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     

Study on the Effect of Polypyrrole and Polypyrrole/Graphene Oxide Nanoparticles on the Microstructure,Electrical and Tensile Properties of Polypropylene Nanocomposites

In this article Polypropylene/Polypyrrole (PP/PPy) and Polypropylene/polypyrrole-graphene oxide (PP/PPy-GO) nanocomposites were prepared by melt mixing. PPy nanoparticles and PPy-GO nanocomposite were prepared by chemical polymerization and served as nanofillers. FTIR, XRD and SEM analysis were used for the characterization of PPy and PPy-GO composites. The effects of PPy and PPy-GO loading level on the morphology, tensile and electrical properties of PP-based nanocomposites were examined. It was found that the Young's modulus and tensile strength increased with the increase of nanofiller content. Tensile results also showed that PPy-GO composite significantly affected the mechanical properties of PP based nanocomposites compared to the PPy nanoparticles. It was observed that the addition of 1% wt. PPy-GO into PP, increased the Young's modulus about 30% compared as with pure PP. Electrical conductivity measurements showed that conductivity of PP nanocomposites increased up to 1 × 10^?3 S/cm for PP/PPy-GO nanocomposites. It was also observed that PP-g-MA improved the distribution of PPy and PPy-GO nanocomposites and affected the morphology, electrical and mechanical properties of PP-based nanocomposites.     

One‐step synthesis of highly conductive PPy/graphite nanosheets/Gd3+ composites

Highly conductive polypyrrole/graphite nanosheets/Gd³⁺ (PPy/nanoG/Gd³⁺) composites are fabricated via in situ polymerization using p‐toluenesulfonic acid as a dopant and FeCl₃ as an oxidant. The effects of the graphite nanosheets and Gd³⁺ loading on the electrical conductivity are investigated. The maximum conductivity of PPy/nanoG/Gd³⁺ composites about 17.86 S/cm found with 3 wt% graphite nanosheets and 6 wt% Gd³⁺ at room temperature. The results showed that the high‐aspect‐ratio structure of graphite nanosheets played an important role in forming a conducting network in PPy matrix. Thermal gravimetric analysis demonstrates an improved thermal stability of PPy in the PPy/nanoG/Gd³⁺ composites. The microstructures of PPy/nanoG/Gd³⁺ are evidenced by the SEM and TEM examinations. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Conducting Composites of Polyurethane Resin and Polypyrrole: Solvent‐Free Preparation,Electrical, and Mechanical Properties

Summary: Three methods were used for solvent‐free preparation of conducting composites of PUR and PPy. In all cases, PUR was prepared from TDI and hydroxol 15‐W as polyol cross‐linker, whereas PPy was obtained upon oxidative coupling of Py using ferric chloride as oxidant. In method 1, PPy powder was dispersed in hydroxol. After addition of TDI the mixture was cured to yield the final product. In method 2, ferric chloride and Py were dissolved in hydroxol and a PPy dispersion was obtained. Then TDI was added and the final product was obtained upon curing. In method 3, Py was dissolved in TDI and ferric chloride dissolved in hydroxol. Then the two solutions were mixed and cured resulting in the simultaneous formation of PPy and PUR. Method 1 led to composites with a specific electrical conductivity σ of 10^?10 S · cm^?1 and a Shore A hardness of 40 to 55. Using methods 2 and 3, composites with σ values of 10^?7 S · cm^?1 and a hardness of 30 to 40 were obtained. Presence of moisture increased the σ values and decreased the hardness. Due to the solvent‐free preparation, the maximum PPy content of the samples was limited to 10 wt.‐%. The studies also demonstrated that the conductivity was mainly dependent on the amount of ferric chloride present in the sample and not on the PPy content, suggesting that the conductivity was ionic.

Flow diagram of different preparation methods for PUR–PPy composites.     

Electrically conductive composites of polyurethane derived from castor oil with polypyrrole‐coated peach palm fibers

Electrically conducting fibers were prepared through in situ oxidative polymerization of pyrrole (Py) in the presence of peach palm fibers (PPF) using iron (III) chloride hexahydrate (FeCl₃·6H₂O) as oxidant. The polypyrrole (PPy) coated PPF displayed a PPy layer on the fibers surface, which was responsible for an electrical conductivity of (2.2 ± 0.3) × 10⁻¹ S cm⁻¹, similar to the neat PPy. Electrically conductive composites were prepared by dispersing various amounts of PPy‐coated PPF in a polyurethane matrix derived from castor oil. The polyurethane/PPy‐coated PPF composites (PU/PPF–PPy) exhibited an electrical conductivity higher than PU/PPy blends with similar filler content. This behavior is attributed to the higher aspect ratio of PPF–PPy when compared with PPy particles, inducing a denser conductive network formation in the PU matrix. Electromagnetic interference shielding effectiveness (EMI SE) value in the X‐band (8.2–12.4 GHz) found for PU/PPF–PPy composites containing 25 wt% of PPF–PPy were in the range −12 dB, which corresponds to 93.2% of attenuation, indicating that these composites are promising candidates for EMI shielding applications. POLYM. COMPOS., 38:2146–2155, 2017. © 2015 Society of Plastics Engineers     

Interfacial synthesis of polypyrrole/graphene composites and investigation of their optical,electrical and electrochemical properties

We report the development of a novel route for the synthesis of polypyrrole/graphene (PPy/GR) composites by liquid ? liquid interfacial polymerization, where GR and the initiator were dispersed in the aqueous phase and the monomer was dissolved in the organic phase. The synthesized samples were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, ultraviolet–visible spectroscopy, Raman spectroscopy, X‐ray diffraction, thermogravimetric analysis, electrochemical and electrical conductivity measurements. Structural analysis reveals a uniform dispersion of GR sheets in the PPy matrix. The composites showed noticeable improvement in thermal stability and electrical conductivity (8.45 S cm^?1) and excellent electrochemical reversibility in comparison with pure PPy. A specific capacitance of 260 F g^?1 at a current density of 100 mA g^?1 was achieved for the composite during the charge–discharge process. © 2013 Society of Chemical Industry     

High electrical conductive polymethylmethacrylate/graphite composites obtained via a novel pickering emulsion route

In this work, high electrically conductive Polymethylmethacrylate/graphite (PMMA/G) composites with a specific core-shell structure were synthesized via Pickering emulsion (solid-stabilized emulsion) route. The electrical conductivity of the core-shell composites was measured by a four-point probe resistivity determiner and a very high value of 9.8?×?10^?3 S/cm (10¹³ times higher than virgin PMMA) was obtained at 30 wt% graphite. However, the electrical conductivity of the PMMA/G composites gained through traditional blend process was relatively lower and the value only reached 9.4?×?10^?9 S/cm at same graphite loading fraction. Contact angle measurement was applied to determine the surface free energy of the modified graphite which was cladded by Al(OH)₃. The morphology of the core-shell composites was observed by SEM and optical microscopy. Dynamic rheology analysis was employed to study the structural change by the interconnection of the graphite flakes and the formation of the networks in the composites. The interconnected networks of the core-shell composites were more easily constructed when compared with the composites obtained by the traditional blending process.     

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.     

Effects of polymerization medium on electrical conductivity and optical properties of organic semiconductor-based polypyrrole

The effects of tetrabutylammonium tetrafluoroborate (TBAFB), tetrabutylammonium hexafluorophosphate (TBAPF₆), and paratoluene sulfonoicacid (PTSA) polymerization mediums on the electrical conductivity and optical properties of the polypyrrole (PPy) have been investigated. The electrical conductivity and optical properties of the samples polymerized in presence of TBAFB, TBAPF₆, and PTSA organic salts change with medium of prepared polymer. The electrical conductivity of the TBAFB, PTSA, and TBAPF₆ samples at 27°C were found to be 3.43 × 10⁻¹, 4.48 × 10⁻², and 1.60 × 10⁻⁴ (S/cm), respectively. The lowest optical band gap of the polymer was found to be 2.23 eV. The refractive index dispersion of the samples obeys single oscillator model. The obtained results suggest that polymerization medium changes electrical conductivity and optical properties of the PPy. POLYM. ENG. SCI., 47:1016–1020, 2007. © 2007 Society of Plastics Engineers     

Conducting Shape Memory Polyurethane‐Polypyrrole Composites for an Electroactive Actuator

Summary: Electroactive shape memory composites were prepared using polyurethane block copolymer and conducting polypyrrole by chemical oxidative polymerization. The electrical conductivity, thermal and mechanical properties, and morphology of the composites were investigated, and a voltage‐triggered shape memory effect was demonstrated. The polyurethane synthesized had a transition temperature near 46 °C. The presence of polypyrrole increased the conductivity of the composites, and a high conductivity of the order of 10^?2 S/cm was obtained at 6–20 wt.‐% polypyrrole. Such a conductivity of composites was enough to show electroactive shape recovery by heating above the transition temperature of 40–45 °C due to melting of the polycaprolactone soft segment domain. Thus a good shape recovery of 85–90% could be obtained in the shape recovery test with bending mode when an electric field of 40 V was applied.

Electroactive shape recovery behavior of PU/PPy composite.     

Preparation of conducting polyacrylonitrile/polypyrrole composite films by electrochemical synthesis and their electrical properties

Electrically conducting polyacrylonitrile (PAN)/polypyrrole (PPy) composite films were prepared by electrochemical polymerization of pyrrole in an insulating PAN matrix under various polymerization conditions and their electrical properties were studied. The conductivities of PAN/PPy composite films peeled off from the platinum electrode he lie in the range of 10^?2–10^?3 s/cm, depending on the preparation conditions: The conductivity increased with the concentrations of the electrolyte and the monomer, but it decreased with the polymerization temperature of pyrrole and the applied potential.     

Synthesis and properties of conducting polypyrrole,polyalkylanilines, and composites of polypyrrole and poly(2‐ethylaniline)

Conducting polymers of alkylanilines, pyrrole, and their conducting composites were synthesized by oxidation polymerization. The oxidants used were KIO₃ and FeCl₃ for the polyalkylanilines and polypyrrole (PPy), respectively. Among the polyalkylanilines synthesized with KIO₃ salt, the highest conductivity was obtained with poly(2‐ethylaniline) (P2EAn) with a value of 4.10 × 10^?5 S/cm. The highest yield was obtained with poly(N‐methylaniline) with a value of 87%. We prepared the conducting composites (PPy/P2EAn and P2EAn/PPy) by changing synthesis order of P2EAn and PPy. The electrically conducting polymers were characterized by IR spectroscopy, ultraviolet–visible spectroscopy, thermogravimetric analysis, and X‐ray diffraction spectroscopy. From the results, we determined that the properties of the composites were dependent on the synthesis order of the polymers. The thermal degradation temperature of PPy was observed to be higher than that of the other polymers and composites. We determined from X‐ray results that the structures of the homopolymers and composites had amorphous regions (88–95%) and crystal regions (5–12%). From the Gouy balance magnetic measurements, we found that the polymers and composites were bipolaron conducting mechanisms. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 241–249, 2006     

Synthesis,characterization and supercapacitors of electrically conductive PPy/graphene/rare earth ions composites

PPy/graphene/rare earth ions (PPy/GR/RE³⁺) were prepared using an in situ chemical polymerization of the monomer in the presence of FeCl₃ oxidant and p-toluenesulfonic acid dopant. The PPy/GR/RE³⁺ composites were characterized by FT-IR spectroscopy, four-point probe conductivity, scanning electron microscopy and transmission electron microscopy. The maximum conductivity of PPy/GR/Gd³⁺ composites is about 9.71 S/cm found with 1 wt% GR and 2 wt% Gd³⁺ at room temperature. The capacitance of the composite electrodes was investigated with cyclic voltammetry. As results of this study, the PPy/GR/Gd³⁺ was effective to obtain fully reversible and very fast faradaic reaction. Hence, the PPy/GR/Gd³⁺ could contribute to the pseudo-capacitive charge storage. The PPy/GR/Gd³⁺ exhibited higher specific capacitance of ~238 F/g at 1 A/g current density. Thermal gravimetric analysis demonstrates an improved thermal stability of PPy in the PPy/GR/Gd³⁺ composites.     

Synthesis of highly conductive PPy/graphene nanosheets/NiO composite using ultrasonic technique

Highly conductive polypyrrole/graphene nanosheets/NiO (PPy/GNS/NiO) composites are fabricated via ultrasound technique using p‐toluenesulfonic acid as a dopant and FeCl₃ as an oxidant. The effects of the GNS and NiO loading on the electrical conductivity are investigated. The maximum conductivity of PPy/GNS/NiO composites about 24.39 S/cm found with 3 wt% GNS and 48.7 wt% NiO at room temperature. The results showed that the high‐aspect‐ratio structure of GNS played an important role in forming a conducting network in PPy matrix. The microstructures of PPy/GNS/NiO are evidenced by the scanning electron microscope and transmission electron microscope examinations. The cyclic voltammetry curves can be seen that the PPy/GNS/NiO composites also have good electrochemical performance, and it can be used as a supercapacitor electrode material. POLYM. COMPOS., 34:997–1002, 2013. © 2013 Society of Plastics Engineers     

Chemical preparation of conducting polyfuran/poly(2‐chloroaniline) composites and their properties: A comparison of their components,polyfuran and poly(2‐chloroaniline)

Conductive homopolymers and composites of poly(2‐chloroaniline) (P2ClAn) and polyfuran (PFu) were synthesized chemically in hydrous and anhydrous media, and their properties were investigated. The polymers and composites were characterized by Fourier infrared spectroscopy, ultraviolet‐visible absorption spectroscopy, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, magnetic susceptibility, and conductivity measurements. It was found that the PFu/P2ClAn composite is thermally more stable than both the P2ClAn/PFu composite and the homopolymers. It was determined from Gouy scale measurements that conducting mechanisms of homopolymers and composites are polaron and bipolaron in nature. It was observed that the conductivity and magnetic susceptibility values changed with a changing amount of the guest polymer in the prepared composites. The conductivity (3.21 × 10^?2 S/cm) of the P2ClAn/PFu (55.8% m/m) composite was found to be higher than the conductivities of both homopolymers (σ_PFu = 1.44 × 10^?5 S/cm; σ_P2ClAn = 1.32 × 10^?3 S/cm). It was determined that the composites synthesized had different conductivities and morphological and thermal properties from changing synthesis order. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2924–2931, 2003     

Electrical conductivity modeling of carbon‐filled liquid‐crystalline polymer composites

Electrically conductive resins are needed for bipolar plates used in fuel cells. Currently, the materials for these bipolar plates often contain a single type of graphite powder in a thermosetting resin. In this study, various amounts of two different types of carbon, carbon black and synthetic graphite, were added to a thermoplastic matrix. The resulting single‐filler composites were tested for electrical conductivity, and electrical conductivity models were developed. Two different models, the Mamunya and additive electrical conductivity models, were used for both material systems. It was determined how to modify these models to reduce the number of adjustable parameters. The models agreed very well with experimental data covering a large range of filler volume fractions (from 0 to 12 vol % for the carbon black filled composites and from 0 to 65 vol % for the synthetic graphite filled composites) and electrical conductivities (from 4.6 × 10^?17 S/cm for the pure polymer to 0.5 S/cm for the carbon black filled composites and to 12 S/cm for the synthetic graphite filled composites). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3293–3300, 2006     

Synthesis and study of thermal and electrical behaviour of some polyaromatic amines

Samples of polyaromatic amines were synthesised by chemical and electrochemical methods, using different amounts of electrolytes for the purpose of doping the polymer. These polymers were found to show electrical conductivity in the range 10^?12–10^?6 S/cm. A study of conductivity at various temperatures indicates the semiconducting behaviour of these polymers. Thermal analysis shows that these polymers have high thermal stability.     

Synthesis,Electrical Properties and Stability of Polypyrrole-Containing Conducting Polymer Composites

Conducting polymer composites of polyethylene and polypyrrole (PE/PPy), polypropylene and polypyrrole (PP/PPy) and poly(methyl methacrylate) and polypyrrole (PPMA/PPy) were prepared by means of a chemical modification method resulting in a network-like structure of polypyrrole embedded in the insulating polymer matrix. The content of polypyrrole determined by elemental analysis varied from 0·25 to 17wt%. Electrical conductivity of compression-moulded samples depended on the concentration of polypyrrole and reached values from 1×10^-11 to 1 S cm^-1. The morphology of the composites and blends was studied by low-voltage scanning electron microscopy. The stability of PP/PPy composites was investigated by thermogravimetric analysis and by conductivity measurements during heating–cooling cycles. There was only a small drop in conductivity caused by the annealing of PP/PPy composites in air at temperatures up to 80°C. The results of thermogravimetric analysis showed a stabilizing effect of PPy on PMMA/PPy composites against thermal degradation. The antistatic properties of PMMA/PPy composites were demonstrated. © 1997 SCI.     

Supercritical carbon dioxide assisted preparation of conductive polypyrrole/cellulose diacetate composites

Supercritical carbon dioxide (SC‐CO₂) has been used to assist the preparation of conductive polypyrrole/cellulose diacetate (PPy/CDa) composites by in situ chemical oxidative polymerization. The morphology and conductivity of resulted composites were investigated with scanning electron microscopy and four‐probe method, respectively. With the assistance of strong swelling effect of SC‐CO₂, composite films were obtained with a macroscopically homogeneous structure and conductivity up to 10^?1 S cm^?1 order of magnitude. Increasing the pressure of SC‐CO₂ increased conductivity, while increasing the temperature decreased conductivity. For comparison, PPy/CDa composite was also prepared with conventional oxidative method in aqueous solution. From the viewpoint of conductivity and environmental protection, the SC‐CO₂ method showed its superiority over the conventional one. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4575–4580, 2006     

A study on electrical and thermal conductivities of ethylene–octene copolymer/expandable graphite composites

A series of ethylene–octene copolymer (EOC) composites have been prepared by melt‐mixing with different weight ratios of expandable graphite filler (0–50% by weight). Electrical conductivity [both alternating current (AC) and direct current (DC)] and thermal conductivity studies were carried out. Effect of filler loading and frequency on electrical conductivity was studied. DC conductivity has increased from 1.51 × 10^?13 S cm^?1 to 1.17 × 10^?1 S cm^?1. Percolation threshold by DC and also AC methods was observed at about 16 vol% of the filler. Real part of permittivity was found to be decreasing with increase in frequency while conductivity was increasing. Thermal conductivity was also found to be increasing gradually from 0.196 to 0.676 Wm^?1 K^?1 which is about 245% increase. Graphite not only increases the electrical and thermal conductivities but at and above 40 wt%, also acts as a halogen‐free, environmental friendly flame retardant. Shore‐A hardness of EOC/graphite composites shows that even with high graphite loading, the hardness is increased from about 50–68 only so that the rubbery nature of the composite is not affected very much. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers