Synthesis and characterization of a conducting polyaniline/TiO2−SiO2 composites

Polyaniline/TiO₂?SiO₂ composites were prepared by an in situ chemical oxidation polymerization approach in the presence of hybrid TiO₂?SiO₂ fillers. The obtained polyaniline/TiO₂?SiO₂ composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FTIR), X‐ray diffraction (XRD), thermogravimetry (TG), and current?voltage (I?V) measurements. SEM picture shows a variation in morphology of polyaniline (PANI) from fiber shape to relatively regular particle shape with increasing TiO₂?SiO₂ contents in the composites. The floccule‐like structures were observed by high resolution TEM, which may help improve the efficiency of conductive network. SEM, XRD, TG, and FTIR spectra all reveal that a relatively strong interaction exist between TiO₂?SiO₂ and PANI. The I?V characteristics in such composites indicate that the charge transport is mainly governed by the space charge effects, which occurs at the interface between the conducting PANI and TiO₂?SiO₂. Meanwhile, PANI/TiO₂?SiO₂ composites exhibit significant increase in conductivity than PANI/TiO₂ or PANI/SiO₂. The reasons about high conductivity of PANI/TiO₂?SiO₂ have also been discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2288–2295, 2013     

A robust and coarse surface mesh modified by interpenetrating polymer network hydrogel for oil‐water separation

A robust and coarse surface mesh was fabricated by introducing a hydrogel coating with interpenetrating polymer network (IPN) structure on stainless steel mesh. The IPN hydrogel was prepared by crosslinking polymerization of acrylic acid (AA) followed by condensation reaction of polyvinyl alcohol (PVA) and glutaraldehyde (GA) at room temperature. As a result, the roughness of modified mesh was enhanced obviously and oil droplet underwater showed a larger contact angle. The hydrogel‐coated surface showed an underwater superoleophobicity with an oil contact angle of 153.92 ± 1.08^°. Besides, stable wettability was observed. The mesh can selectively separate oil from water with a high separation efficiency of above 99.8%. This work provides a facile method to strengthen the coating and enhance the efficiency of oil‐water separation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41949.     

3D-Printed thermoplastic polyurethane/graphene composite with porous segregated structure: Toward ultralow percolation threshold and great strain sensitivity

Low-percolation threshold and large deformation capacity are two critical attributes of the strain sensor, which determine its sensitivity and stability respectively. However, endowing these two attributes to the strain sensor simultaneously is still a great challenge in this field. In this work, the strain sensor with the three-dimensional porous segregated structure constructed by graphene wrapped thermoplastic polyurethane (TPU) particles was fabricated successfully through the selective laser sintering technology. Results demonstrated that the percolation threshold of the composite is only 0.2 wt% and the strain gage factor can reach as high as 668.3, which represents the excellent sensitivity of the strain sensor. Furthermore, after 10 circles of stretching at the 15% strain, resistance-strain behavior of the strain sensor shows great repeatable, which represents the remarkable stability. Therefore, the highly sensible and stable strain sensor was fabricated successfully, which will provide the guidance for the manufacture of the high-performance strain sensor.     

Li‐ion conductivity in PEO‐graphene oxide nanocomposite polymer electrolytes: A study on effect of the counter anion

Graphene oxide (GO) has been prepared by modified Hummer's method for their incorporation as nanofiller in designing nanocomposite polymer electrolytes (NCPEs). Prior to use the GO nanofillers has been characterized by TEM, FTIR, and Raman studies to elucidate their nanostructure, functionality, and purity. The various poly(ethylene oxide) (PEO)‐based NCPEs has been prepared by incorporating GO nanofillers in presence of three different lithium salts, viz., CF₃SO₃Li, LiTFSI, and LiNO₃ as the source of Li‐ions and then casted into free standing polymeric films. The change in PEO crystallinity has been studied considering their full width half maximum values of respective diffraction peaks in the XRD spectra. The Li‐ion conductivity of various NCPEs has been studied from impedance spectroscopy. All the NCPE films show optimum value of Li‐ion conductivity with 0.3% GO nanofiller content irrespective of the source of Li‐ions used. But, variation of the Li‐ion conductivity values is occurred for all the three studied lithium salts. Both LiTFSI and LiNO₃ salts display Li‐ion conductivity in the order of 10^?4 S cm^?1 whereas CF₃SO₃Li in the order of 10^?6 S cm^?1, all in presence of 0.3% GO nanofillers. The change in conductivity values of the NCPEs has been explained by correlating with Argand plots and also with change in PEO crystallinity, which occurs due to various relaxation processes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46336.     

Interfacial polymerization of poly(2,5‐dimethoxyaniline) and its enhanced capacitive performances

The poly(2,5‐dimethoxyaniline) (PDMA) were synthesized through interfacial polymerization method using three various organic solvent/water reaction systems. As comparison with conventional chemical polymerized PDMA, the interfacial polymerization can produce uniform nanoparticular PDMA, especially for using high density (higher than water) solvent as organic phase. The capacitive performances of interfacial polymerized PDMA can be benefited from its uniform morphologies and loose packing structure. The specific capacitance of interfacial polymerized PDMA using carbon tetrachloride is 194 Fg^?1 at current density of 50 mA cm^?2, which has 59% enhancement over 122 Fg^?1 of conventional PDMA at the same current density. The energy density of interfacial polymerized PDMA is 39 Wh kg^?1 at current density of 5 mA cm^?2 and the power density is 28,421 W kg^?1 at current density of 50 mA cm^?2. The energy density has improvement in different extent as comparison with that of conventional PDMA. The enhanced capacitive performances can be attributed to the increased ionic conductivity induced by the loose molecular packing structure and uniform morphology produced by the interfacial polymerization process. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40666.     

Preparation of conductive polyaniline/nylon‐6 composite films by polymerization of aniline in nylon‐6 matrix

Polyaniline (PANI)/Nylon‐6 composite films were prepared by oxidative polymerization of aniline (ANI) inside host Nylon‐6 film. Such a composite has the desired electro‐active and mechanical properties to serve as a self‐standing functional unit. Comparative studies on sorption of ANI by Nylon‐6 matrix from various ANI containing media were conducted revealing superior ANI uptake from neutral ANI solution in water. ANI content was measured to be as high as 12%. Spectroscopic measurements showed that hydrogen bonding seemed to play important role in ANI sorption by Nylon‐6 matrix. Polymerization was monitored using atomic force microscopy and conductivity measurements. The morphology studies showed the appearance of PANI nanodomains on Nylon‐6 surface in the early stages of the polymerization. Eventually the domains coalesced during polymerization forming a continuous PANI layer. The conductivity measurements confirmed the change of the morphology from isolated islands to continuous conducting surface by drastic increase in conductivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hybrid polyaniline–TiO2 nanocomposite Langmuir–Blodgett thin films: Self‐assembly and their characterization

Polyaniline (PANi)–titanium dioxide (TiO₂) nanocomposite materials were prepared by chemical polymerization of aniline doped with TiO₂ nanoparticles. Surface pressure–area (π‐A) isotherms of these nanocomposites show phase transformations in the monolayer during compression process. Multiple isotherms indicate that the monolayer of the nanocomposite material can retain its configuration during compression‐expansion cycles. Langmuir–Blodgett thin films of PANi–TiO₂ nanocomposite were deposited on the quartz and indium tin oxide coated conducting glass substrates. Fourier transfer infrared spectroscopy and UV–visible spectroscopy study indicates the presence of TiO₂ in PANi, whereas X‐ray Diffraction study confirmed the anatase phase of TiO₂ and particle size (～nm) of PANi–TiO₂. The morphology of Langmuir–Blodgett films of these nanocomposites was also characterized by atomic force microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41386.     

Electrochemical synthesis and In situ spectroelectrochemistry of conducting NMPy‐TiO2 and ZnO polymer nanocomposites for Li secondary battery applications

Poly(N‐methylpyrrole) (PNMPy), poly(N‐methylpyrrole‐TiO₂) (PNMPy‐TiO₂), and poly (N‐methylpyrrole‐ZnO) (PNMPy‐ZnO) nanocomposites were synthesized by in situ electropolymerization for cathode active material of lithium secondary batteries. The charge–discharging behavior of a Li/LiClO₄/PNMPy battery was studied and compared with Li/LiClO₄/PNMPy‐nanocomposite batteries. The nanocomposites and PNMPy films were characterized by cyclic voltammetry, in situ resistivity measurements, in situ UV–visible, and Fourier transform infra‐red (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The differences between redox couples (ΔE) were obtained for polymer nanocomposites and PNMPy films. During redox scan, a negative shift of potential was observed for polymer nanocomposite films. Significant differences from in situ resistivity of nanocomposites and PNMPy films were obtained. The in situ UV–visible spectra for PNMPy and polymer nanocomposite films show the intermediate spectroscopic behavior between polymer nanocomposites and PNMPy films. The FTIR peaks of polymer nanocomposite films were found to shift to higher wavelengths in PNMPy films. The SEM and TEM micrographs of nanocomposite films show the presence of nanoparticle in PNMPy backbone clearly. The result suggests that the inorganic semiconductor particles were incorporated in organic conducting PNMPy, which consequently modifies the properties and morphology of the film significantly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41526.     

Fabrication and characterization of mesoporous carbon nanosheets using halloysite nanotubes and polypyrrole via a template‐like method

A novel synthesis route for mesoporous carbon (MC) nanosheets were developed using halloysite nanotubes (HNTs), a type of natural clay that is structurally and chemically similar to mineral kaolinite, as inorganic matrix and using polypyrrole (PPy) as carbon precursor by a template‐like method. First, PPy/HNT hybrids were prepared by in situ oxidative polymerization. Carbon (C)/HNT hybrids were further obtained by pyrolysis of the PPy/HNT hybrids. MC was obtained after the removal of inorganic template by hydrochloric acid/hydrofluoric acid mixture at the end. Both the C/HNT and the MC were characterized by Fourier transform infrared spectroscopy analysis, X‐ray diffraction, Raman spectra measurement, and high‐resolution transmission electron microscopy. The MC was also characterized with specific surface area (BET). The results showed that the MC obtained was almost amorphous carbon. The increase in the ratio of [HNTs template]/[pyrrole monomer] led to an increase in the BET‐specific surface area. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Electrical properties and the role of inhomogeneities at the polyvinyl alcohol/n‐inp schottky barrier interface

In this work, we have investigated the electrical properties of Au/n‐InP contacts with a thin layer of polyvinyl alcohol (PVA) as an interlayer. The current–voltage (I–V) and capacitance–voltage (C–V) measurements are carried out in the temperature range of 175–425 K. The Au/PVA/n‐InP Schottky structure show nonideal behaviors and indicates the presence of a nonuniform distribution of interface states. The temperature dependent interface states densities (N_SS), ideality factor and barrier height are obtained. An abnormal decrease in zero‐bias barrier height (BH) and increase in the ideality factor ( ) with decreasing temperature have been explained on the basis of the thermionic emission theory with Gaussian distribution (GD) of the BHs due to the BH inhomogeneities. The experimental I–V characteristics of Au/PVA/n‐InP Schottky diode has revealed the existence of a double GD with mean BH values of ( ) of 1.246 and 0.899 eV and standard deviation ( ) of 0.176 and 0.137 V, respectively. Consequently, the modified conventional activation energy versus plot gives and Richardson constants ( ) and the values are 1.17 and 0.71 eV and 9.9 and 6.9 A/cm² K², respectively, without using the temperature coefficient of the BH. The effective Richardson constant value of 9.9 A/cm² K² is very close to the theoretical value of 9.4 A/cm² K² for n‐InP. The discrepancy between Schottky barrier heights estimated from I–V and C–V measurements is also discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39773.     

Fabrication of large‐scale superhydrophobic composite films with enhanced tensile properties by multinozzle conveyor belt electrospinning

Large‐scale superhydrophobic composite films with enhanced tensile properties were prepared by multinozzle conveyor belt electrospinning. First, a strategy of conveyor belt electrospinning was introduced for large‐scale fabrication since the conveyor belt can expand the electrospinning area unlimitedly. During the electrospinning (or electrospraying) process, certain kinds of fibers are combined on the conveyor belt in one electrospinning (or electrospraying) step. The superhydrophobicity of electrospun film can be achieved by the presence of PS beads and bead‐on‐string PVDF fibers, while submicron PAN fibers are responsible for the improvement of mechanical properties. The result shows that CA value of the surface comprising of PS beads and bead‐on‐string PVDF fibers could reach up to 155.0°. As the submicron PAN fibers increased, the value of CA decreased, changing from 155.0° to 140.0°, meanwhile the tensile strength of composite film was enhanced from 1.14 to 4.12 MPa correspondingly which is beneficial to putting the films into practice. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39735.     

Highly efficient electrically conductive networks in carbon‐black‐filled ternary blends through the formation of thermodynamically induced self‐assembled hierarchical structures

Highly efficient electrical conductive networks were constructed in carbon‐black (CB)‐filled polyoxymethylene (POM)–thermoplastic polyurethane (TPU)–polyamide 6 (PA6) ternary blends through the formation of a hierarchical structure composed of a minor PA6 phase as droplets inside one major phase (TPU) and CB particles localized at the TPU–PA6 interface by thermodynamically induced self‐assembly. The hierarchical structure was thermodynamically predicted on the basis of the minimization of total interfacial energies and confirmed by electron microscopy. The degrees of the TPU phase continuity before and after the addition of PA6 were determined by solvent‐extraction experiments. The percolation threshold of CB decreased by 50% compared to that in the POM–TPU binary blend because of the more efficient formation of a CB conductive network through CB‐covered PA6 domains inside the TPU phase. The hierarchical structure not only increased the electrical conductivity of the composites but also improved their thermal stability in comparison with the simple structure formed by the homogeneously dispersed CB particles in POM. The method reported in this article can offer possibilities for improving the comprehensive properties of the conductive composites and the widening of their applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45877.     

Crosslinked epoxy microspheres: Preparation,surface‐initiated polymerization,and use as macroporous silica porogen

In this article, we report the preparation of crosslinked epoxy microspheres with diameters of 5–10 μm prepared via phase‐inverted phase separation induced by polymerization in the thermosetting blend of epoxy and poly(ε‐caprolactone). The surfaces of the epoxy microspheres were functionalized to bear 2‐bromopropionyl groups, which were further used as initiators to obtain poly(glycidyl methacrylate) (PGMA) grafted epoxy microspheres via the surface‐initiated atom transfer radical polymerization approach. The PGMA‐grafted epoxy microspheres were then employed to react with 3‐aminopropyltrimethoxylsilane (APTMS) to obtain the functionalized epoxy microspheres, the surface of which contained a great number of trimethoxysilane groups. A co‐sol–gel process between the APTMS‐functionalized epoxy microspheres and tetraethoxysilane was performed, and organic–inorganic glassy solids were obtained. The organic–inorganic glasses were used as precursors for accessing macroporous silica materials via pyrolysis at elevated temperatures. The hierarchical porosity of the resulting macroporous silica was investigated by means of field emission scanning electronic microscopy, transmission electronic microscopy, and surface‐area Brunauer–Emmett–Teller (BET) measurements. We found that the macroporous silica possessed BET surface areas in the range 183.9–235.2 m²/g, depending on the compositions of their precursors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electropolymerization of aniline in phosphonium‐based ionic liquids and their application as protective films against corrosion

Conductive polyaniline (PANI) films were deposited on mild steel by an electropolymerization technique in the presence of different types of phosphonium‐based ionic liquids, including tetrabutylphosphonium bromide, tetraoctylphosphonium bromide, and ethyltributylphosphonium diethylphosphate. The formation of the PANI films was followed by repetitive cyclic voltammetry scans and was confirmed with diffuse reflectance infrared Fourier transform spectroscopy. The morphology, surface roughness parameters, and grain sizes of these coatings were evaluated by atomic force microscopy. The corrosion behavior of the bare and PANI‐coated electrodes was investigated by potentiodynamic polarization, open‐circuit potential, and electrochemical impedance spectroscopy techniques in a simulated marine environment in 3.5 wt % aqueous NaCl solutions. The quantum chemical parameters of the PANI composite films were also calculated with parametric method 3, a semi‐empirical quantum mechanical method. The theoretical conclusions were found to be consistent with the reported experimental data. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43923.     

Polymer–protein interaction,water retention,and biocompatibility of a stimuli‐sensitive superporous hydrogel containing interpenetrating polymer networks

The swelling of a superporous hydrogel containing poly(acrylic acid‐co‐acrylamide)/O‐carboxymethyl chitosan interpenetrating polymer networks (SPH‐IPN) was sensitive toward the pH, ionic strength, and temperature stimuli. With insulin as a model drug, polymer–protein interaction was detected, and it was physical rather than covalent. Freezing water was the majority of the imbibed water in the swollen SPH‐IPNs, and the water‐retention ability of the polymer against compression and time of exposure at 37°C was improved as the amount of the O‐carboxymethyl chitosan network increased. A 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide (MTT) assay on AD293 and RBL‐2H3 cells and an in situ lactate dehydrogenase assay and morphological study on rat intestine confirmed that the SPH‐IPNs had satisfactory biocompatibility. These pronounced properties suggested that the SPH‐IPNs could be developed as an attractive peroral delivery vehicle for peptide and protein drugs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of a polyaniline/poly(butyl acrylate–vinyl acetate) composite as a novel conducting polymer composite

This is the first report on the preparation and characterization of a polyaniline/poly(butyl acrylate–vinyl acetate) composite. The composite was prepared by the emulsion polymerization of aniline in a medium containing poly(butyl acrylate–vinyl acetate). Films prepared from the composite (cast from an aqueous medium) had excellent mechanical properties and could be stretched up to 900%. The resultant composite was soluble in common organic solvents, and a stable water‐based dispersion could also be prepared. An electrical conductivity of 2.2 S cm^?1 was obtained. Cyclic voltammograms revealed that the composite was electroactive. It had excellent adhesion to either glass or steel plate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2525–2531, 2003     

Laccase‐catalyzed synthesis of polypyrrole‐multiwalled carbon nanotube composites as energy storage materials for capacitors

Multiwalled carbon nanotubes (MWNTs) were coated with polypyrrole (PPy) using in situ enzymatic polymerization of pyrrole catalyzed by a laccase (benzenediol:oxygen oxidoreductase, EC 1.10.3.2) from Trametes versicolor. Transmission electron microscopy revealed that the MWNTs were uniformly coated with very thin layers of PPy without any indication of globular polymer aggregate formations. The enzymatic synthesis of the MWNTs/PPy composites was quite simple being performed in a one‐pot aqueous solution (pH 4.0) under mild reaction conditions. The potential of the composites with respect to the development of energy storage devices was demonstrated by fabricating a two‐electrode coin cell capacitor (diameter 20 mm, thickness 1.6 mm) utilizing the composites as electrode materials. The capacitance of the cell was 28.0 F g^?1 for the electrode material as measured by a galvanostatic charge–discharge method. The energy density and power density were 2.55 and 805 W kg^?1, respectively, which were close to those of the capacitors classified as ultracapacitors. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43307.     

Synthesis and characterization of modified bismaleimide/polysulfone semi‐interpenetrating polymer networks

The present work reports a new method of preparing semi‐interpenetrating polymer network (semi‐IPN) membranes through in situ polymerization of bismaleimide (BMI) within polysulfone (PSF). It was found that BMI could be polymerized at ambient conditions in the presence of a proton donor and PSF without the use of an initiator or a catalyst. Chemical structure characterization of these semi‐IPNs by Fourier transform infrared attenuated total reflection (FTIR‐ATR) revealed the possibility of imide cleavage and formation of amic acid when BMI polymerization was continued for a longer time while X‐ray photoelectron spectroscopy (XPS) revealed the protonation of imide nitrogen at shorter polymerization time. It was also found that size of thermoset BMI phase within the PSF thermoplastic has a significant impact on glass‐transition temperature of resulting semi‐IPN. By controlling the thermoset/thermoplastic phase separation of semi‐IPNs through dope composition and formation techniques, gas separation membranes with comparable selectivity and permeance that were up to 12 times higher than corresponding PSF membranes were formed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 369–379, 2006     

Porosity,mechanical properties,and damping ratio of particulate‐filled polymer composite for precision machine tools

Particulate‐filled polymer composites (PFPC) have received a great deal of attention in the field of precision machine tools because of their excellent vibration‐alleviating property. However, applications of PFPC in the field of precision machine tools are restricted by its limited mechanical strength. The pores in PFPC are one of the key influences on its mechanical properties, such that the porosity determines the overall mechanical properties of the PFPC directly. In this paper, the relationship between porosity and mechanical properties (compressive strength, flexural strength, elasticity modulus) and damping ratio of PFPC was studied systematically. A strong correlation between the porosity and the mechanical properties and damping ratio of PFPC was found. The results show that the mechanical properties (damping ratio) of PFPC deteriorated (increased) dramatically with increasing porosity. An empirical formula was proposed for the relation between the porosity and the mechanical properties (and damping ratio) of PFPC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44435.