Structural,mechanical, and electrical properties of electropolymerized polypyrrole composite films

Electrochemical polymerization of pyrrole in a solution containing dissolved poly(vinyl alcohol) (PVA) produces a homogeneous, free‐standing, flexible, and conductive polymer film. The films were characterized using infrared spectroscopy, wide‐angle X‐ray diffraction analysis, and scanning electron microscopy. The appearance of standard and some new absorption bands for polypyrrole (PPy) and PVA confirms the composite formation. The mechanical properties of conducting PVA + PPy films were studied and found to be improved with respect to the control PPy films. The electrical conductivity of the PVA + PPy films was measured by using standard four‐ and two‐probe methods. The conductivity of the films was found to depend on the pyrrole content. These conducting composites were further used as gas sensors by observing the change in current with respect to ammonia gas. It was observed that the current decreases when these composites were exposed to ammonia gas. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2511–2517, 2001     

Preparation of conducting composites of polypyrrole using supercritical carbon dioxide

Supercritical carbon dioxide, saturated with pyrrole, was brought into contact with oxidant‐impregnated films of poly(chlorotrifluoroethylene) (PCTFE), crosslinked poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and porous crosslinked polystyrene (PS) in order to form conducting composites via the in situ polymerization of pyrrole. The two nonporous hosts—PCTFE and crosslinked PDMS—did not form conducting composites with polypyrrole (PPy). On the other hand, the electrical conductivity of the PPy composites with carbon dioxide‐swollen PMMA and porous PS ranged from 1.0 × 10^?4 S/cm to 3.0 × 10^?5 S/cm. In these two cases, the level of pyrrole polymerized on the surface or in the pores of the host polymer was sufficient to attain the interconnected conducting polymer networks necessary for electrical conductivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1113–1116, 2003     

Conductive polyaniline/poly(methyl methacrylate) films obtained by electropolymerization

Electrochemical polymerization of aniline, on a Pt foil electrode coated with poly(methyl methacrylate) (PMMA), produces a homogeneous, free-standing, flexible, and conductive polymer film. The conductivity of the films depends on the aniline content and reaches 0.1–0.2 S/cm for films having aniline content of 15% or more. The optimum thickness of precoated PMMA to obtain durable conducting films was found to be in the range of 10–15 μm. Cyclic voltammetric investigation revealed that aniline exhibits a similar electrochemical behavior on a PMMA coated platinum electrode similar to a bare Pt surface. The film gives a fast and reproducible response against ammonia gas within a concentration range of 1.0–0.01%. Scanning electron micrographs indicate that the films have a rough structure consisting of globular regions. © 1996 John Wiley & Sons, Inc.     

Composite nanofibers of conducting polymers and hydrophobic insulating polymers: Preparation and sensing applications

Various conducting polymer/hydrophobic insulating polymer (CP/HIP) composite nanofibers have been prepared by electrospinning and vapor deposition polymerization (VDP) with benzoyl peroxide (BPO) as oxidant. BPO is soluble in N,N-dimethylformamide (DMF) and can form homogenous solutions with hydrophobic polymers such as poly(methyl methacrylate) (PMMA) and polystyrene (PS). High-quality nanofibers of PMMA or PS containing a certain amount of BPO were produced by electrospinning and used as the templates for VDP of pyrrole, 3,4-ethylenedioxythiophene (EDOT), and aniline. The non-woven mats of the resulting CP/HIP composite fibers can be used as the high-sensitive sensing elements of gas sensors. A gas senor based on polypyrrole (PPy)/PMMA composite fibers was fabricated for sensing ammonia or chloroform vapor, and exhibited greatly improved performances comparing with those of the device based on a PPy flat film.     

Conductive polypyrrole composite films prepared using wet cast technique with a pyrrole–cellulose acetate solution

Conductive polypyrrole‐cellulose acetate films were prepared from cellulose acetate (CA) solution of pyrrole (Py) using wet cast method. In the composite films, Py was used as a solvent for CA which was dissolved with different concentration. Then, to prepare PPy–CA composite film, the Py viscous solution of CA was cast on glass plate and immersed in FeCl₃ aqueous solution. When the CA film was formed in the aqueous solution, the polymerized PPy particles having about 1 μm diameter were formed in composite film. The resultant composite films were characterized, showing good film fabrication and electrical conductivity of around 6.9 × 10^?4 to 3.6 × 10¹ S/cm. POLYM. ENG. SCI., 54:78–84, 2014. © 2013 Society of Plastics Engineers     

Preparation and properties of conducting arachidic acid/polypyrrole composite langmuir–blodgett films

Electrically conducting arachidic acid/polypyrrole (PPy) composite films were prepared by exposing the arachidic acid LB films containing ferric chloride to pyrrole vapor. The optimum conditions to deposit matrix LB film were the subphase temperature of 23–25°C, pH of 6.0 and ferric chloride concentration of 5.0 × 10⁻⁵ M. The formation of PPy in the arachidic acid matrix LB films was confirmed by UV-visible spectra, FTIR spectra, and scanning electron micrographs. The average thickness of the composite LB films prepared at 0°C was 1525 Å. The composite films prepared at lower temperatures have more uniform surface and exhibit higher electrical conductivity than the films prepared at higher temperatures do. The in-plain conductivity and the transverse conductivity of the composite film were 10⁻³−10⁻² S/cm and 10⁻⁶S/cm, respectively, and, thus, the conductivity anisotropy was about 10³ © 1996 John Wiley & Sons, Inc.     

Polypyrrole/carbon nanotube composites: Molecular modeling and experimental investigation as anti-corrosive coating

In this work we present a computational method based on molecular mechanics (MM) and dynamics (MD), to predict mechanical properties of polypyrrole (PPy)/polyaminobenzene sulfonic acid-functionalized single-walled carbon nanotubes (CNT-PABS) and PPy/carboxylic acid-functionalized single-walled carbon nanotubes (CNT-CA) composites. Furthermore, experiments were carried out to assess the anticorrosive features of the PPy film and CNT-PABS and CNT-CA PPy reinforced composite coatings. Computational bulk models of PPy/CNT-PABS and PPy/CNT-CA were implemented at atomistic scale and composite coatings were grown in situ onto carbon steel (OL 48-50) electrodes. PPy, PPy/CNT-PABS and PPy/CNT-CA computational models and films were investigated concerning mechanical properties by using computational tools. The obtained films were assessed experimentally as anticorrosive materials using potentiodynamic measurements, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results clearly confirmed that the CNT-PABS and CNT-CA are properly dispersed in the composite coatings and have beneficial effect on mechanical integrity. Moreover, the anticorrosion protecting ability of the composite coatings is significantly higher than the one characteristic to pure PPy. The Young's moduli generally increased with increasing of CNT content and values ranged from 2.67 GPa in the case of pure PPy to 4.15–4.61 GPa in the case of PPy/CNT-PABS composite system.In agreement with earlier results from the literature for conducting polymer organic coatings, the higher conductivity of material leads to a more efficient anticorrosion protection capability, our results exhibited an enhance of conducting features even for very low mass of CNT-PABS or CNT-CA loaded in composites coatings therefore, an improvement of anticorrosion protecting ability.     

Preparation and properties of transparent and conducting nylon 6-based composite films

Highly transparent and conducting polypyrrole–(PPy–N) and polyaniline–nylon 6 (PAN) composite films could be easily obtained by immersing nylon 6 films containing pyrrole or aniline into an oxidant solution such as aqueous FeCl₃ solution or aqueous (NH₄)₂S₂O₈ solution containing HCl. The conductivity, transmittance, and mechanical properties of these composite films were affected by the preparative conditions. The maximum conductivity and transmittance of the PPy–N composite films were 10^?3 S/cm and about 75% at 550 nm, and in the case of the PA–N composite films, 10^?2 S/cm and 75%, respectively. The morphology of PPy–N and PA–N composite films depended on the polymerization conditions, which might be due to the difference in the polymerization speed of pyrrole or aniline in polymer matrices. These PPy–N and PA–N composite films exhibited good environmental stability and excellent mechanical properties. © 1994 John Wiley & Sons, Inc.     

Polypyrrole–poly(heptamethylene p,p′-bibenzoate) conducting materials. Synthesis and characterization

Polypyrrole–poly(heptamethylene p,p′-bibenzoate) conducting materials, PPy–P7MB/ClO₄, were obtained by anodic coupling of pyrrole into a polybibenzoate inert matrix, using perchlorate anions as dopant agent. P7MB is a main-chain liquid crystalline polybibenzoate with adequate mechanical properties and elastic modulus of 1.4GPa at room temperature. The method of synthesis, galvanostatic or potentiostatic electrodeposition, is responsible for differences in the PPy–P7MB/ClO₄ films electrochemical response. FTIR spectra show the complex structures of P7MB and the composite conducting material. The conductivity of PPy–P7MB/ClO₄ films maintains a relatively high value, σ = 13.74Scm^?1, in spite of the insulating effect of polybibenzoate. Film micrographs reveal the typical cauliflower morphology exhibited by polypyrrole and the evolution of film growth with time.     

Polypyrrole/carbon nanotube composites: Molecular modeling and experimental investigation as anti-corrosive coating

In this work we present a computational method based on molecular mechanics (MM) and dynamics (MD), to predict mechanical properties of polypyrrole (PPy)/polyaminobenzene sulfonic acid-functionalized single-walled carbon nanotubes (CNT-PABS) and PPy/carboxylic acid-functionalized single-walled carbon nanotubes (CNT-CA) composites. Furthermore, experiments were carried out to assess the anticorrosive features of the PPy film and CNT-PABS and CNT-CA PPy reinforced composite coatings. Computational bulk models of PPy/CNT-PABS and PPy/CNT-CA were implemented at atomistic scale and composite coatings were grown in situ onto carbon steel (OL 48-50) electrodes. PPy, PPy/CNT-PABS and PPy/CNT-CA computational models and films were investigated concerning mechanical properties by using computational tools. The obtained films were assessed experimentally as anticorrosive materials using potentiodynamic measurements, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results clearly confirmed that the CNT-PABS and CNT-CA are properly dispersed in the composite coatings and have beneficial effect on mechanical integrity. Moreover, the anticorrosion protecting ability of the composite coatings is significantly higher than the one characteristic to pure PPy. The Young's moduli generally increased with increasing of CNT content and values ranged from 2.67 GPa in the case of pure PPy to 4.15–4.61 GPa in the case of PPy/CNT-PABS composite system.In agreement with earlier results from the literature for conducting polymer organic coatings, the higher conductivity of material leads to a more efficient anticorrosion protection capability, our results exhibited an enhance of conducting features even for very low mass of CNT-PABS or CNT-CA loaded in composites coatings therefore, an improvement of anticorrosion protecting ability.     

Preparation and electrochemistry of nanostructured PPy/graphite nanosheets/rare earth ions composites for supercapacitor

Highly conductive PPy/graphite nanosheets/rare earth ions (PPy/nanoG/RE³⁺) composites were prepared via in‐situ polymerization with p‐toluenesulfonic acid as a dopant and FeCl₃ as an oxidant. The microstructures of nanoG and PPy/nanoG/RE³⁺ were characterized by the SEM and TEM examinations. It was found that nanoG and PPy nanospheres formed the uniform composite with the PPy nanospheres embedded on the nanoG surface and/or filled between the nanoG. The effects of nanoG and RE³⁺ on the electrical conductivity and electrochemical performance of the composites were investigated. The results showed that the nanoG and RE³⁺ as the filler had effect on the conductivity and electrochemical performance of PPy/nanoG/RE³⁺ composites, which played an important role in forming a conducting network in PPy matrix. A specific capacitance of as high as 175 F/g at a current density of 1 A/g was achieved over the PPy/nanoG/Gd³⁺ composite. The capacitance of the PPy/nanoG/Gd³⁺ composite decreased only 5.1% after 800 charging/discharging cycles at a current density of 1 A/g. POLYM. ENG. SCI., 54:2731–2738, 2014. © 2013 Society of Plastics Engineers     

Electrically conducting polyaniline‐PBMA composite films obtained by extrusion

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

Preparation of poly(vinylidene fluoride)–polypyrrole composite films by electrochemical synthesis and their properties

Composite films of poly(vinylidenc fluoride–polypyrrole (PVDF–PPy) were prepared by electrochemical polymerization of pyrrole on a very thin PVDF matrix film (～ 0.5 μm). The polymerization was carried out in aqueous media using stainless steel, coated with PVDF matrix, as a working electrode, and p-toluene sulfonate (PTS), as a dopant. The films were prepared at different voltages for different durations of time in order to optimize the conditions of composite formation. The resulting films were characterized by studying IR spectra, conductivity, SEM, XRD, and tensile strength measurements. The mechanical properties of the composites were found to have improved, while the conductivity remained more or less same as that of pure PPy. © 1995 John Wiley & Sons, Inc.     

Preparation of a porous conducting polymer film by electrochemical synthesis–solvent extraction method

Porous conducting polypyrrole (PPy) films have been obtained by electrochemical synthesis–solvent extraction method. The results of scanning electron microscopy (SEM) show that the size and the distribution of pores can be controlled during the electrochemical synthesis. The porous PPy films have sufficiently good mechanical properties, and electrochemical voltammetric studies imply that the porous films also have high electrical conductivity and good electrochemical reversibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 303–307, 2004     

Conducting poly(styrene‐co‐divinylbenzene)/polypyrrole PolyHIPE composite foam prepared by chemical oxidative polymerization

Conducting poly(styrene‐co‐divinylbenzene)/polypyrrole (PPy) polyHIPE (polymerized high internal phase emulsion) composite foams were synthesized via chemical oxidative polymerization method. The effect of solvent and dopant type on the surface morphology and electrical conductivity of composite foams has been investigated. SEM micrographs showed that the morphology of PPy thin film on the internal surface of poly(styrene/divinylbenzene) (poly(St‐co‐DVB) polyHIPE support foam strongly depends on the solvent and dopant type used. Incorporation of dodecylbenzene solfunic acid‐sodium salt (DBSNa) as a dopant in chloroform solvent resulted in formation of a PPy thin film with higher molecular compact structure and electrical conductivity on the support foam as compared to other solvents and another dopant used. Fourier‐transform infrared spectroscopy was used to correlate the electrical conductivity of composite foams to their PPy structural parameters. As expected, the extended conjugation length of PPy in the presence of DBSNa dopant is the main reason for higher electrical conductivity of resultant composite foam. Electrical conductivity measurements revealed that the chemical aging of various conducting foams follows the first‐order kinetic model, which is a representative of a reaction‐controlled aging mechanism. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Conducting polymer blends of polypyrrole with polyvinyl acetate,polystyrene, and polyvinyl chloride based toxic gas sensors

Blends of the conducting polymer, polypyrrole (PPy), and in the insulating host polymers, polyvinyl acetate (PVAc), polystyrene (PS), and polyvinyl chloride (PVC) resin, have been prepared chemically. Threshold conductivities occur at about 5% for PPy in blends with host polymers. The characterizations of these blends were done by FTIR, UV‐visible, differential scanning calorimetric (DSC), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA). The products of the blends have electrical conductivity comparable to PPy and mechanical properties similar to hosting polymers. The response mechanism of the conducting blends to a selection of gases and vapors was investigated using two techniques, measurement of conductance and mass changes using a four‐point probe method, and a X‐ray fluorescence (XRF) device, respectively. These responses of blends to toxic gases and vapors are more well explained. Prepared films were exposed to hydrogen halides (HCl, HBr, and HI), hydrogen cyanide, halogens (Cl₂, Br₂, and I₂), monochloroacetic acid (MCAA), 1‐3‐5 trichloromethyl benzene (TCMB), methylbenzyl bromide (MBB), bromoacetone (BA), and cyanogen bromide (CB). The changes of conductivity of polymers frequently observed are partly due to one stage in the two‐stage sorption, perhaps involving the swelling of the polymer, then diffusion gases into polymer chains. The swelling of polymers is a slow process, therefore, preswelled polymer films tend to decrease the response times of blends with respect to gases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 49–62, 2003     

One pot synthesis of free standing highly conductive polymer nanocomposite films: Towards rapid BTX vapor sensor

In this work, we report the synthesis of robust, flexible, and free standing PMMA/NGP (nanographitic platlets) composite by one‐pot polymerization technique for sensing organic vapors. The synergy between the NGPs and PMMA matrix through strong interaction results in remarkable electrical and sensing properties of the composite system. The chemical structure and morphology of as‐prepared PMMA/NGP composites were investigated by using FTIR, XRD, and SEM techniques. The electrical conductivity of the prepared PMMA/NGP composites increases with increasing concentration of NGPs owing to the formation of conductive paths within the composite due to the quantum tunneling mechanism. The electrical conductivity of PMMA/NGP composites with different NGP concentration shows a percolation behavior with percolation threshold of ～1.2 wt%. The temperature dependent conductivity studies of the PMMA/NGPs were studied to understand the charge transport mechanism in the composite films by using Mott's Variable range hopping model. The PMMA/NGP composite have been evaluated for detection of benzene, toluene, and xylene vapors and were found to exhibit fast response, rapid recovery, and excellent repeatability. The sensitivity along with the flexibility of PMMA/NGP composite films opens up a new opportunity to fabricate the sensor in any shape as per the requirement of modern electronics. POLYM. ENG. SCI., 58:1074–1081, 2018. © 2017 Society of Plastics Engineers     

Examining the use of TiO2 to enhance the NH3 sensitivity of polypyrrole films

Polypyrrole/Titanium dioxide (PPy/TiO₂) composite thin films were prepared by polymerizing the monomer pyrrole in aqueous solution containing a certain amount of TiO₂ particles at room temperature, and their response to ammonia (NH₃) gas was examined systematically. Compared with the pristine PPy film, which reached the saturation at the concentration of NH₃ beyond 200 ppm, the composite films showed more stable response and higher sensitivity. Furthermore, the PPy/TiO₂ composite thin films exhibited a low detection limit of 2 ppm. The film thickness, which had a strong influence on the film sensitivity to NH₃, could be controlled by varying the polymerization time. The sensitivity to NH₃ gas of the samples with different content of TiO₂ and different molar ratio of PPy/TiO₂/oxidant was studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrical properties and EMI shielding characteristics of polypyrrole–nylon 6 composite fabrics

Polypyrrole (PPy) was polymerized both chemically and electrochemically in sequence on nylon 6 woven fabrics, giving rise to polypyrrole–nylon 6 composite fabrics (PPy–N) with a high electric conductivity. The stability of the composite prepared by electrochemical polymerization (ECP) on chemical oxidative polymerization (COP) fabric was better than that of the composite prepared solely by the COP process, since the AQSA dopant was able to strongly interact with the PPy main chain and had a large molecular structure. The temperature dependence of the conductivity of the composites was verified over four heating and cooling cycles. The change in conductivity over these four repeated heating and cooling cycles was affected by the interaction between the thermal stability of the dopant and the rearrangement of the PPy main chain. The electromagnetic interference shielding efficiency (EMI SE) values were in the range 5–40 dB and depended on the conductivity and the layer array sequence of the conductive fabric. The composites with a high conductivity represented reflection‐dominant EMI shielding characteristics, which are typical of the EMI shielding characteristics of metals. However, composites with low conductivity showed absorption‐dominant EMI shielding characteristics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1969–1974, 2003