Preparation and dielectric properties of sulfonated poly(aryl ether ketone)/acidified graphite nanosheet composites

Percolative dielectric composites of sulfonated poly(aryl ether ketone) (SPAEK) and acidified graphite nanosheets (AGSs) were fabricated by a solution method. The dielectric constant of the as‐prepared composite with 4.01 vol % AGSs was found to be 330 at 1000 Hz; this was a significant increase compared to that of pure SPAEK. Through the calculation, a low percolation threshold of the AGS/SPAEK composite was confirmed at 3.18 vol % (0.0318 volume fraction) AGSs; this was attributed to the large surface area and high conductivity of the AGSs. Additionally, our percolative dielectric composites also exhibited good mechanical performances and good thermostability, with a tensile strength of 71.7 MPa, a tensile modulus of 1.91 GPa, a breaking elongation of 16.4%, and a mass loss temperature at 5% of 336°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40028.     

Sulfonated poly(arylene ether ketone)s prepared by direct copolymerization as proton exchange membranes: Synthesis and comparative investigation on transport properties

Sulfonated poly(aryl ether ketone)s (SPAEK) copolymers were synthesized by aromatic nucleophilic polycondensation from 3,3′, 5,5′‐tetramethyl‐4, 4′–biphenol, 1,4‐bis(4‐fluorobenzoyl) benzene, and disulfonated difluorobenzophenone. The SPAEK membranes did not exhibit excessive swelling in hot water and at the same time show the proton conductivities in the range of 0.030 S/cm to 0.099 S/cm at 80°C. The methanol diffusion coefficients of the SPAEK membranes were in the range of 4.7 × 10^?7 to 8.1 × 10^?7cm²/s measured at 25°C. The transport properties of this series of SPAEK copolymers were compared to poly(aryl ether ether ketone)s (SPEEK), poly(aryl ether ether ketone ketone)s (SPEEKK), and Nafion® membranes. It was found that the transport properties (including proton conductivity and methanol permeability) follows the trend of SPEEKK‐60 < SPAEK‐60 < SPEEK‐60 < Nafion® 117, the order of which is also attributed to the differences in the chemical structure of the polymers and the membrane morphology. In general, this novel series of SPAEK membranes possess various advantages, such as low cost of the initial monomers, high thermal and mechanical stability, and low methanol permeability while simultaneously possessing sufficient proton conductivity, which makes them notably promising as proton exchange membrane (PEM) materials in direct methanol fuel cell (DMFC) applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of microstructural functional polyaniline layers on SPEEK/HPW proton exchange membranes

In this study, a method is developed to fabricate sulfonated poly (ether ether ketone)/phosphotungstic acid‐polyaniline (SPEEK/HPW‐PANI) membranes by in situ polymerization of aniline for the purpose of decreasing the weight loss of HPW in the membranes. The synthesis involves the production of a SPEEK/HPW hybrid membrane followed by different layer of PANI coatings on the membrane surface, and subsequent treatment using drying in vacuum procedures. The scanning electronic microscopy images showed that HPW had good compatibility with SPEEK polymers and energy dispersive X‐ray spectroscopy revealed the successfully doping with HPW and polymerization of PANI. The surface of SPEEK/HPW‐PANI becomes more compact than that of SPEEK/HPW and pure SPEEK, which may lead to reduce the water uptake and swelling property. The proton conductivity was found for the SPEEK/HPW‐PANI‐5 composite membrane (91.53 mS/cm at 80°C) higher than that of pure SPEEK membrane (68.72 mS/cm at 80°C). Better thermal stability was determined in both SPEEK/HPW and SPEEK/HPW‐PANI membranes than pristine SPEEK membrane. Therefore, PANI is a good potential coating for organic–inorganic hybrid e.g. SPEEK/HPW membrane materials to improve their hydrothermal stable properties and SPEEK/HPW PANI is a material that shows promise as a proton exchange membranes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41033.     

Molecular composites obtained by polyaniline synthesis in the presence of p‐octasulfonated calixarene macrocycle

Polyaniline (PANI) molecular composites were synthesized by chemical oxidative polymerization of the aniline and aniline dimer, N‐phenyl‐1,4‐phenylendiamine, in the presence of a macrocycle, calix[8]arene p‐octasulfonic acid (C8S), using ammonium peroxidisulfate as oxidant. The macrocycle has acted both as acid dopant and surfactant to obtain processable PANI‐ES. The PANI/calix[8]arene p‐octasulfonic acid composite was also obtained by a simple doping of PANI emeraldine base form with calix[8]arene sulfonic acid. The structure of materials was confirmed by Fourier transform infrared, UV–vis and nuclear magnetic resonance spectroscopy. All synthesized composite materials are amorphous and soluble in chloroform, dimethylsulfoxide, NMP, showing excellent solution‐processing properties combined with electrical conductivity. Cyclic voltammetry evidenced a good electroactivity for the composite films. Dielectric properties (dielectric constant and dielectric losses) were determined and are comparable with those of other PANI/ionic acid polymer composites. Preliminary studies have evidenced a high dielectric constant (10⁴ at 100 Hz) and electrical conductivity of 6 × 10^?3 S/cm for PANI composites. From sulfur elemental analysis of the PANI/calixarene, it results that the content in macrocycle is ～30% (weight). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhancement of physical properties of electroactive polyimide nanocomposites by addition of graphene nanosheets

Electroactive polyimide (EPI) nanocomposites with amino‐capped aniline trimer and 4′‐(4,4′‐isopropylidene‐diphenoxy)bis(phthalic anhydride) as monomers, and functionalized with carboxyl‐graphene nanosheets, were prepared by thermal imidization. The as‐prepared electroactive polyimide/graphene nanocomposite (EPGN) materials were then characterized by Fourier transform infrared spectroscopy and transmission electron microscopy. In situ monitoring of the redox behavior of the as‐prepared EPGN materials was performed by cyclic voltammetry studies. The effects of material composition on the mechanical, thermal, thermal transport, dielectric and molecular barrier properties of EPGN membranes were investigated by dynamic mechanical analysis, TGA, DSC, the transient plane source technique, LCR meter and gas permeability analyzer, respectively. It should be noted that all the properties of the EPGN membranes were found to improve substantially over those of non‐electroactive polyimide and EPI. For example, upon loading of 1 wt% graphene, EPGN membranes were found to have an increase of over 20%, 5%, 65% and 20% in mechanical strength, thermal stability, thermal conductivity and dielectric constant, respectively, and a reduction of over 20% in gas permeability. © 2013 Society of Chemical Industry     

Cross‐linked Poly(arylene ether ketone) Proton Exchange Membranes with High Ion Exchange Capacity for Fuel Cells

Sulfonated poly(arylene ether ketone) (SPAEK) possessing the pendant carboxylic acid groups was synthesized. The carboxylic acid groups of SPAEK were reacted with a cross‐linking reagent to prepare a cross‐linked membrane with a high ion exchange capacity (IEC), a high oxidative stability, and an excellent mechanical strength. The cross‐linking hindered the mobility of the polymer chains and thus strongly affected the water uptake and the methanol permeability of the membranes. Also, as the cross‐linker used in this study bore sulfonic acid groups, cross‐linking did not lead to a noticeable loss of the proton conductivity. The cross‐linked SPAEK membrane with 20% cross‐linking density, CSPAEK‐20% membrane, exhibited a high proton conductivity of 0.045 S cm^–1 associated with a high IEC value of 1.78 mmol g^–1 but a low methanol permeability of 4.3 × 10^–7 cm² s^–1. The CSPAEK‐20% membrane also showed excellent cell performance and oxidation resistance.     

Poly(vinyl alcohol)‐based polymeric membrane: Preparation and tensile properties

A series of poly(vinyl alcohol) (PVA)‐based single‐layer organic polymeric membranes were prepared via the crosslinking of PVA with different amounts of formaldehyde. Meanwhile, for comparison, both a three‐layer organic polymeric membrane and a hybrid composite membrane were also prepared by the layer‐upon‐layer method. Their thermal stability and tensile properties were investigated to examine the effect of crosslinking on the membrane performances. Thermogravimetric analysis and differential scanning calorimetry thermal analyses showed that the thermal degradation temperature of the single‐layer crosslinked membrane C reached up to 325°C. Tensile testing indicated that the three‐layer organic polymeric membrane E had excellent tensile strength among these single‐layer and three‐layer membranes. The swelling properties revealed that the swelling degree value of these membranes decreased with an increase in methanol concentration; this suggests that they were not easily swollen by the methanol solution, which is meaningful for the separation of organic mixtures. Field emission scanning electron microscopy images exhibited that the crosslinking of functional groups impacted their structures and confirmed that their mechanical properties were related to their structures. These findings suggest that the crosslinking of functional groups is an effective method for adjusting the tensile strength of PVA‐based organic polymeric membranes and related hybrid composite membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Modified polyaniline and its effects on the microstructure and antistatic properties of PP/PANI‐APP/CPP composites

Polypropylene (PP) composites that contain poly(aniline) (PANI) and ammonium polyphosphate crystalline form II (APP‐II) have both antistatic and flame‐retardant properties. In the present study, double anti‐functional PANI was prepared via in situ polymerization in the presence of APP‐II. Analysis of the Fourier transform infrared spectra demonstrated that PANI was synthesized successfully with APP‐II and that modified PANI (PANI‐APP) was obtained. Next, PP/PANI‐APP/chlorinated poly(propylene) (CPP) and PP/PANI/CPP composites were prepared. The results showed that the volume resistivity of the PP/PANI‐APP/CPP composite was at least 100 times less than that of the PP/PANI/CPP composite. The microstructures of the corresponding composites were investigated carefully by scanning electron microscopy and wide angle X‐ray diffraction. The areas of the conductive regions and the percentage crystallinity of PP in the PP/PANI‐APP/CPP composite were distinctly higher than those in the PP/PANI/CPP composite, i.e., by about 10% and 7%, respectively. In addition, experimental analyses of the limiting oxygen index and thermogravimetry showed that the PP/PANI‐APP/CPP composite had advantages compared with PP in terms of its flame‐retardant properties thermal stability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40732.     

Synthesis of processible doped polyaniline‐polyacrylic acid composites

Processible composites of emeraldine salt form of polyaniline (PANI) with polyacrylic acid (PAA) are synthesized and studied for their structural, electrical, mechanical, thermal, and electrochemical properties. The processible conducting composites of various weight percentage from 20 wt % to 90 wt % (of PANI) have been prepared by mixing the PANI and PAA under vigorous stirring and sonication conditions. Self‐standing films of electroactive homogeneous composites are obtained by solution casting method. A significant improvement in processibility, crystallinity, and thermal stability is observed in the composites; however, the electrical conductivity decreased remarkably as the percentage of PANI is decreased in the composites. The 60 wt % PANI‐PAA composite showed crystalline structural property with orthorhombic crystal system and cell parameters as a = 5.93Å, b = 7.57Å, and c = 10.11Å. The 60 wt % PANI‐PAA composite also showed better thermal stability and highest capacitance amongst all the composites and used as an active material for development of electrochemical capacitors (parallel plate assembly). The processible composites based electrochemical capacitors using 0.5 M NaClO₄‐Acetonitril electrolyte showed super capacitance with ease in fabrication and cost effectiveness in comparison to other similar materials based capacitors. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal conductivity of PVDF/PANI-nanofiber composite membrane aligned in an electric field

Poly(vinylidene fluoride)(PVDF) is a semi-crystalline thermoplastic polymer with excellent thermal stability,electrochemical stability and corrosion resistance, which has been widely studied and applied in industrial nonmetallic heat exchanger and piezoelectric-film sensor. In this study, polyaniline(PANI) nanofibers were synthesized using dodecylbenzene sulfonic acid as the surfactant. The obtained PANI nanofibers were blended in PVDF matrix to enhance thermal conductivity and tensile strength of composite materials. Electric field was applied for the orientation of membrane structure during membrane formation. Scanning electron microscope(SEM) images exhibited that the PANI nanofibers were well-dispersed in the composite membranes. The structure of composite membranes was more orderly after alignment. X-ray diffraction(XRD) and differential scanning calorimetry(DSC) indicated that the content of PANI nanofibers contributed to the transformation of PVDF from α-phase to β-phase. Both the tensile strength and thermal conductivity of composite membranes were significantly improved. This tendency was further enhanced by the application of electric field. The maximum tensile strength was obtained when the content of PANI nanofibers was 3 wt%, which was 46.44% higher than that of pure PVDF membrane. The maximum thermal conductivity of composite membranes after alignment was 84.5% greater than that of pure PVDF membrane when the content of PANI nanofibers was 50 wt%. The composite membrane is a promising new potential material in heat transfer field and the mechanism explored in this study would be informative for further development of similar thermal conductive polymeric materials.     

Fabrication of honeycomb‐patterned polyaniline composite films containing cellulose triacetate with high conductivity and mechanical stability

Polyaniline (PANI) biocomposites were prepared via in situ polymerization of aniline monomer with cellulose triacetate (CTA) and by using ammonium persulfate as an initiator in an aqueous solvent. The composites exhibited high solubility in organic solvents due to the incorporated CTA component, and enabled the fabrication of honeycomb‐patterned thin films by casting the PANI composite solutions under humid conditions. The honeycomb‐patterned PANI–CTA composite films showed a high conductivity corresponding to about 1.5 S/cm, good mechanical stability, and high flexibility. The composites have a potential advantage comparing to pure PANI because of biodegradability and high solubility due to included CTA. These composite films can usefully be applied in the field of bio‐nanotechnology and medicine including micro‐structured electrode surfaces, filters for cell sorting, and bio‐interfaces and so on. POLYM. COMPOS., 37:2649–2656, 2016. © 2015 Society of Plastics Engineers     

Preparation and characterization of phosphoric acid composite membrane by radiation induced grafting of 4‐vinylpyridine onto poly(ethylene‐co‐tetrafluoroethylene) followed by phosphoric acid doping

Preparation of phosphoric acid composite membranes by radiation induced grafting of 4‐vinylpyridine (4‐VP) onto electron beam irradiated poly(ethylene‐co‐tetrafluoroethylene) film followed by phosphoric acid doping was investigated. The effect of grafting parameters (monomer concentration, absorbed dose, reaction time, and temperature) on the degree of grafting (G%) in the membrane precursor and its relation with the amount of acid doped was studied. The proton conductivity of the obtained membranes was evaluated in correlation with G% and temperature using ac impedance. Fourier transform infrared, thermal gravimetric analysis, X‐ray diffraction, and universal mechanical tester were used to investigate chemical composition, thermal resistance, structure, and mechanical properties of the membranes, respectively. The membranes of 34 and 49% recorded high proton conductivity in the magnitude of 10^‐2 S cm^‐1 without humidification. The membranes were also found to have reasonable mechanical integrity together with thermal stability up to 160°C. The obtained membranes are suggested to be less‐water dependent and have potential for testing in high temperature polymer electrolyte membrane fuel cell. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhanced microwave absorbing properties of lightweight films based on polyaniline/aliphatic polyurethane composites in X band

Polymer blends based on nanostructured polyaniline (PANI) doped with hydrochloric acid (HCl) and para‐toluene sulfonic acid (PTSA) introduced into aliphatic polyurethane matrix (PU) are synthesized to produce flexible thin composite films for microwave absorbers. The effects of dopant type, PANI content and film thickness on morphologies, dielectric and microwave absorption properties in the X‐band are studied. It reveals that real and imaginary parts of the complex permittivity are proportional to filler concentrations and type of doped PANI. The PANI‐PTSA/PU films show higher permittivity and better microwave absorbing properties than PANI‐HCl/PU for the same weight fraction of PANI. The minimum reflection loss RL_(dB) values for the PANI‐PTSA/PU are ?37 dB at (20% PANI and 11.6 GHz) and ?30 dB at (15% PANI and 11.3 GHz) for thicknesses of 1.2 and 1.6 mm, respectively. These high values of reflection losses make the obtained lightweight and flexible composites promising radar absorbing materials (RAM). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40961.     

Improving the dielectric performance of poly(vinylidene fluoride)/polyaniline nanorod composites by stretch‐induced crystal transition

The introduction of conductive polyaniline (PANI) can significantly improve the dielectric constant of polymer‐based materials. However, there is a drawback of high dielectric loss. Herein, a simple and efficient stretching process was applied to improve the dielectric performance of poly(vinylidene fluoride)/PANI (PVDF/PANI) nanorod films through the stretch‐induced crystal transition from non‐polar α‐crystal to polar β‐crystal in PVDF and the oriented distribution of PANI nanorods. XRD, DSC and Fourier transform IR analyses indicate that the stretched PVDF and stretched PVDF/PANI films possess a high content of β‐crystal at the stretching temperature of 135 °C under a stretching ratio of 200%–400%. Furthermore, the stretched PVDF/PANI film with 10 wt% PANI displays a high dielectric constant of 338 at 100 Hz, which is increased by 20% compared to non‐stretched PVDF/PANI film (281). More importantly, the corresponding dielectric loss is reduced from 0.31 for the non‐stretched film to 0.17 for the stretched film. © 2018 Society of Chemical Industry     

Effect of surface functionalization on the properties (rheological,mechanical, and dielectric) and microtopography of PEN/CPEN‐f‐CNTs nanocomposites

Novel carboxylic poly(arylene ether nitrile)s (CPEN) functionalized carbon nanotubes (CPEN‐f‐CNTs) were successfully prepared by a simple and effective solvent–thermal route. The CPEN‐f‐CNTs were subsequently used as the novel filler for preparation of high performance poly(arylene ether nitrile)s (PEN) nanocomposites. The SEM characterization of the PEN nanocomposites revealed that the CPEN‐f‐CNTs present better dispersion and interfacial compatibility in the PEN matrix, which was confirmed by the linear rheological analysis (Cole–Cole plots) as well. Consequently, the improved thermal stability (increased initial and maximum decomposition temperature) and enhanced mechanical properties (tensile strength and modulus) were obtained from nanocomposites using CPEN‐f‐CNTs. More importantly, the PEN/CPEN‐f‐CNTs nanocomposites not only show a high dielectric constant but also have low dielectric loss. For example, a dielectric constant of 39.7 and a dielectric loss of 0.076 were observed in the PEN composite with 5 wt% CPEN‐f‐CNTs loading at 100 Hz. Therefore, the flexible PEN/CPEN‐f‐CNTs nanocomposites with outstanding mechanical, thermal and dielectric properties will find wide application in the high energy density capacitors. POLYM. COMPOS., 37:2622–2631, 2016. © 2015 Society of Plastics Engineers     

Palladium and platinum sorption on a thiocarbamoyl‐derivative of chitosan

Novel proton exchange membranes are solvent‐cast from N,N‐dimethylacetamide (DMAc) solutions of the crosslinked poly(arylene ether ketone) copolymer with pendant carboxylic acid group (C‐SPAEK) via poly(ethylene glycol) (PEG) with different amounts. These membranes are formed as a result of physical and chemical crosslinking. In this study, ¹H‐NMR and FTIR have been used to confirm the chemical structures of the copolymers. Mechanical and thermal properties, swelling and proton conductivity are affected by the crosslinker (PEG) content in the copolymers. Compared to the noncrosslinked C‐SPAEK membrane, the crosslinked membranes become more flexible and greatly reduced water uptake and swelling ratio with only slight sacrifice in proton conductivities. And the crosslinked membranes keep higher proton conductivities without a sharply decrease at higher temperature. These results show that the crosslinked membranes have potential applications as proton exchange membranes for fuel cell. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High dielectric constant polyaniline/epoxy composites via in situ polymerization for embedded capacitor applications

Polyaniline (PANI)/epoxy composites with different polyaniline (PANI) contents were successfully developed by in situ polymerization of aniline salt protonated with camphorsulfonic acid within epoxy matrices and fully characterized. The influence of PANI loading levels on various properties was also explored. Dielectric and electrical properties of PANI/epoxy composites were studied for samples in parallel plate configuration. A PANI/epoxy composite prepared in this fashion reached a high dielectric constant close to 3000, a dielectric loss tangent less than 0.5 at room temperature and 10 kHz. The hardener type was also found as a critical parameter for the dielectric properties of PANI/epoxy composites. The distribution of the conductive element clusters within the polymer matrix was studied by SEM and correlated to the dielectric behavior of the composite films.     

Study on mechanical and thermal properties of composites of cis‐ and trans‐polyisoprene blends filled with polyaniline

In this study, the effect of polyaniline (PANI) as filler has been investigated on the mechanical and thermal properties of blends of cis‐polyisoprene (CPI) and trans‐polyisoprene (TPI) by dynamic mechanical analyzer and transient plane source technique, respectively. The samples blend composites with different concentration of PANI have been prepared by solution casting method and characterized through X‐ray diffraction. Experimental results from mechanical and thermal measurements show that incorporation of PANI in CPI/TPI blends increases glass transition temperature, mechanical properties and thermal properties whereas decreases damping property. This increase in different properties is only upto a certain amount of PANI and over this amount an entirely apposite behavior is observed. This observed behavior of mechanical and thermal properties is explained on the basis of crystallinity and crosslink density. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Melt‐processed polyaniline nanofibers/LDPE/EAA conducting composites

The melt‐processable polyaniline nanofibers doped with superfluous dodecylbenzenesulfonic acid (PANI‐DBSA) were synthesized using the interfacial polymerization and thermal doping technique. Conducting composites composed of PANI‐DBSA nanofibers, low‐density polyethylene (LDPE), and ethylene‐acrylic acid copolymer (EAA) as compatibilizer were prepared by melt processing. The effects of PANI‐DBSA nanofibers on the electrical conductivity, and mechanical properties, and morphological structure of the composites were investigated. As a result, the conducting composites had lower percolation threshold (4 wt%) due to the easy formation of conducting paths for fibrillar‐like PANI‐DBSA in the LDPE matrix, which was also confirmed by the frequency dependence of the real part of the AC conductivity. The Scanning electron microscopy (SEM) images indicated that the PANI‐DBSA nanofibers were dispersed uniformly in the matrix. The mechanical properties of the composites were improved at the low PANI‐DBSA load (about 1 wt%), but they were deteriorated at high PANI‐DBSA content. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers