Electrically conductive nanocomposites of polyaniline with poly(vinyl alcohol) and methylcellulose

Electrically conductive nanocomposites of HCl‐doped polyaniline (PANI–HCl) nanocolloid particles with water‐soluble and film‐forming polymers such as poly(vinyl alcohol) (PVA) and methylcellulose (MC) were prepared by the redispersion of preformed MC‐coated submicrometric PANI–HCl particles in PVA and MC solutions under sonication for 1 h and the casting of the films from the dispersions followed by drying. The submicrometric polyaniline (PANI) particles were prepared by the oxidative dispersion polymerization of aniline in an acidic (1.25M HCl) aqueous ethanol (30 : 70) medium with MC as a steric stabilizer. The particles contained 4.7 wt % MC and had a conductivity of 7.4 S/cm. They had an oblong shape of 203 nm (length) and 137 nm (breadth). Sonication broke the oblong‐shaped particles to sizes of ～10 nm in the PVA matrix and ～60 nm in the MC matrix. The electrical conductivity of these films was measured, and the percolation threshold was determined. The composites had the characteristics of a low percolation threshold at a volume fraction of PANI of 2.5 × 10^?2 in the PVA matrix and at a volume fraction of 3.7 × 10^?2 in the MC matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Formation mechanism of polyaniline self‐assembled needles and urchin‐like structures assisted by magnesium oxide

The polyaniline (PANI) morphological structure is strongly correlated with the preparation procedure, yielding diverse geometries such as nano‐tubes, belts, rods, fibres and particles. In this study, the synthesis of a novel PANI morphology of consisting of hollow needles and urchin‐like structures is presented and its formation mechanism is explained. The polymer was synthesized by chemical oxidative polymerization of aniline in the presence of magnesium oxide as a structural directing agent. The morphological study of the urchin‐like PANI was conducted using scanning electron microscopy and in situ monitoring of needle growth was done using optical microscopy. The structure and functional groups of these novel structures were characterized using Fourier transform infrared spectroscopy. Additionally, the formation mechanism is modelled based on the multi‐layer theory where a core–shell structure exists between the polymer (shell) and the magnesium oxide particles (core). © 2014 Society of Chemical Industry     

Synthesis and characterization of poly(methyl methacrylate–butyl acrylate–acrylic acid)/polyaniline core–shell nanoparticles in miniemulsion media

Conductive polymer particles, polyaniline (PANI)‐coated poly(methyl methacrylate–butyl acrylate–acrylic acid) [P(MMA–BA–AA)] nanoparticles, were prepared. The P(MMA–BA–AA)/PANI core–shell complex particles were synthesized with a two‐step miniemulsion polymerization method with P(MMA–BA–AA) as the core and PANI as the shell. The first step was to prepare the P(MMA–BA–AA) latex particles as the core via miniemulsion polymerization and then to prepare the P(MMA–BA–AA)/PANI core–shell particles. The aniline monomer was added to the mixture of water and core nanoparticles. The aniline monomer could be attracted near the outer surface of the core particles. The polymerization of aniline was started under the action of ammonium persulfate (APS). The final product was the desired core–shell nanoparticles. The morphology of the P(MMA–BA–AA) and P(MMA–BA–AA)/PANI particles was characterized with transmission electron microscopy. The core–shell structure of the P(MMA–BA–AA)/PANI composites was further determined by Fourier transform spectroscopy and ultraviolet–visible measurements. The conductive flakes made from the core–shell latexes were prepared, and the electrical conductivities of the flakes were studied. The highest conductivity of the P(MMA–BA–AA)/PANI pellets was 2.05 S/cm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrically conductive composites based on epoxy resin containing polyaniline–DBSA‐ and polyaniline–DBSA‐coated glass fibers

Four kinds of polyaniline (PANI)‐coated glass fibers (GF–PANI) combined with bulk PANI particles were synthesized. GF–PANI fillers containing different PANI contents were incorporated into an epoxy–anhydride system. The best conductivity behavior of the epoxy/GF–PANI composites was obtained with a GF–PANI filler containing 80% PANI. Such a composite shows the lowest percolation threshold at about 20% GF–PANI or 16% PANI (glass fiber‐free basis). The PANI‐coated glass fibers act as conductive bridges, interconnecting PANI particles in the epoxy matrix, thus contributing to the improvement of the conductivity of the composite and the lower percolation threshold, compared with that of a epoxy/PANI–powder composite. Particularly, the presence of glass fibers significantly improves the mechanical properties, for example, the modulus and strength of the conductive epoxy composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1329–1334, 2004     

Synthesis and characterization of poly(butyl acrylate–methyl methacrylate)/polyaniline core–shell latexes

Poly(butyl acrylate–methyl methacrylate) [P(BA–MMA]/polyaniline (PANI) core–shell complex particles were synthesized with a two‐step emulsion polymerization method with P(BA–MMA) as the core and PANI as the shell. The first step was to prepare P(BA–MMA) latex particles as the core via soapless emulsion polymerization. The second step was to prepare P(BA–MMA)/PANI core–shell particles. Sodium dodecyl sulfate was fed into the P(BA–MMA) emulsion as a surfactant, and this was followed by the addition of the aniline monomer. A bilayer structure of the surfactant over the surfaces of the core particles was desired so that the aniline monomer could be attracted near the outer surface of the core particles. In some cases, dodecyl benzene sulfonic acid was added after 2 h when the polymerization of aniline was started. The final product was the desired core–shell particles. The morphology of P(BA–MMA) and P(BA–MMA)/PANI particles was observed with transmission electron microscopy. The thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry. Furthermore, conductive films made from the core–shell latexes were prepared, and the electrical conductivities of the films were studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 823–830, 2007     

Synthesis by in situ chemical oxidative polymerization and characterization of polyaniline/iron oxide nanoparticle composite

Polyaniline (PANI) is a well‐studied material and is the pre‐eminent electrically conducting organic polymer with the potential for a variety of applications such as in batteries, microelectronics displays, antistatic coatings, electromagnetic shielding materials, sensors and actuators. Its good environmental as well as thermal stability and electrical conductivity tunable by appropriate doping make PANI an ideal active material for several applications. In this paper, we report the synthesis of water‐dispersible colloidal PANI/iron oxide composite nanoparticles using an in situ chemical oxidation polymerization method in a micellar medium of sodium dodecylsulfate, where the cores (iron oxide) are embedded in a PANI matrix layer. Transmission electron micrographs showed evidence of the formation of an iron oxide core/PANI shell composite with a thin layer of PANI over the iron oxide cores. The results of thermogravimetric, Fourier transform infrared and UV‐visible analysis indicated that the iron oxide nanoparticles could improve the composite thermal stability possibly due to the interaction between iron oxide particles and PANI backbone. We believe that the synthetic route described can also be adapted for the assembly of hierarchical structures of other metal oxides or hydroxides onto various cores. Copyright © 2010 Society of Chemical Industry     

Sol–gel process of alkoxysilane in emulsifier‐involved aqueous emulsions: A one‐pot synthetic route to emulsions of core‐shell composite particles and their applications

In this work, a one‐pot route to prepare emulsions of silica/polymer core‐shell composite particles was developed through the direct sol–gel processing of alkoxysilane on the surface of newly synthesized template polymer particles in emulsifier‐involved aqueous emulsions. It included two continuous steps: first, the polymer emulsions were synthesized through emulsion polymerization, and second, the template particles in the emulsions were directly coated with silica via sol–gel reaction of precursors without adding ethanol or removing emulsifiers. The size and morphology of the composite particles were characterized, and the results showed that the silica/polymer composite particles with core‐shell structure could be prepared only on the basis of cationic template emulsions, and the in situ‐coating reaction of sol–gel precursors carried on easier with the increasing of the positive charge density on the surface of template particles. The films formed from the composite emulsions were found to have superior optical and flame‐retardant properties compared to polymer films, owing to the core‐shell composite microstructure of the particles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of polyaniline/polyacrylate composites and their application for electromagnetic interference shielding

Polyaniline (PANI) deposited polyacrylate (PA) powders were prepared by chemical polymerization of aniline in hydrochloric acid with dispersed PA powders. The powders, after dedoped with ammonia water, were re‐doped with camphorsulfonic acid (CSA) to render them conductive, and conductive PANI/polyacrylate composite coatings (PANI/PA) were prepared by bead milling of these CSA‐doped PANI (PANI–CSA) deposited polyacrylate powders (PANI–CSA/PA). It was found that aniline was polymerized preferentially at the surfaces of the powders and PANI deposited powders were obtained as indicated by the scanning electronic microscopy images. The amount of deposited PANI increased with the aniline/polyacrylate weight ratio in feed, and no isolated PANI particles was found. UV–Vis and Fourier transformed infrared spectra indicated that the PANI layer was physically adhered to the PA powders, and not chemically. Conductivities of the PANI–CSA/PA powders and the PANI/PA coatings increased with the amounts of PANI–CSA and a percolation threshold of 0.2 and 0.3 was demonstrated, respectively. Electromagnetic interference shielding measurements showed that the shielding effectiveness of the PANI/PA coatings increased with PANI–CSA loadings, and shielding effectiveness as high as 60 dB can be achieved with the coatings. POLYM. COMPOS., 27:627–632, 2006. © 2006 Society of Plastics Engineers     

Polyaniline − carbon nanohorn composites as thermoelectric materials

Thermoelectric materials can convert heat into electricity when a temperature gradient is present. The investigation of conductive polymers such as polyaniline (PANI ) and poly(3,4‐ethylenedioxythiophene) as active materials for thermoelectric generators in the room temperature range is gaining interest because of several key advantages offered by these materials. The relative ease of solution processing, their mechanical stability and flexibility together with low density and low thermal conductivity make conductive polymers suitable for integration in a thermoelectric generator. Polymers offer remarkably low thermal conductivity values but modest Seebeck coefficient and electrical conductivity. In this work, polymer/inorganic nanocomposites of PANI with carbon particles such as single wall carbon nanohorns (SWCNHs ) were prepared via solution mixing of the precursors in order to increase the electrical conductivity by means of polymer matrix/nanohorn electronic junctions. The electrical conductivity and Seebeck coefficient were estimated on PANI /SWCNH films and pressed pellets and through‐plane thermal conductivity was determined on films. The thermal stability of PANI /SWCNH composites was evaluated by means of TGA /DSC coupled with residual gas analysis. It was found that a proper concentration of SWCNHs in PANI ?(+/?)‐camphor‐10‐sulfonic acid (CSA) film was effective in increasing the electrical conductivity without decreasing the Seebeck coefficient. © 2017 Society of Chemical Industry     

Synthesis of polypyrrole-coated core/shell nanoparticles

The synthesis, physical characterization and scale-up of conductive, re-dispersible core/shell nanoparticles containing polypyrrole (PPy) in the shell are described. The compressed powders/films show a DC conductivity which is considerably higher than that of commercial standard products based on PEDOT/PSS ('AL 4083' from H.C. Starck). The particles have excellent film-forming properties since thin films (50-100 nm) made by spin-coating from aqueous dispersions of the particles have an AFM film roughness of <15 nm even before annealing. The materials were tested as hole injection/smoothening layers in fluorescent OLED devices, and are in a comparable range to PEDOT/PSS-based materials in respect to performance (film forming, luminance, efficiency, and lifetime).     

Synthesis and characterization of high molecular weight polyaniline for organic electronic applications

High molecular weight polyaniline (PANI) was synthesized by a combined procedure incorporating various synthesis methods. Temperature and open circuit potential of the reaction mixture were collected to monitor the reaction progress. The polymer is characterized by various techniques including gel permeation chromatography, dynamic light scattering, infrared spectroscopy, solid‐state nuclear magnetic resonance, and differential scanning calorimetry for elucidating the molecular architecture obtained by this method. As‐synthesized PANI was found to possess high molecular weight, reduced branching, reduced cross‐linking, and to predominantly consist of linear polymer chains. This polymer was also found to be more stable in solution form. J–V characteristics of as‐synthesized PANI films indicate a high current density which is due to increased free pathways and less traps for the charge transport to occur in PANI films. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Synthesis and characterization of poly(fluorinated acrylate)/silica hybrid nanocomposites

The nanocomposite particles (NPs) with inorganic silica as core and fluorinated polymer shell have been in situ synthesized via emulsion polymerization. The chemical composition and core‐shell structure were characterized by Fourier‐transform infrared spectrometry and transmission electron microscopy. The results showed that silica nanoparticles were encapsulated in latex particles, with single‐ and multicore morphologies coexisting. Thermal gravimetric analysis also suggested the successful encapsulation of silica into NPs with enhanced thermal stability. The surface properties of the latex films produced from the core‐shell particles were also investigated by contact angle method and water absorption measurement. Both fluorinated polymer and silica contributed to less water absorption ratio and lower surface‐free energy, which was composed of larger polar component and smaller disperse component, just reversed as usual. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyaniline/silver nanocomposites synthesized via UV–Vis‐assisted aniline polymerization with a reversed micellar microemulsion system

Polyaniline (PANI)/silver (Ag) nanocomposites were successfully synthesized within a sodium dodecyl sulfate reverse micro‐emulsion system and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, ultraviolet spectrometry, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and electrochemical methods. The results show that the core‐shell nanoparticles of less than 100 nm may be synthesized with PANI as shell formed around a core of nanoparticle. PANI/Ag nanocomposite prepared by this method has better thermal stability, higher conductivity, and electrochemical performance. The maximum conductivity (95.5 S/cm) was obtained when W₀ (water‐oil ratio) is 22. Cyclic voltammograms results show that PANI/Ag prepared by this method has a high response current and large capacitance. Polarization results show that E_corr (174.1 mV) and I_corr (50.6 μA/cm²) are better than the results for PANI and for PANI/Ag prepared by micro‐emulsion method. PANI/Ag nanocomposites prepared by the current method have potential applications in electrode materials, capacitors, conductive adhesives, and anticorrosion materials. POLYM. COMPOS. 37:1064–1071, 2016. © 2014 Society of Plastics Engineers     

Epoxy‐based adhesives filled with flakes ag‐coated copper as conductive fillers

The flake core–shell Cu‐Ag powders are prepared and characterized. Isotropic conductive adhesives (ICAs) filled with flake silver‐coated copper was prepared by using epoxide resin as matrix and tetraethylenepentamine as curing agent. The flake silver‐coated copper was characterized by scanning electron microscopy, X‐ray diffraction, energy dispersive X‐ray spectroscopy, and TG‐DTA. The results show Ag content in the surface of coated copper is up to 96.32%. Oxidation resistance of flake Cu‐Ag powders with high surface Ag content is improved greatly investigated by TG‐DTA. And bulk resistivity and shear strength of ICAs are measured. It was found that the percolation threshold of ICAs filled with flake Cu‐Ag powders is as low as 40 wt%. The ICAs have good overall performances. And the main influence factor on electric resistivity was analyzed. POLYM. COMPOS., 38:846–851, 2017. © 2015 Society of Plastics Engineers     

Polyaniline matrix containing nickel ferromagnet

Metallic nickel (Ni) was successfully dispersed onto a polyaniline (PANI) matrix by a simple one‐step electrochemical method. Ni particles as deposited onto the polymer seemed to be much smaller compared to those deposited onto bare Pt. The size of the Ni deposits was found to be influenced by the electrolytic bath composition and potential sweep rate. The PANI matrix thus dispersed with Ni particles exhibited ferromagnetic behavior and a lower electrical conductance. The decrease in conductivity may be attributed to the partial blockage of the conductive path by the Ni particles thus embedded in the polymer matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 321–327, 2006     

Incorporation of 4‐aminobenzene functionalized multi‐walled carbon nanotubes in polyaniline for application in formic acid electrooxidation

Incorporation of carbon nanotubes (CNTs) in conducting polymer can lead to new composites with enhanced electrical and mechanical properties. However, the development of such composites has been hampered by the inability to disperse CNTs in polymer matrix due to the lack of chemical compatibility between polymers and CNTs. Covalent sidewall functionalization of carbon nanotube provides a feasible route to incorporate carbon nanotube in polymer. In this work, 4‐aminobenzene groups were grafted onto the surface of multi‐walled carbon nanotube (MWNT) via C? C covalent bond. Polyaniline (PANI)/MWNT composites were fabricated by electrochemical polymerization of aniline containing well‐dissolved functionalized MWNTs. The obtained composites can be used as catalyst supports for electrooxidation of formic acid. Cyclic voltammogram results show that platinum particles deposited in PANI/MWNT composite films exhibit higher electrocatalytic activity and better long‐term stability towards formic acid oxidation than that deposited in pure PANI films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of waterborne polyurethane/polyaniline codoped with dodecyl benzene sulfonic acid and hydrochloric acid blends

A conductive poly(aniline codoped with dodecyl benzene sulfonic acid and hydrochloric acid) [PANI‐D/H, yield: 32.2%, intrinsic viscosity ([η]): 1.39 dL/g, electrical conductivity: 7.3 S/cm] was synthesized by chemical oxidative polymerization from aniline‐dodecylbenzene sulfonic acid salt (A‐DS)/aniline‐hydrochloric acid salt (A‐HS) (6/4M ratio) in an aqueous system. Waterborne polyurethane (WBPU) dispersion obtained from isophorone diisocyanate/poly(tetramethylene oxide)glycol/dimethylol propionic acid/ethylene diamine/triethylene amine/water was used as a matrix polymer. The blend films of WBPU/PANI‐D/H with various weight ratios (99.9/0.1–25/75) were prepared by solution blending/casting. Effect of PANI‐D/H content on the mechanical property, dynamic mechanical property, hardness, electrical conductivity, and antistaticity of WBPU/PANI‐D/H blend films was investigated. The dynamic storage modulus and initial tensile modulus increased with increasing PANI‐D/H content up to 1 wt %, and then it was significantly decreased about the content. With increasing PANI‐D/H content, the glass transition temperature of soft segment (T_gs) and hard segment (T_gh) of WBPU/PANI‐D/H blend films were shifted a bit to lower the temperature. The tensile strength and hardness of WBPU/PANI‐D/H blend films increased a little with increasing PANI‐D/H content up to 0.5 wt %, and then it was dramatically decreased over the content. The elongation at break of WBPU/PANI‐D/H decreased with an increase in PANI‐D/H content. From these results, it was concluded that 0.5–1 wt % of PANI‐D/H was the critical concentration to reinforce those various properties of WBPU/PANI‐D/H blend films prepared in this study. The electrical conductivity of WBPU/ultrasonic treated PANI‐D/H (particle size: 0.7 μm) blend films prepared here increased from 4.0 × 10^?7 to 0.33 S/cm with increasing PANI‐D/H content from 0.1 to 75 wt %. The antistatic half‐life time (τ_1/2) of pure WBPU film was about 110 s. However, those of WBPU/ultrasonic treated PANI‐D/H blend films (τ_1/2: 8.2–0.1 s, and almost 0 s) were found to decrease exponentially with increasing PANI‐D/H content (0.1–9 wt %, and above 9 wt %). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 700–710, 2004     

Preparation of high‐k composites with low dielectric loss based on the double‐layer coaxial structure of inorganic/polymer

This study presents a novel and simple modification of cladding multiwalled carbon nanotubes (MWCNTs) using organic polymer and inorganic nanoparticles to synthesize a product, which has a double‐cladding coaxial structure and can be applied as filler in the dielectric field. The first layer of MWCNTs was coated with polyaniline (PANI) through the oxidation–reduction reaction mechanism using Ce(NH₄)₂(NO₃)₆ as oxidizing agent and metal precursor of cerium oxide. Cerium ions on the second cladding layer of MWCNTs were directly deposited from the solution to the surface of the PANI layer forming the double‐cladding hybrid (CeO₂/PANI@MWCNTs). The external inorganic layer provides an insulating shell, which can prevent the contact between the conductive particles and hinder the migration of electrons between the MWCNTs. The intermediate layer of PANI provides the bonding between CeO₂ and the conductive core of MWCNTs, which also shows lower conductivity than carbon nanotubes. The CeO₂/PANI@MWCNTs were compounded with epoxy (EP) resin and formed a dielectric material with the advantage of reducing dielectric loss while ensuring high dielectric constant. The dielectric constant of the coated MWCNTs/EP composites was 194.90 at 10³ Hz with the content of fillers reaching 30 wt %, which is 28 times that of the pure EP. Accordingly, the dielectric loss of 30 wt % coated MWCNTs/EP composites was only 0.09 at 10³ Hz, which is only 2.25 times that of the pure EP. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46299.     

Carbon nanotubes/polyaniline nanocomposite coatings: Preparation,rheological behavior,and their application in paper surface treatment

Conventional cellulosic paper, rendered electro‐conductive, may hold considerable promise for diversified applications in such areas as electro‐magnetic interference shielding and energy storage. Here, an electro‐conductive cellulosic paper was prepared by surface application of multi‐walled carbon nanotubes (MWCNTs)/polyaniline (PANI) nanocomposites onto a conventional base paper. MWCNTs/PANI nanocomposites were prepared by in situ polymerization of aniline with different contents of MWCNTs and used as electro‐conductive filler for the fabrication of electro‐conductive surface‐coated paper. The achieved MWCNTs/PANI nanocomposites exhibited a core‐shell structure, as evidenced by TEM. Effects of feeding ratios of MWCNTs on the rheological behavior of nanocomposite coatings, as well as the mechanical properties and electrical conductivity of surface‐coated paper were studied. Results revealed that the rheological behavior of the nanocomposite coatings showed strong dependence on the MWCNTs content. Moreover, both the electro‐conductivity and mechanical properties of surface‐coated paper were improved as a function of surface application of MWCNTs/PANI nanocomposites, particularly, in presence of an optimum content of MWCNTs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46329.     

Narrow‐disperse or monodisperse crosslinked and functional core–shell polymer particles prepared by two‐stage precipitation polymerization

Narrow‐disperse and monodisperse cross‐linked core–shell polymer particles containing different functional groups, such as esters, hydroxyls, chloromethyls, carboxylic acids, amides, cyanos, and glycidyls, in the shell layers in the micrometer size range were prepared by a two‐stage precipitation polymerization in the absence of any stabilizer. Commercial divinylbenzene (DVB), containing 80% DVB, was precipitation polymerized in acetonitrile without any stabilizer as the first‐stage polymerization and was used as the core. Several functional monomers, including methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2‐hydroxyethyl methacrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, t‐butyl acrylate, i‐octyl acrylate, acrylic acid, acrylamide, acrylonitrile, styrene, and p‐chloromethyl styrene, were incorporated into the shells during the second‐stage polymerization. The resulting core–shell polymer particles were characterized with scanning electron microscopy and Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1776–1784, 2006