene composite synthesized by in situ chemical oxidation polymerization with sodium dodecyl sulfate, Synth. Met. 184 (2013) 29e34. [165] S.Y. Davydov, To the theoretical analysis of the work function changes of platinum group metals adsorbed on (110) W, Appl. Surf. Sci. 376 (2016) 261e268.

207

208

CHAPTER 7 Polyaniline-Based Composites and Nanocomposites

[166] T. Nishino, K. Takano, K. Nakamae, Elastic modulus of the crystalline regions of cellulose polymorphs, J. Polym. Sci. Part B Polym. Phys. 33 (11) (1995) 647e1651. [167] D.Y. Liu, X.W. Yuan, D. Bhattacharyya, Characterisation of solution cast cellulose nanofibreereinforced poly (lactic acid), Express Polym. Lett. 4 (1) (2010) 26e31. [168] N. Lin, J. Yu, P.R. Chang, Poly (butylene succinate)-based biocomposites filled with polysaccharide nanocrystals: structure and properties, Polym. Compos. 32 (3) (2011) 472e482. [169] U. Geyer, T. Heinze, A. Stein, Formation, derivatization and applications of bacterial cellulose, Int. J. Biol. Macromol. 16 (6) (1994) 343e347. [170] Z. Mo, Z. Zhao, H. Chen, Heterogeneous preparation of celluloseepolyaniline conductive composites with cellulose activated by acids and its electrical properties, Carbohydr. Polym. 75 (4) (2009) 660e664. [171] G. Nystro¨m, A. Razaq, M. Strømme, Ultrafast all-polymer paper-based batteries, Nano Lett. 9 (10) (2009) 3635e3639. [172] M. Strømme, A. Mihranyan, What to do with all these algae, Mater. Lett. 57 (3) (2002) 569e572. [173] K. Gelin, A. Bodin, P. Gatenholm, Characterization of water in bacterial cellulose using dielectric spectroscopy and electron microscopy, Polymer 48 (26) (2007) 7623e7631.  ´ , G.R. Davies, S.J. Eichhorn, Elastic modulus and stress-transfer properties [174] A. Sturcova of tunicate cellulose whiskers, Biomacromolecules 6 (2) (2005) 1055e1061. [175] B.M. Cherian, L.A. Pothan, T. Nguyen-Chung, G. Mennig, M. Kottaisamy, A novel method for the synthesis of cellulose nanofibril whiskers from banana fibers and characterization, J. Agri. Food Chem. 56 (14) (2008) 5617e5627. [176] A. Alemdar, M. Sain, Isolation and characterization of nanofibers from agricultural residueseWheat straw and soy hulls, Bioresour. Technol. 99 (6) (2008) 1664e1671. [177] L. Nyholm, G. Nystro¨m, A. Mihranyan, Toward flexible polymer and paper-based energy storage devices, Adv. Mater. 23 (33) (2011) 3751e3769. [178] M.L. Auad, T. Richardson, W.J. Orts, Polyaniline-modified cellulose nanofibrils as reinforcement of a smart polyurethane, Polym. Int. 60 (5) (2011) 743e750. [179] D.Y. Liu, G.X. Sui, D. Bhattacharyya, Synthesis and characterisation of nanocellulosebased polyaniline conducting films, Compos. Sci. Technol. 99 (2014) 31e36. [180] E. Tkalya, M. Ghislandi, W. Thielemans, Cellulose nanowhiskers templating in conductive polymer nanocomposites reduces electrical percolation threshold 5-fold, ACS Macro Lett. 2 (2) (2013) 157e163. [181] M.J. Silva, A.O. Sanches, E.S. Medeiros, L.H.C. Mattoso, C.M. McMahan, J.A. Malmonge, Nanocomposites of natural rubber and polyaniline-modified cellulose nanofibrils, J. Therm. Anal. Calorim. 117 (1) (2014) 387e392.