Preparation and electrochemical properties of polyaniline/reduced graphene oxide composites

Polyaniline (PANI)/reduced graphene oxide (rGO) composites were synthesized by in situ oxidative polymerization of aniline on reduced graphene sheets. Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and scanning electron microscopy were used to characterize the composites. The results indicated PANI/rGO composites were produced and contained covalent bonds between the functional groups of PANI and rGO. A uniform coating of PANI on the rGO sheets had a synergistic effect on the properties of the composites. The electrochemical properties of the PANI/rGO composites produced using different feed ratios of aniline to rGO were studied. The results showed that the composites exhibited a maximum specific capacitance of 797.5 F/g at 0.5 A/g and minimum charge transfer resistance of 0.98 Ω when the feed ratio of aniline to rGO was 2:1. These values were superior to those of pure PANI and rGO. The composites also displayed excellent cycling stability, with specific capacitance retention of 92.43% after 1000 cycles. These stable structural composites show promise for the development of new supercapacitor applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46103.     

A sensitive voltammetric sensor based on synergistic effect of graphene–polyaniline hybrid film for quantification of calcium antagonist lercanidipine

A chemically modified sensor based on the synergistic effect of graphene and polyaniline for electrochemical sensing of calcium antagonist lercanidipine (LCP) has been developed. Scanning electron microscopy, electrochemical impedance spectroscopy, square‐wave voltammetry, and cyclic voltammetry were utilized to characterize the morphology and electroanalytical performance of the fabricated sensor. Under optimized conditions, reduction peak current was linear over the wide concentration range from 5 to 125 ng mL^?1 with correlation coefficient of 0.9998. The limit of detection and the limit of quantification were found to be 1.94 and 5.89 ng mL^?1. The developed sensor also exhibited good reproducibility and long‐term stability. In addition, the proposed method was successfully applied to the determination of LCP in pharmaceutical formulation which is proved by recovery studies. Graphene–polyaniline composites are expected to be promising material for biosensing applications because of the ease of fabrication, excellent electrochemical performance, and high electroactive surface area. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40959.     

Thermal,electrical, and dielectric properties of reduced graphene oxide–polyaniline nanotubes hybrid nanocomposites synthesized by in situ reduction and varying graphene oxide concentration

In this study, reduced graphene oxide (RGO) has been introduced as conductive filler within polyaniline (PAni) nanotubes (PAniNTs) by in situ chemical reduction method to enhance the properties of PAniNTs. The effect of varied concentration of in situ reduced GO on the structural, thermal, electrical, and dielectric properties of RGO–PAniNTs nanocomposites have been investigated by high resolution transmission electron microscope, X‐ray diffraction, Fourier transform infrared, thermogravimetric analysis, I–V characteristics, and impedance analyzer. The enhanced thermal stability of the nanocomposites has been analyzed from the derivative thermogravimetric curves in terms of onset and rapid decomposition temperature. The transport mechanisms have been studied by fitting the nonlinear I–V characteristics to the Kaiser model. The dielectric relaxation phenomena have been investigated by permittivity and modulus formalisms. Characteristic relaxation frequency of RGO–PAniNTs nanocomposites shifts toward higher frequency with increasing RGO concentration indicating a distribution in conductivity relaxation. The distribution of relaxation time has been studied by fitting the imaginary modulus spectra of the nanocomposites to Bergman modified KWW function. The ac conductivity spectra are fitted to the Jonscher's power law equation and enhanced conductivity value of 1.26 × 10⁻³ S cm⁻¹ is obtained for 40 wt % of RGO compared to 1.22 × 10⁻⁴ S cm⁻¹ for PAniNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45883.     

Influence of monomeric concentration on mechanical and electrical properties of poly(styrene-co-acrylonitrile) and poly(styrene-co-acrylonitrile/acrylic acid) yarns electrospun

Two series of copolymers were synthesized by emulsion polymerization: poly(styrene-co-acrylonitrile) P(S:AN) and P(S:AN-acrylic acid) P(S:AN-AA). The monomeric concentrations in both series were: 0:100, 20:80, 40:60, 50:50 (wt%:wt%), and 1 wt% of AA. The copolymers were dissolved in N,N-dimethylformamide (4–10 wt%) and were electrospun. Polymeric yarns were collected using a blade collector. The synthesized and fabricated materials were characterized by known techniques. Mechanical and electrical properties of polymeric yarns indicated a dependence of monomeric concentration. Elastic modulus increases as acrylonitrile concentration increases (up to 30 MPa). Yarns were submitted to degradation process into saline solution, where the acrylic acid content kept a constant elastic modulus at long times. The electrical current into yarns was higher when the concentration is 50:50 wt%:wt% (1.2 mA). The cytotoxicity results showed a cell viability close to 100% for yarns without AA.     

Poly(styrene–maleic anhydride) functionalized graphene oxide

In this study, poly(styrene–maleic anhydride) functionalized graphene oxide (SMAFG) was fabricated with in situ polymerization. The sample was characterized with Raman spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, and ultraviolet–visible absorption. The results of the experiments show that the thermal stability of SMAFG was improved significantly, and it also possessed a good dispersion in N,N‐dimethylformamide, N,N‐dimethylacetamide, aniline, and certain organic solvents. The calculated Hildebrand parameter of SMAFG was 23.8 MPa^1/2. This new method will broaden the applications of graphene, and the experiment showed that it could effectively improve the strength of polyamide 6 (PA6) compared with the pure PA6 fiber. The tensile strength of the SMAFG/PA6 composite fiber improved 29%, and the Young's modulus improved 33%, so this kind of functionalized graphene oxide can be used in the preparation of polymeric composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41987.     

Synthesis and electrochemical properties of graphene oxide/nanosulfur/polypyrrole ternary nanocomposite hydrogel for supercapacitors

A method for synthesizing Graphene oxide (GO)/nano‐sulfur/polypyrrole (PPy) ternary nanocomposite hydrogel is depicted. The higher surface area of GO, PPy porous structure and their excellent conductivity are utilized, and the GO hydrogel can be made easily. The products are characterized by field‐emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, and electrochemical workstation. The results demonstrated that GO/nano‐S/PPy ternary nanocomposite hydrogel is successfully synthesized. The electrochemical properties are investigated by cyclic voltammetry, galvanostatic charge/discharge measurements, and cycling life in a three‐electrode system in 1M Li₂SO₄ electrolyte solution. The GO/nano‐S/PPy ternary nanocomposite hydrogel exhibit a high specific capacitance of 892.5 F g^?1 at scan rates of 5 mV s^?1 and the capacitance retain about 81.2% (594.8 F g^?1) of initial capacitance (732.5 F g^?1) after 500 cycles at a current density of 1 A g^?1. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40814.     

Pressure‐crystallized piezoelectric structures in binary fullerene C70/poly(vinylidene fluoride) based composites

The effective fabrication of polar crystalline structures of poly (vinylidene fluoride) (PVDF), such as beta and gamma, is crucial to the development of piezoelectric polymer devices. In this study, we report the effect of pressure on binary fullerene C70/PVDF‐based composite with an overall good C70 dispersion, which was prepared by an easy physical and mechanical route. The C70/PVDF composites were crystallized in a piston‐cylinder high‐pressure apparatus, and the polymeric crystalline structures totally with extended‐chain piezoelectric beta‐ or gamma‐form lamellae were successfully achieved in the composite samples by varying temperature, pressure, crystallization time, and composite composition. The c‐axis thickness of the extended‐chain beta‐form lamellae of PVDF in the composites increased and decreased with the increase of the applied temperature and pressure, respectively, and it increased with the increase of crystallization time. Although C70 was found to be negative for the rapid formation of beta‐form PVDF crystals, it played an important role in the growth of a beta‐form PVDF nanowire with extended‐chain crystalline substructures. The template‐free formation of such piezoelectric nanowires was attributed to a C70‐induced self‐assembly of the polymer, driven by physical interactions at high pressure. The pressure‐crystallized C70/PVDF composites, self‐reinforced with unique one‐dimensional piezoelectric structures, may diversify niche applications in advanced functional polymeric devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1823–1833, 2013     

The conductive network made up by the reduced graphene nanosheet/polyaniline/polyvinyl chloride

In this work, due to the effective interfacial interactions between reduced graphene oxide (RGO) planes and polyaniline (PANI) chains, a conductive network was designed and fabricated by in situ polymerization of aniline monomer on the RGO planes. Then, the polyvinyl chloride (PVC) was modified with the conductive network by simple solution blending. A significant enhancement in the conductive properties of PVC films was obtained with a 4.0 wt % RGO and 7.0 wt % PANI loading. When the PANI was coated on RGO, the PANI was easier to connect mutually and enhanced the conductivity network for composites. Thermal analysis of the composite films showed the thermal stability of PVC was also improved after modified. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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

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

Room temperature CO sensing by polyaniline/Co3O4 nanocomposite

Polyaniline/cobalt oxide (PANI/Co₃O₄) nanocomposites have been investigated for their sensitivity towards carbon monoxide (CO) gas at room temperature. The Co₃O₄ nanoparticles were prepared by ultrasound assisted coprecipitation method and then incorporated into the PANI matrix. Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy, powder X‐ray diffraction, and field emission scanning electron microscopy have been used to characterize the nanomaterials. The PANI/Co₃O₄ nanocomposite sensors were found to be highly selective to CO gas at room temperature. A significantly high response of 0.81 has been obtained for 75 ppm CO concentration with a response time of 40 s. Based on the observations of the sensing study, a mechanism for CO sensing by the nanocomposite has been proposed. Influence of humidity on the sensor response towards CO has also been studied and the results presented. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44115.     

Reduced graphene oxide/silica nanocomposite-reinforced anticorrosive fluorocarbon coating

Reduced graphene oxide-silica (rGO/SiO₂) nanocomposite filler was prepared with a ball milling process and then modified using a coupling agent of NH₂C₃H₆Si(OC₂H₅)₃ (KH-550) to improve its dispersion in the fluoroethylene vinyl ether (FEVE) coating. The surface properties and morphologies of the modified rGO/SiO₂ (M-rGO/SiO₂) nanocomposite filler and M-rGO/SiO₂-reinforced FEVE coating were characterized by using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Electrochemical impedance spectroscopy (EIS) and Tafel polarization curves were applied to illustrate the corrosion resistance of the coating. The results showed that the M-rGO/SiO₂ composite can disperse well in the coating and efficiently extend the corrosion path, enhancing the anti-corrosion property of the FEVE coating. Therefore, the |Z|_{0.01 Hz} of M-rGO/SiO₂ reinforced FEVE coating maintained at around 10¹⁰ Ω·cm² in the 30 days test cycle and a protection efficiency of up to 95.18% was achieved.     

Poly(2,6‐di(thiophene‐2‐yl)‐3,5bis(4‐(thiophene‐2‐yl)phenyl)dithieno [3,2‐b;2',3'‐d]thiophene)/carbon nanotube composite for capacitor applications

A novel monomer, 2,6‐di(thiophene‐2‐yl)‐3,5bis(4‐(thiophene‐2‐yl)phenyl)dithieno[3,2‐b;2',3'‐d]thiophene ( Th₄DTT) has been synthesized and used as an electro‐active material. It has been electropolymerized onto glassy carbon (GC) electrode in sodium dodecyl sulfate (SDS) solution (0.1 M) together with multi‐walled carbon nanotubes (MWCNT). A good capacitive characteristics for P(Th₄DTT)/MWCNT composite has been obtained by electrochemical impedance spectroscopy (EIS), which is, to our best knowledge, the first report on capacitor behavior of a dithienothiophene. A synergistic effect has been resolved by Nyquist, Bode‐magnitude—phase and admittance plots. Specific capacitance of the conducting polymer/MWCNT, calculated from cyclic voltammogram (CV) together with area and charge formulas, has been found to be 20.17 F g^?1. Long‐term stability of the capacitor has also been tested by CV, and the results indicated that, after 500 cycles, the specific capacitance is 87.37% of the initial capacitance. An equivalent circuit model of R_s(C₁(R₁(Q(R₂W))))(C₂R₃) has been obtained to fit the experimental and theoretical data. The double layer capacitance (C_dl) value of P(Th₄DTT)/MWCNT (4.43 mF cm^?2) has been found to be 25 times higher than P(Th₄DTT) (C_dl= 0.18 mF cm^?2). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40061.     

Electromagnetic interference shielding properties of PEDOT/PSS–halloysite nanotube (HNTs) hybrid films

Poly(3,4‐ethylenedioxythiophene)/poly(4‐styrene sulfonate) (PEDOT/PSS) films hybridized with halloysite nanotubes (HNTs) were for the first time investigated for electromagnetic interference (EMI) shielding. The hybridization of the HNTs induced EMI properties for the pristine PEDOT/PSS films, and the content of the HNTs in the hybrid films significantly influenced the EMI properties of the hybrid films. The highest EMI shielding effectiveness of the hybrid film is ?16.3 dB in the measured frequency range from 2 to 13 GHz for the PEDOT/PSS film hybridized with 75% HNTs, using a sample with 4.5 mm thick. The contribution of EMI shielding effectiveness in the hybrid films is mainly due to dielectric loss rather than magnetic loss. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44242.     

Development of flexible sensors using knit fabrics with conductive polyaniline coating and graphite electrodes

The aim of this study was to develop flexible sensors with cotton and polyester knit fabrics as substrates coated with polyaniline (PAni) doped with hydrochloric acid or phosphoric acid. The deposition of PAni onto the knit, polymerization synthesis, and doping of the aniline monomer were performed via an in situ reaction. Graphite dispersion was used to obtain the electrodes of the sensors, which were prepared differently for each substrate. The main evaluation of the sensors was carried out in a humidity chamber under nitrogen (N₂) with the application of drying and wetting cycles. Significant differences were observed in the responses of the sensory devices to humidity, according to the dopant and substrate types. In all tests, the sensor response to variations in the ambient conditions was very good, with a rapid response to changes in the relative humidity, a good sensitivity (up to 34%), and a high reversibility (ca. 70–100%). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44785.     

Piezoresistive behavior of graphene nanoplatelets/carbon black/silicone rubber nanocomposite

Silicon rubber (SR) filled with carbon black (CB) and carbon black (CB)/graphene nanoplatelets (GNPs) hybrid fillers are synthesized via a liquid mixing method. The effects of filler type on the electrical properties and piezoresistive properties (near the region of the percolation) of the conductive SR composites are studied. It is suggested that the conductivity of the composite filled with CB/GNPs hybrid fillers in the mass ratio of 2 : 4 is much higher than that in other ratio. Percolation threshold for CB/GNPs/SR is found to be 0.18 volume fractions lower than CB/SR. Moreover, force rang and linearity of GNPs/CB/SR is higher than CB alone filling system. And the repeatability of the GNPs/CB/SR composites is better than CB/SR. Not repetitive index () of them is 0.1 and 0.18, respectively. The results suggest that the GNPs/CB/SR composites provide a new route toward fabrication of flexible piezoresistive sensors with high performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39778.     

Influence of a graphene oxide additive and the conditions of membrane formation on the morphology and separative properties of poly(vinylidene fluoride) membranes

In this article, we present our study of the influence of a graphene oxide (GO) additive and the method of preparation on the properties of membranes. Poly(vinylidene fluoride) (PVDF)/GO membranes were obtained by an inverse phase method, which was conducted by two different methods. The first one was based on solvent evaporation, and the second method was a coagulation bath in distilled water. Our studies clearly showed that the introduction of the GO nanoadditive into the polymer membrane matrix played a major role in the pore process formation, and it also contributed to the reduction of the contact angle, and this led to an improvement in the hydrophilic properties of the obtained membranes. Furthermore, the PVDF/GO membrane preparation process had a direct influence on the thickness and porosity. Both of these factors had a direct influence on the transport properties of the membrane. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42789.     

Polypyrrole-coated fiber-scaffolds: Concurrent linear actuation and sensing

Conducting polymers such as polypyrrole (PPy) can be deposited on various substrates to obtain conductive electroactive coatings. While electrochemical coatings are generally considered to be more effective, chemical coatings are more industrially suitable, especially on complex substrates. In this work, we aimed to explore the electro-chemo-mechanical response of conductive fiber scaffolds (CFS) prepared by coating PPy (chemically) on glucose-gelatin nanofibre scaffolds. Electroactivity was readily observed in both aqueous and propylene carbonate solutions of lithium bis(trifluoromethanesulfonyl)imide, with mainly anion activity in both cases. A higher actuation response was achieved in the aqueous solutions with strain in the range of 1.2% and stress in the range of 3 kPa. Under both cyclic voltammetry and square wave potential steps driving, stable actuation for over 100 cycles was maintained. In addition to actuation, the CFS samples exhibited concurrent sensory properties, in sensing current densities and mechanical load. The PPy-coated CFS material functioning as both an actuator and a sensor is envisaged to have potential applications in smart materials, soft robotics or e-skin. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48533.     

Piezoelectric coaxial filaments produced by coextrusion of poly(vinylidene fluoride) and electrically conductive inner and outer layers

The development of new thermoplastic polymer‐based piezoelectric sensors with filament geometry is described. These filaments are appropriate for integration into textiles and provide new possibilities in the design and development of low‐cost flexible sensors produced at high rates. The developed three‐layered piezoelectric monofilaments have been produced by coextrusion using poly(vinylidene fluoride) and two different polypropylene‐based electrically conductive polymers. Filaments with about 800‐µm diameter, producing electrical signals proportional to the mechanical deformation applied, were obtained. The signal output has been found adequate for straightforward use with conventional piezoelectric signal conditioning systems. One of the conductive polymers tested allowed better filament geometry and process stability. This article describes the coextrusion production process and the results obtained in the electromechanical tests performed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40710.     

Humidity switching properties of sensors based on multiwalled carbon nanotubes/polyvinyl alcohol composite films

Multiwalled carbon nanotubes (CNTs) were used as the conductive filler of composites for switching type humidity sensor. The CNTs were oxidized by mixed acids (H₂SO₄ : HNO₃) at a mild temperature to modify carboxylic acid (COOH) groups on the surface of the nanotubes. The dispersibility of acid treated CNTs (CNTs‐COOH) in water is much improved, which is beneficial for dispersing CNTs in the polyvinyl alcohol (PVA) matrix without external additives. The obtained CNTs‐COOH/PVA sensors show nonlinear response to relative humidity (RH), that is, switching properties. The resistances of the sensors remain constant before 80% relative humidity (RH) and then increase sharply with RH, indicating excellent switching characteristic of the sensors. The 10 wt % CNTs‐COOH/PVA sensor shows a sensitivity (ΔR/Ro) of 32.3 at 100% RH. The humidity switching properties of CNTs‐COOH/PVA are much better than that of pristine CNTs/PVA. The improvements are attributed to the improved balance between the dispersibility of CNTs‐COOH and electrical conductivity of the composite films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39726.     

Solvothermally reduced graphene oxide/polyimide composites: Structures and thermal and mechanical properties

Solvothermally reduced graphene oxide (SRGO)/polyimide (PI) composites were prepared by in situ polymerization. The structures and components were carefully investigated by X-ray diffraction. Thermal properties were measured by thermogravimetry and dynamic thermomechanical analysis. Mechanical properties were carefully evaluated by tensile testing and scanning electron microscopy. The SRGO/PI composites exhibit extremely high tensile strength and elastic modulus, which is 30% higher than that of pure PI film. Meanwhile, the thermal stability of SRGO/PI composites also displays an obvious enhancement. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47164.