Layer-by-layer assembly of graphene/polyaniline multilayer films and their application for electrochromic devices

Graphene/polyaniline (PANI) multilayer films were prepared via alternate deposition of negatively charged graphene oxide (GO) and positively charged PANI upon electrostatic interaction, followed by the reduction of their GO components with hydroiodic acid. The thickness of the multilayer film increased linearly with the number of its bilayers and that of each bilayer was measured to be about 3 nm. Cyclic voltammetry studies indicated that these thin composite films were electroactive, and their redox reactions were related to the insertion-extraction of counter ions in PANI layers. Furthermore, the composite films were tested to be promising electrode materials for electrochromic devices even without using the conventional indium tin oxide (ITO) electrodes.     

Synthesis of nanoporous platinum thin films and application as hydrogen sensor

A nanoporous platinum (np-Pt) thin film based hydrogen sensor was fabricated and studied. The np-Pt thin films were fabricated through a method of chemical dealloying and coarsening starting from a CuPt alloy. The alloy thin films of Cu_xPt_1?x were deposited by sputtering copper and platinum at the same time. The dealloying process completely removed the copper from the film. We demonstrate a method to control the porosity of np-Pt by a method of coarsening. Scanning electron microscopy confirmed the presence of porosity with size ranging from a few nanometers to tens of nanometers. A sensor device with four electrodes was fabricated on the np-Pt thin films using a stainless steel mask and by sputtering copper. The electrical characteristics of the sensor exhibit marked sensitivity or current changes in the presence of hydrogen. The results demonstrate that np-Pt thin films configured as a gas sensor have high sensitivity to hydrogen.     

Spectroscopic and electrical properties of polyaniline/CeO2 composites and their application as humidity sensor

Polyaniline/CeO₂ composites were synthesized by in situ chemical polymerization method using ammonium persulphate as an oxidizing agent. This is the single step polymerization process for the direct synthesis of emeraldine salt phase of polymer. The polymers were characterized by using FTIR spectral analysis, SEM, and XRD studies. Formation of conducting emeraldine salt phase is confirmed by spectroscopic techniques. High temperature conductivity measurements show “thermal activated behavior.” The change in resistance with respect to percentage relative humidity (% RH) is observed, when the pressed pellets of the polymer were exposed to the broad range of humidity (humidity ranging between 10 and 95% RH). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5533–5537, 2006     

Aqueous chemical route deposition of nanocrystalline ZnO thin films as acetone sensor: Effect of molarity

Nanocrystalline ZnO thin films were deposited onto glass substrate using a simple and inexpensive aqueous chemical method at low temperature (90 °C). The concentration of precursor solution was varied in order to study its effect on structural, morphological, and gas response properties. Field-emission scanning electron microscopy (FESEM) images indicate the growth of ZnO with hexagonal shaped nanostructure. Further these films were used to explore gas response properties towards acetone, propanol and ethanol vapors. The sensor response was found to be decreased with increase in precursor concentration. The highest sensor response of 92% was observed towards acetone for the film deposited at 0.05 M at an operating temperature of 350 °C. The higher vapor response towards acetone is attributed to size and surface morphology of the film deposited at 0.05 M.     

The interaction of thin polyaniline films with various H‐phosphonates: Spectroscopy and quantum chemical calculations

The conducting form of polyaniline (PANI) is formed by doping of non‐conducting PANI base usually by protonic acids. An alternative way of doping, consisting in an interaction via hydrogen bonding, has been previously proven for H‐phosphonates. In this study, PANI base films are exposed to various H‐phosphonates, changes in the structure of the films are analyzed by ultraviolet–visible, infrared, and Raman spectroscopies and spectroscopic data are compared with quantum chemical calculations. According to our results, the interaction of the PANI base films with H‐phosphonates is realized by hydrogen bonding between the imine nitrogen of PANI and the hydroxy group of the H‐phosphonate tautomeric form, i.e., phosphite. This is in the contrast to the PANI powders doped with H‐phosphonates where both interacting phosphite and non‐interacting H‐phosphonate forms were observed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46728.     

Synthesis and studies of exceptionally crystalline polyaniline thin films

Highly crystalline camphor sulfonic acid (CSA)‐doped polyaniline (PANI) thin films cast from m‐cresol and N‐methylpyrrolidone (NMP) were investigated. PANI powder prepared by chemical oxidative polymerization subjected to doping–de‐doping–re‐doping procedures was cast into thin films using NMP and m‐cresol as solvents. X‐ray diffraction (XRD) reveals the presence of exceptionally highly crystalline or rather ordered regions in the PANI film samples prepared from m‐cresol. Atomic force microscopy (AFM) images also support the presence of crystalline regions on the surface of these films. The DC electrical conductivity of m‐cresol‐cast PANI is found to be quite high, and much higher than that of NMP‐cast PANI. The free‐carrier absorption tail extending to the near‐infrared region observed in the optical absorption spectrum of the m‐cresol‐cast PANI films suggests a metallic nature and regular structural arrangement in these films. Both inter‐chain and intra‐chain ordering brought about as a result of CSA doping, secondary doping effect of m‐cresol and ultrasonication are suggested to be the prime factors contributing towards the observed excellent crystallinity of these PANI films as evident from the XRD and AFM studies. The marked thermal stability of the m‐cresol‐cast PANI films is also established based on the variation of DC electrical conductivity with temperature and on thermogravimetric analysis. Copyright © 2012 Society of Chemical Industry     

Use of natural rubber prophylactics waste as a potential filler in styrene–butadiene rubber compounds

Owing to the unstable nature of the latex compound and the strict specifications in the quality of latex products such as condoms and examination gloves, the rejection in the latex industry comes to about 10 to 15% of the rubber consumed. These latex rejects contain about 95% rubber hydrocarbon of very high quality. A cost-effective technique has been developed for the reuse of natural rubber (NR) prophylacties waste in styrene–butadiene rubber (SBR). The influence of powdered latex rejects on the curing characteristics, mechanical properties, and failure behavior of SBR has been investigated. More emphasis is placed on the effect of both particle size and the loading of latex waste filler. Swelling studies were carried out to establish the degree of crosslinking of SBR and to assess the extent of interaction between the matrix and latex waste filler of varying particle sizes. A three layer model has been set up to study the diffusion of sulfur from the matrix phase to the filler phase. Scanning electron microscopy has been used to analyze the particle morphology, filler dispersion, and filler-matrix interface adhesion. The results of the study revealed that NR prophylactics rejects can be used effectively as a potential filler in SBR up to about 40 phr loading. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of Cu1-xZnxO composite thin films for sensor application

Cu_1-xZn_xO composite thin films were prepared using industrially applicable spray pyrolysis technique for volatile organic compound (VOCs) sensor application. Sensing properties for different concentration of VOCs such as acetone, ethanol and methanol were studied at different sensor operating temperature. XRD studies on prepared thin films confirmed formation of CuOZnO composite thin films with presence of different peaks for monoclinic structured CuO and hexagonal structure ZnO, it was also observed that formation of composite material improves sensing property towards VOCs. Granular morphology observed from SEM images were also contributed to enhance sensitivity of Cu_1-xZn_xO thin films. Hot probe experiment reveals that all the thin films were p-type in conductivity nature. Maximum electrical conductivity was achieved for Cu_0.75Zn_0.25O composite thin films, which also showed highest sensing property for VOCs. Cu_0.75Zn_0.25O thin films were selective towards ethanol and were capable of detecting 1 ppm of ethanol at operating temperature of 290 °C.     

Dichlorocarbene modification of natural rubber and its role as a modifier in blends of natural rubber and hydrogenated nitrile rubber

Dichlorocarbene modification of natural rubber (NR) carried out by alkaline hydrolysis of chloroform in presence of cetyl trimethyl ammonium bromide as phase‐transfer catalyst was investigated. Extent of chemical reaction was characterized by estimation of chlorine content and FTIR studies. Rate of dichlorocarbene addition depends on the time and temperature of reaction. Reaction carried out at 60°C for 2 h yielded a material with a chlorine content of 15%. Chemical modification of NR was accompanied by introduction of chlorine through cyclopropyl ring to the main chain of NR as revealed from FTIR studies. As level of chlorination increased, the physical nature of NR changed from a soft flexible state to a hard nontacky form. Blends of NR with hydrogenated nitrile rubber (HNBR) containing three to seven parts of dichlorocarbene‐modified NR (DCNR) of chlorine content 15% could be prepared by conventional mill mixing. Incorporation of DCNR into blends of NR and HNBR promoted polar interaction between the chlorine segments and acrylonitrile segments of the blend as shown from the shift in characteristic IR absorption peaks and shift in T_g from DSC studies. As a consequence, DCNR acted as an interface modifier in blends of NR and HNBR. Blends of NR and HNBR containing DCNR showed a considerable improvement in cure behavior, physical properties, and ageing characteristics in oil, ozone, and high temperature compared to pure blends of NR and HNBR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4401–4409, 2006     

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     

环氧化天然橡胶的研究与应用

环氧化天然橡胶（ENR）是由NR化学改性而成,笔者阐述了环氧化天然橡胶制备原理和方法、环氧化天然橡胶性能及应用研究、环氧化天然橡胶共混改性研究,其中包括ENR与PVC共混体系的研究、ENR其它共混体系的研究和ENR改性的研究.     

Controlled synthesis of Mg(OH)2 thin films by chemical solution deposition and their thermal transformation to MgO thin films

The chemical solution deposition of Mg(OH)₂ thin films on glass substrates and their transformation to MgO by annealing in air is presented. The chemical solution deposition consists of a chemical reaction employing an aqueous solution composed of magnesium sulfate, triethanolamine, ammonium hydroxide, and ammonium chloride. The as-deposited films were annealed at different temperatures ranging from 325 to 500?°C to identify the Mg(OH)₂-to-MgO transition temperature, which resulted to be around 375?°C. Annealing the as-deposited Mg(OH)₂ films at 500?°C results in homogeneous MgO thin films. The properties of the Mg(OH)₂ and MgO thin films were analyzed by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV–Vis spectroscopy, and by circular transmission line model. Results by X-ray diffraction show that the as-deposited thin films have a brucite structure (Mg(OH)₂), that transforms into the periclase phase (MgO) after annealing at 500?°C. For the as-deposited Mg(OH)₂ thin film, a nanowall surface morphology is found; this morphology is maintained after the annealing to obtain MgO, which occurred with the evident formation of pores on the nanowall surface. The assessed chemical composition from X-ray photoelectron spectroscopy yields Mg_0.36O_0.64 (O/Mg ratio of 1.8) for the as-deposited Mg(OH)₂ film, where the expected stoichiometric composition is Mg_0.33O_0.67 (O/Mg ratio of 2.0); the same assessment yields Mg_0.60O_0.40 (O/Mg ratio of 0.7) for the annealed thin film, which indicates the obtainment of a MgO material with oxygen vacancies, given the deviation from the stoichiometric composition of Mg_0.50O_0.50 (O/Mg ratio of 1.0). These results confirm the deposition of Mg(OH)₂ films and the obtainment of MgO after the heat-treatment. The energy band gap of the films is found to be 4.64 and 5.10?eV for the as-deposited and the film annealed at 500?°C, respectively. The resistivity of both Mg(OH)₂ and MgO thin films lies around 10⁸?Ω·cm.     

Thermal aging properties and chemical resistance of blends of natural rubber and epoxidized low molecular weight natural rubber

Studies into solvent resistance and aging properties of blends of natural rubber and epoxidized low molecular weight natural rubber were carried out. Vulcanization of the blends using the semi‐efficient vulcanization (semi‐EV) system was found to have curing advantages over conventional vulcanization (CV) and efficient vulcanization (EV) systems. The rheological properties (cure time, t₉₀, and scorch time, t₂), solvent resistances, and aging properties of the vulcanizates were found to improve as the level of epoxidized low molecular weight natural rubber in the blends increases. The mechanical properties of the blends were also found to be within the accepted level for NR vulcanizates. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1733–1739, 2005     

Optical,electrical and morphological properties of transparent binary doped polyaniline thin films synthesized by in situ chemical bath deposition

The development of polymeric thin films has attracted attention in the optoelectronics field due to their transparency. The aim of the research presented was to obtain transparent polyaniline thin films by easy in situ oxidative polymerization of aniline with ammonium persulfate in the presence of a binary doping agent–poly(vinyl alcohol) mixture. Poly(acrylic acid), 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid or sodium dodecylsulfate were mixed with hydrochloric acid to form the binary doping agents. Polyaniline thin films were produced during aniline polymerization on Corning glass slides immersed in the mixture in order to study their optical, electrical and morphological properties. The optical absorption coefficient and the energy band gap were evaluated by optical transmission of the films in the UV‐visible spectral region. The optical absorption coefficient of all polyaniline films was of the order of 10⁴ cm^?1 with a maximum transmittance up to 80% at 550 nm. In order to investigate the effect of the mixture on the surface morphology and roughness of the films, atomic force microscopy was used. In general, surface roughness was reduced threefold by adding a mixture and optical transmission was increased by 20–30% without significantly affecting the absorption coefficient and the band gap of polyaniline. Islands and needle‐like structures on the film surfaces were obtained from various mixtures affecting the conductivity; for example, 0.17 S cm^?1 was obtained from needle‐like morphology, while 1.9 × 10^?4 S cm^?1 was obtained from island morphology. Raman spectroscopy studies confirmed the presence of poly(vinyl alcohol) in the thin films. Copyright © 2011 Society of Chemical Industry     

环氧化天然橡胶的研究及应用进展

环氧化天然橡胶(ENR)具有良好的耐油性、气密性和粘着性,同时还具备一些特殊性能,是一种具有广阔应用前景的橡胶材料。本文介绍了近年环氧化天然橡胶的制备、结构、性能、改性和应用的研究工作,并对其研究趋势进行了展望。     

Use of natural rubber‐g‐polystyrene as a compatibilizer in casting natural rubber/polystyrene blend films

Natural rubber/polystyrene (NR/PS) blend films with weight ratios of 70/30, 60/40, and 50/50 were prepared using polystyrene grafted natural rubber copolymers (NR‐g‐PS) as the compatibilizer. Copolymers with molar ratios of 90/10, 80/20, and 70/30 were synthesized via emulsion copolymerization using tert‐butyl hydroperoxide/tetraethylene pentamine as an initiator. The copolymers were subsequently added into the blends at 0, 5, 10, 15, 20, 25, and 30 phr. The mixtures were cast into films by the solution‐casting method using toluene as the casting solvent. Mechanical and morphological properties of the prepared films were investigated. The film prepared from 80/20 NR‐g‐PS showed higher tensile and tear strength, as well as finer domain size of the dispersed phase, than those prepared from 90/10 and 70/30 NR‐g‐PS. However, the mechanical properties of the films were decreased at high loading of the copolymers. In addition, themogravimetric analysis revealed that weight loss was decreased upon introduction of the compatibilizer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 826–831, 2005     

Formation of single-walled carbon nanotube thin films enriched with semiconducting nanotubes and their application in photoelectrochemical devices

Single-walled carbon nanotube (SWCNT) thin films, containing a high-density of semiconducting nanotubes, were obtained by a gel-centrifugation method. The agarose gel concentration and centrifugation force were optimized to achieve high semiconducting and metallic nanotube separation efficiency at 0.1 wt% agarose gel and 18,000g. The thickness of SWCNT films can be precisely controlled from 65 to 260 nm with adjustable transparency. These SWCNT films were applied in photoelectrochemical devices. Photocurrents generated by semiconducting SWCNT enriched films are 15-35% higher than those by unsorted SWCNT films. This is because of reducing exciton recombination channels as a result of the removal of metallic nanotubes. Thinner films generate higher photocurrents because charge carriers have less chances going in metallic nanotubes for recombination, before they can reach electrodes. Developing more scalable and selective methods for high purity semiconducting SWCNTs is important to further improve the photocurrent generation efficiency by using SWCNT-based photoelectrochemical devices.     

Synthesis of polysilane-acrylamide copolymers by photopolymerization and their application to polysilane-silica hybrid thin films

Various polysilane-acrylamide block copolymers have been prepared from photopolymerization of acrylamide-type monomers using poly(methylphenylsilane) (PMPS) as a macro-photo-radical initiator. The acrylamide block in the copolymers improved the hydrophilic property of PMPS. These PMPS-acrylamide block copolymers have been applied to formation of PMPS-silica hybrid thin films via sol-gel reaction. Homogeneous and transparent PMPS-silica hybrid thin films were obtained from a few PMPS-acrylamide block copolymers. It was found for these hybrid thin films based on hydrogen bonding formation between amide group and silanol group. The surface properties of hybrid thin films were evaluated by water contact angle measurement, scanning electron microscope (SEM), and atomic force microscope (AFM) images.     

Preparation and self‐assembly of polyaniline nanorods and their application as electroactive actuators

To improve the performance of ion‐exchange polymer–metal composite (IPMC) actuators, an electrical pathway material for enhancing the surface adhesion between the membrane and the metal electrodes of the IPMC was studied. As an efficient electrical pathway material, polyaniline nanorods (PANI‐NRs) doped with p‐toluene sulfonic acid (TSA) were synthesized with a template‐free method. The factors affecting polyaniline morphology were studied with various dopant concentrations and oxidant feeding rates. Highly conductive PANI‐NRs were formed when they were synthesized with ammonium persulfate at a 5.0 mL/min oxidant feeding rate and doped with 0.125M TSA. The conductivity of the PANI‐NRs was 1.15 × 10^?1 S/cm, and their diameters and lengths were 120–180 nm and 0.6–2 μm, respectively. To apply the membrane as an actuator, perfluorosulfonated ionomer (Nafion)/PANI‐NR blends were prepared by solution blending and casting. The actuating ability of the three‐layered membrane consisting of Nafion/PANI‐NR blends was then examined and compared with that of Nafion only. The actuating ability of the IPMC was improved when Nafion/PANI‐NRs were used as electrical pathways. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010