Fabrication and properties of solution‐cast polyaniline/carboxymethylchitin blend films

Blend films consisting of polyaniline in emeraldine base form (PANI EB) dispersed in partially cross‐linked carboxymethylchitin (CM‐chitin) were prepared by solution casting, and characterized for their physical, thermal, and electrical properties. Homogeneous and mechanically robust blend films were obtained having PANI EB contents up to 50 wt % in the CM‐chitin matrix. FTIR spectra confirm intimate mixing of the two blend components. The thermal stability of the blend films increased with increase of PANI EB content, suggesting the formation of an intermolecular interaction, such as hydrogen bonding, between PANI EB and CM‐chitin chains. The addition of PANI EB into the pure CM‐chitin film resulted in a decrease in electrical conductivity of the films owing to disruption of ionic conduction of the CM‐chitin structure. After doping the blend films by immersion in HCl solution, the electrical conductivity of the HCl‐doped films increased with increase of the PANI EB content to a maximum value of the order of 10^?3 S/cm at 50 wt % PANI EB content. The electrical conductivity of the blend films was also dependent on the HCl concentration as well as on the type of acid dopant. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyaniline nanotubes: conditions of formation

The courses of aniline oxidation with ammonium peroxydisulfate in aqueous solutions of strong (sulfuric) and in weak (acetic) acids, followed by temperature and acidity changes, are different. In solutions of sulfuric acid, granular polyaniline (PANI) was produced; in solutions of acetic acid, PANI nanotubes were obtained. The external diameter of the nanotubes was 100–300 nm, the internal cavity 20–100 nm, and the length extended to several micrometres. The morphology of PANI, granular or tubular, depends on the acidity conditions during the reaction rather than on the chemical nature of the acid. PANI nanotubes were also produced when aniline was oxidized in the absence of any acid. The bulk conductivity of PANI prepared in solutions of acetic acid was 0.08–0.27 S cm^?1, depending on the acid concentration. Protonated PANI prepared in sulfuric and acetic acids were deprotonated with ammonium hydroxide to obtain PANI bases and the ammonium salt of the protonating acid. FTIR spectroscopy showed the differences in the molecular structure of the PANI bases. Irrespective of whether the polymerization was performed in solutions of sulfuric or acetic acid, PANI had hydrogen sulfate counter‐ions only. The PANI morphology is thus not controlled by the nature of counter‐ions. The acidity of the reaction medium determines the protonation of monomer, oligomer and polymer species. The chemistry of aniline oxidation is likely to be affected especially by the protonation of an intermediate in the pernigraniline form. It is proposed that, in the course of aniline oxidation, pH‐dependent self‐assembly of aniline oligomers predetermines the final PANI morphology. Copyright © 2005 Society of Chemical Industry     

Novel conducting polyaniline blends with cyanoresin

Novel conducting polyaniline (PANI)/cyanoresin (Cyan) blends were prepared by the addition of Cyan/dimethylformamide solutions to aniline monomer/dopant solutions and the in situ chemical oxidative polymerization of aniline with ammonium persulfate as an oxidant in aqueous p‐toluene sulfonic acid solutions. The PANI/Cyan blends were prepared with various compositions (5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, and 70:30), and blend films of PANI/Cyan were obtained with a casting method. The conductivity of the PANI/Cyan blend films was 10^?7 to 10^?2 S/cm, which was measured by a four‐probe technique. The tensile strength of the blend films was maintained with an increasing amount of PANI (up to 50 wt %), and this was attributed to intermolecular interactions such as hydrogen bonding between PANI and Cyan and a reinforcing effect through blending. This hypothesis was corroborated by Fourier transform infrared spectroscopy. Field emission scanning electron microscopy and thermogravimetric analysis were also used to investigate the morphology and thermal properties of the conducting PANI/Cyan blend films, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1035–1042, 2005     

聚苯胺薄膜在不同质子酸溶液中的生长

在H2SO4、HCl、HNO3和H3PO4质子酸水溶液中采用原位聚合法在石英基片上制备了聚苯胺薄膜.通过对薄膜试样进行红外光谱(FT-IR)、紫外光谱、扫描电镜(SEM)、导电性能的测试研究不同种类质子酸对聚苯胺薄膜厚度及导电性能的影响.实验结果表明,试样的掺杂程度和薄膜分子链共轭长度是提高试样导电性能的重要因素,质子酸的氧化性对薄膜生长和导电性能也会产生影响.     

Polyaniline prepared in the presence of various acids: a conductivity study

Polyaniline (PANI) was prepared by the oxidation of aniline in the presence of various inorganic and organic acids at 20 °C and ?50 °C. When strong acids were used, the conductivity of the protonated PANI was typically 1–10 S cm^?1. The results indicate that the protonation of PANI in media containing carboxylic acids was achieved with the help of sulfuric acid produced during the reaction with ammonium peroxydisulfate. The conductivity of PANI prepared under such conditions was reduced. Partial benzene‐ring sulfonation has been proposed to explain the wide range in conductivity of PANI bases, 10^?11–10^?7 S cm^?1. The densities of the samples reflect the nature of the acid used. The densities of the corresponding PANI bases exhibit much less variation. Molecular weight and degree of crystallinity of PANI are higher when the polymerization is carried out at ?50 °C. The conductivity of the PANI is determined mainly by way of protonation. The effects of molecular weight and of crystallinity on PANI conductivity are marginal. Copyright © 2004 Society of Chemical Industry     

Impact of hydroquinone on thermal and electrical properties of plasticized [poly(vinyl alcohol)]0.7(LiBr)0.3(H2SO4) solid acid membrane

A novel multi‐component system containing poly(vinyl alcohol), lithium bromide, sulfuric acid, ethylene carbonate and hydroquinone was prepared using a solution‐casting technique. The presence of hydroquinone as a reducing agent in the inorganic–organic membrane structure thus produced was thought to lead to enhanced thermal stability of the membrane. The activation energy for the thermal decomposition of the product samples increased with increasing hydroquinone doping. The ionic conductivities of the films were determined from AC impedance measurements in the temperature range 300–373 K. The maximum conductivity was found to be 1.75 × 10^?3 S cm^?1 for a film doped with 4 wt% hydroquinone. The results give some insight into the potential utility of the membrane as a proton‐conducting solid polymer electrolyte. Copyright © 2011 Society of Chemical Industry     

Electrically conducting polyaniline‐PBMA composite films obtained by extrusion

Poly(n‐butyl methacrylate) (PBMA)–polyaniline (PANI) composite films were obtained by extrusion by use of two methods: the first method consisted of polymerizing a thin layer of PANI, with Cl^? as dopant, on the extruded film of PBMA; the second method was based on blends of PBMA and PANI produced by the extrusion of the two polymers by using dodecylbenzene sulfonic acid (DBSA) as dopant. The thermal properties, electrical conductivity, and morphology of the composite films obtained were measured. The sensitivity of the composites films as detectors of hydrogen peroxide and ammonia was evaluated. The change in the electrical resistance on exposure to different aqueous solutions of these components shows a linear behavior. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 179–183, 2003     

Synthesis and characterization of polyaniline films using Fenton reagent

The chemical oxidation of aniline to form polyaniline (PANI) films and powder samples was made using Fenton reagent as an oxidizing agent in aqueous sulfuric acid medium. The PANI films were monitored by using the quartz crystal microbalance and the electronic absorption techniques. The optimum concentration was determined and the results were justified by measuring the UV–vis absorption spectra for the in situ PANI films. The conductivity for the PANI films and powder samples, prepared in different conditions, was measured. Also, the IR spectra, X‐ray and the thermogravimetric analysis for the PANI powder formed in the bulk were measured and compared with the polymer prepared using ammonium peroxydisulfate. A preliminary investigation to the dielectric properties of the polymer powder was measured and discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrochromic properties of polyaniline thin film nanostructures derived from solutions of ionic liquid/polyethylene glycol

By exploiting the templating ability, wetting properties and the capability of the ionic liquid, 1-ethyl,3-methylimidazolium bromide to furnish the anionic dopant, nanostructured thin films of polyaniline (PANI) have been fabricated from an aqueous solution of the monomer encompassing this organic moiety by electropolymerization. These films have been compared to films synthesized from a medium based on a conventional polymeric surfactant, polyethylene glycol 400 (PEG). The template/dopant controls pore structure and assembly patterns as an interconnected network of nanofibrils of 50-500 nm in length and 10-40 nm in diameter constitutes the PANI films derived from the ionic liquid-based solution whereas the dominant microstructural attribute of the PANI films obtained from the PEG-containing formulation are abutting nanoparticles with elongated shapes. The effect of the different thin film nanostructures on their electrochromic properties is evident from the higher coloration efficiency, transmission modulation (in the NIR region), larger charge capacity, enhanced cycling stablity and faster color-bleach rates observed for the PANI films obtained from the ionic liquid medium as compared to that shown by the PANI films fabricated from the PEG solution. The outstanding optical and electrochemical behavior of the films, in particular, for the film derived from the ionic liquid-based solutions indicate that such recyclable and environmentally benign reaction media are most useful especially for transposing PANI films to large area substrates for electrochromic window applications.     

复合酸掺杂PVA/PANI/Ag复合膜的电化学制备及性能研究

采用电化学法制备了硫酸(H2SO4)和磺基水杨酸(SSA)共掺杂的导电聚乙烯醇/聚苯胺(PVA/PANI)复合膜,采用正交设计法优化了工艺条件,研究了沉积银电流密度和时间、拉伸对复合膜电导率的影响。采用红外光谱、X射线衍射、扫描电镜对复合膜进行表征。结果表明,最佳条件下获得的PVA/PANI复合膜的电导率为22.72 S/cm;在此复合膜上以50 mA/cm2沉积2 min银可使复合膜的电导率提高到1250 S/cm;对2种复合膜进行适当的拉伸可使其电导率分别提高20.74 %和18.04 %。复合膜有一定程度的结晶,经拉伸后其结晶度有所提高。     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

Control of polyaniline conductivity and contact angles by partial protonation

Many studies require a specific value of conductivity when investigating conducting polymers. The conductivity of polyaniline can efficiently be controlled by partial protonation of the polyaniline base. Although this is a simple task in principle, practical guidelines are missing. In the present study, the changes in the conductivity of polyaniline base after immersion in aqueous solutions of various acids are reported. Polyaniline base has been reprotonated in aqueous solutions of picric, camphorsulfonic and phosphoric acids. The conductivity of partially reprotonated polyaniline varied between 10⁻⁹ and 10⁰ S cm⁻¹. The relation between the pH of a phosphoric acid solution, which was in equilibrium with polyaniline, and the conductivity σ is pH = 0.77 − 0.64 log(σ [S cm⁻¹]). The wettability, i.e. water contact angles, can similarly be set by partial protonation to between 78° for polyaniline base and 44° for polyaniline reprotonated in 1 mol L⁻¹ phosphoric acid. In solutions of picric acid, the transition from the non‐conducting to the conducting state occurs over a narrow range of acid concentrations, and the tuning of conductivity is consequently difficult. Phosphoric acid is well suited for the control of conductivity of polyaniline because of the moderate dependence of the conductivity on the acid concentration or pH. Copyright © 2007 Society of Chemical Industry     

The development of flaws containing γ′-crystalline alumina regions in barrier anodic films on aluminium

Transmission electron microscopy has been employed to study the formation and development of regions containing γ′-crystalline alumina surrounding flaws in anodic barrier films formed on aluminium in aqueous ammonium borate solutions. The formation of crystalline alumina islands at these localized sites becomes more readily evident when the forming voltage approaches about 100 V and they grow radially with further increase in the forming voltage.The radial growth of the islands and their population density is influenced by increase of bulk temperature of the electrolyte, but is almost unaffected by the concentration of the electrolyte and applied anodizing current density. The population density of the flaws and, hence, γ′-crystalline alumina islands is strongly dependent on the surface condition of the metal and varies from about 2.4 x 10⁸ cm^?2 on the as-received specimen to less than 10⁵ cm^?2 on the electropolished specimen.The islands of crystalline alumina are thought to form in the vicinity of flaws in the original substrate, by conversion of the barrier film formed by the usual ionic processes, due to local Joule heating effects.     

Effect of acids on in situ polyaniline film formation

The chemical oxidation of aniline with ammonium persulfate (APS) to form polyaniline (PANI) films has been studied in different aqueous acid media such as sulfuric, nitric, phosphoric and acetic acids. A comparison was made between the yields of PANI film deposition during the polymerization from these media with the corresponding one obtained previously from aqueous HCl solution. The degradation of the formed PANI films at the beginning of polymerization obtained at the higher concentrations of HCl is absent when the other acids under consideration were used. The effect of acid concentration on the yield and growth rate of the PANI film was studied. The variation in the yield and growth rate of the polymer films at different acid concentrations was explained on the basis of the electrostatic repulsion and the screening effects. Copyright © 2004 Society of Chemical Industry     

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     

Optimization of the electropolymerization of 1-amino-9,10-anthraquinone conducting films from aqueous media

The optimum conditions for the electrochemical preparation of poly(1-amino-9,10-anthraquinone), PAAQ, films in environmentally safe aqueous solutions were investigated. The conducting polymer films were prepared by electrochemical oxidation of 1-amino-9,10-anthraquinone, AAQ, in sulfuric acid solutions in the potential range from 0.0 to +1.3 V. The influence of scan repetition, scan rate, and monomer concentration on the formation process and the properties of the polymer film were studied. The electrochemical response of the formed polymer film was investigated in both aqueous and non-aqueous media. The polymer films were found to be stable in aqueous acidic media. In non-aqueous solutions, like acetonitrile, dimethyl sulfoxide and dioxin, the polymer films showed remarkable degradation. The best electrochemical response of the PAAQ films was found to be in the potential range between +0.3 and +0.9 V. The presence of quinone units in the polymer film chain suggests promising applications of these conducting polymers in lightweight (rechargeable) batteries, electrochromic display devices, and biosensor and corrosion protection.     

Polyaniline/PVAc blends: Variation with time of structure and conductivity of films cast from aqueous dispersions

Recently, a polymerization process of Anilinium‐Dodecyl Benzene Sulfonic Acid (DBSA) complex in an aqueous dispersion was developed in our laboratories. Simple mechanical mixing of the aqueous PANI–DBSA dispersion with a PVAc aqueous latex leads to highly conductive blends at low PANI–DBSA contents. The percolation threshold of the dried films is extremely low (∼0.5 wt %). The combined aqueous PVAc/PANI–DBSA dispersions exhibit a gradually decreasing electrical conductivity accompanied by a gradually increasing viscosity, with the storage time. However, an aged cast film from these blends maintains its electrical conductivity with time. These phenomena are associated with acidic hydrolytic reactions of the ester group, resulting in the formation of vinyl acetate–vinyl alcohol copolymer and evolution of acetic acid, and also the interaction of the DBSA surfactant with the PVAc, causing swelling and disintegration of PVAc particles. A chemical structural model describing these changes with storage time is suggested. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 760–766, 2001     

Surface graft polymerization of conducting polyaniline on waterborne poyurethane‐urea film and its phenol sensing

Waterborne polyurethane‐ureas (pristine WBPUs: WBPU‐19 and WBPU‐24, fixed soft segment content: 60 wt %) containing dimethylol propionic acid (DMPA)/ethylene diamine (EDA) contents (19/16.8 and 24/11.4 mol %) were prepared. The polyaniline (PANI)‐graft‐WBPU (PANI‐graft‐WBPU) films were prepared by oxidative graft polymerization of aniline on the surface layer of WBPU films. This study focused on the effects of reaction conditions (concentrations/treating times/temperatures of aniline and APS) and DMPA content on the %grafting, conductivity, and mechanical properties of PANI‐graft‐WBPU films. To obtain the maximum %grafting (PANI‐graft‐WBPU‐19: 6.2, and PANI‐graft‐WBPU‐24: 7.4) and conductivity (PANI‐graft‐WBPU‐19: 3.6 × 10^?2S/cm, and PANI‐graft‐WBPU‐24: 4.7 × 10^?2S/cm), the optimum concentrations/treating times/temperatures of aniline and APS, were found to be 0.35M/10 min/25°C and 0.2M/10 min/0°C, respectively. The tensile strength of film samples was found to be increased in the order of PANI‐graft‐WBPU‐19>pristine WBPU‐19>PANI‐graft‐WBPU‐24>pristine WBPU‐24. The PANI‐graft‐WBPU‐19 (%grafting: 6.2) films on exposure to 0–10,000 ppm phenol solutions showed a well‐defined response behavior, demonstrating high promise for application in aqueous phenol sensors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of electrolyte concentration on the properties of the electropolymerized polypyrrole films

The effect of electrolyte concentration on the electropolymerization of pyrrole was investigated by studies of conductivity, tensile strength, and absorption spectra, etc., of polypyrrole films prepared from electrolyte aqueous solutions. The electrolyte salts used in the studies include sodium p-toluenesulfonate (TsONa), NaClO₄, NaNO₃, and KCl. Cyclic voltammetry and elemental analysis were also performed in the studies of the effect of the NaNO₃ concentration. The conductivity, tensile strength, and the counteranion doping degree of conducting polypyrrole films increased obviously with increase of the electrolyte concentration of their polymerization solutions from 0.2 to 1 mol L⁻¹. Further increase of the concentration over 1 mol L⁻¹ has a weak effect on the further improvement of the film quality of polypyrrole. So, 1 mol L₋₁ was recommended for the electrolyte concentration of the polymerization aqueous solutions of pyrrole. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2739–2744, 1997     

Electrical conductivity and mechanical properties of polyaniline/natural rubber composite fibers

Electrically conducting elastomer fibers based on natural rubber (NR) and up to 10% w/w polyaniline (PANI) in its emeraldine base (EB) form were fabricated by a wet spinning process. The resulting fibers at various PANI contents were doped by immersion in aqueous HCl solution, which converted the PANI to the electrically conductive emeraldine salt (ES) form. The morphology of the composite fibers was studied by scanning electron microscopy (SEM). PANI particles were inhomogeneously distributed in the NR matrix. The electrical conductivity of the fibers increased with the increasing PANI‐ES content and leveled off at a value of around 10^?3 S/cm at PANI‐ES concentration of 5% w/w. The fibers retained most of their elasticity upon doping, while the tenacity was somewhat reduced. Gratifyingly, the electrical conductivity of the new elastomer fibers was preserved upon elongational deformation, even if strains as large as 600% were applied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007