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.     

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     

Synthesis of highly conducting nylon-6 composites and their electrical properties

Highly conducting nylon-6 composites are synthesized by exposing nylon-6 films or fabrics impregnated with an oxidizing agent, cupric chloride, simultaneously to aniline and hydrochloric acid vapors. The conductivity of composite films reaches up to 10^?2 S/cm and can be controlled by varying the experimental conditions for the composite synthesis. The effects of the concentration of cupric chloride, exposure time to aniline and hydrochloric acid vapors, and concentration of hydrochloric acid to the polyaniline content and the conductivity of nylon-6/polyaniline composites are analyzed by means of statistical F test. The morphology change of composite films resulting from the synthesis conditions, conductivity in relation to the morphology, and stability of conductivity to ambient air exposure have been investigated.     

Polyaniline-coated silver nanowires

Two non-conducting chemicals, aniline and silver nitrate, dissolved in formic acid solutions, yielded a composite of two conducting products, polyaniline and silver. As the concentration of formic acid increased, an alternative reaction, the reduction of silver nitrate with formic acid to silver became dominant, and the content of silver in the composites increased. The formation of polyaniline was confirmed by UV–visible, FTIR, and Raman spectroscopies. The typical conductivity of composites was 43 S cm^?1 at 84 wt.% of silver. Silver nanowires coated with polyaniline nanobrushes are produced at low concentrations of formic acid, the granular silver particles covered with polyaniline dominate at high acid concentrations.     

Conducting composites of poly(N‐vinylcarbazole), polypyrrole,and polyaniline with 13X‐zeolite

N‐vinylcarbazole (NVC) was polymerized by 13X zeolite alone in melt (65°C) or in toluene (110°C) and a poly(N‐vinylcarbazole) (PNVC)‐13X composite was isolated. Composites of polypyrrole (PPY) and polyaniline(PANI) with 13X zeolite were prepared via polymerization of the respective monomers in the presence of dispersion of 13X zeolite in water (CuCl₂ oxidant) and in CHCl₃ (FeCl₃ oxidant) at an ambient temperature. The composites were characterized by Fourier transform infrared analyses. Scanning electron microscopic analyses of various composites indicated the formation of lumpy aggregates of irregular sizes distinct from the morphology of unmodified 13X zeolite. X‐ray diffraction analysis revealed some typical differences between the various composites, depending upon the nature of the polymer incorporated. Thermogravimetric analyses revealed the stability order as: 13X‐zeolite > polymer‐13X‐zeolite > polymer. PNVC‐13X composite was essentially a nonconductor, while PPY‐13X and PANI‐13X composites showed direct current conductivity in the order of 10^?4 S/cm in either system. However, the conductivity of PNVC‐ 13X composite could be improved to 10^?5 and 10^?6 S/cm by loading PPY and PANI, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 913–921, 2006     

Sustainable conducting polymer composites: study of mechanical and tribological properties of natural fiber reinforced PVA composites with carbon nanofillers

ABSTRACT

Ball milled jute fiber (JF) was added to Polyvinyl Alcohol (PVA)/20 wt.% multi-layer graphene (MLG) composites in various proportions (0, 5, 10, 15 and 20 wt.%) to prepare sustainable and biodegradable conducting polymer composites. Also, PVA/17.5wt.%MLG/2.5wt.%MWCNT/20wt.% JF composite was prepared for comparison purpose. A dynamic mechanical analysis of the composites was conducted to analyze their viscoelastic nature. The electrical conductivity of the composites was measured to study their suitability for various applications. Jute reinforcement increased the electrical conductivity of PVA/MLG nanocomposites. The PVA/20wt.%JF/17.5wt.%MLG/2.5wt.%MWCNT hybrid composite had the highest electrical conductivity of 3.64 × 10^?4 S/cm among all the composites prepared. Multilayered structures of the hybrid composite films were made by hot-pressing, and their effectiveness in electromagnetic interference shielding was tested. The shielding effectiveness of the composites decreased with jute addition. The wear resistance of PVA/MLG/JF composites increased with an increase in the jute content up to an optimum value of 10 wt.%, and then it started deteriorating.     

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     

Preparation of polystyrene–graphite conducting nanocomposites via intercalation polymerization

In situ polymerization of styrene was conducted in the presence of expanded graphite obtained by rapid heating of a graphite intercalation compound (GIC), to form a polystyrene–expanded graphite conducting composite. The composite showed excellent electrically conducting properties even though the graphite content was much lower than in normal composites. The transition of the composite from an electrical insulator to an electrical semiconductor occurred when the graphite content was 1.8 wt%, which is much lower than that of conventional conducting polymer composites. TEM, SEM and other studies suggest that the graphite was dispersed in the form of nanosheets in a polymer matrix with a thickness of 10–30 nm, without modification of the space between carbon layers and the structure of the graphite crystallites. The composite exhibited high electrical conductivity of 10^?2 S cm^?1 when the graphite content was 2.8–3.0 wt%. This great improvement of conductivity could be attributed to the high aspect ratio (width‐to‐thickness) of the graphite nanosheets. The rolling process strongly affected the conductivity and the mechanical properties of the composite. © 2001 Society of Chemical Industry     

Renewable antioxidant properties of suspensible chitosan–polypyrrole composites

Conductive polymers have the ability to capture radicals and have become in focus for antioxidant applications of food packaging or biomedical applications. Unfortunately, the conducting polymers such as polypyrrole are difficult to suspense in solution after chemical or electrochemical polymerization. Chitosan, as a natural polymer from chitin, can be dissolved in diluted acetic acid solutions. In the present study, composites suspensible in diluted acetic acid solutions have been produced by the chemical polymerization of pyrrole in chitosan solution using ammonium persulfate (APS) as the oxidant. FTIR and UV–Vis measurements did identify an attachment of polypyrrole to chitosan.In order to optimize the activity and stability of the composites, the ratios of APS: polypyrrole: chitosan were analyzed. The chitosan–polypyrrole composites were formed as membranes (coatings); impedance measurements indicated their conductivity to be in the range of 10^?3–10^?7 S cm^?1. The antioxidant (radical scavenger activity) properties were determined by the di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium (DPPH) assay. The radical scavenger activity of the composites was found renewable by means of electrochemical cycling.     

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     

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     

Water‐dispersible conducting polyaniline/nano‐SiO2 composites without any stabilizer

A water‐dispersible conducting polyaniline/ nano‐SiO₂ composite, with a conductivity of 0.071 S cm^?1 at 25°C, was prepared by the oxidative polymerization of aniline in the presence of amorphous nano‐SiO₂ particles. And the structure, morphology, thermal stability, conductivity, and electroactivity of this composite were also investigated. This composite has been steadily dispersed in the aqueous solution for about 10–36 h without the need for any stabilizer. It would significantly impulse the commercial applications of conducting polyaniline/nano‐SiO₂ composite as fillers for antistatic and anticorrosion coatings. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Organic–Inorganic Composite Material Polyaniline Ce(IV) molybdate: Thermal and Room Temperature Electrical Conductivity Measurement Studies

An electrically conducting ‘organic–inorganic’ composite material polyaniline Ce(IV) molybdate was prepared by incorporating electrically conducting polymer, i.e., polyaniline into inorganic precipitate of polyvalent metal acid salts i.e., Ce(IV) molybdate. The temperature dependence of electrical conductivity of this composite system with increasing temperatures was measured on compressed pellets by using a 4-in-line-probe dc electrical conductivity-measuring instrument. The values of conductivity lies in the semiconductor region, i.e., they are of the order of 10⁻⁵–10⁻² S cm⁻¹ and obey the Arrhenius equation. The thermal stability of this composite material in terms of dc electrical conductivity retention was studied under isothermal and cyclic techniques and electrical conductivity of composite was found to be sufficiently stable under ambient temperature conditions. The dependence of the electrical conductivity prepared with different concentrations of aniline monomers, on the concentration of conducting phases i.e., polyaniline was showed that electrical conductivity increase followed the percolation threshold.     

Synthesis and characterization of polypyrrolepolyurethane cationomer composites

Poly(ether urethane) cationomers based on poly(oxytetramethylene), 4,4′-bibenzyldiisocyanate, N-methyldiethanolamine as chain extender, and acrylic acid/poly(acrylic acid) as quaternization agent were synthesized. Pyrrole (15 wt.%%) was polymerized in films of the ionomer containing CuCl₂. The films were characterized by dynamic mechanical analysis, thermogravimetry and differential scanning calorimetry. The electric conductivity of the film without polypyrrole is 7.5 · 10^?12 Ω^?1 cm^?1, while incorporation of polypyrrole increases the conductivity to 4.5 · 10^?6 Ω^?1 cm^?1.     

Preparation of conductive polypyrrole composites by in‐situ polymerization

Two kinds of conductive polypyrrole composites were prepared by in‐situ polymerization of pyrrole in a suspension of chlorinated polyethylene powder or in a natural rubber latex using ferric chloride as oxidizing agent. The preparation conditions were studied and the results showed that it is better to swell the chlorinated polyethylene powder with the monomer first, followed by addition of the oxidant, than to add the oxidant first, and that conversion can reach 98% for 6 h at room temperature. The conductivity percolation threshold of the composite is about 12%. The composites can be processed repeatedly, exhibiting a maximum tensile strength over 9 MPa and a maximum conductivity near 1 S cm⁻¹. The polypyrrole/natural rubber composites were prepared successfully by using a nonionic surfactant (Peregal O) as stabilizer at pH less than 3 with a molar ratio of FeCl₃/pyrrole = 2.5 below 45 °C. The latter composites show a low conductivity percolation threshold about 6%, a maximum tensile strength over 10 MPa and a maximum conductivity over 2 S cm⁻¹. The composites were characterized by FTIR and TGA. The polypyrrole/chlorinated polyethylene composites are very stable in air and almost no decrease of conductivity was observed for over 10 months examined. © 1999 Society of Chemical Industry     

Cation‐exchange kinetics and electrical conductivity studies of an ‘organic‐inorganic’ composite cation‐exchanger: Polypyrrole Th(IV) phosphate

Polypyrrole Th(IV) phosphate, an electrically conducting ‘organic‐inorganic’ cation‐exchange composite material was prepared by the incorporation of an electrically conducting polymer, i.e., polypyrrole, into the matrix of a fibrous type inorganic cation‐exchanger thorium(IV) phosphate. The composite cation‐exchanger has been of interest because of its good ion‐exchange capacity, higher chemical and thermal stability, and high selectivity for heavy metal ions. The temperature dependence of electrical conductivity of this composite system with increasing temperatures was measured on compressed pellets by using four‐in‐line‐probe dc electrical conductivity measuring instrument. The conductivity values lie in the semiconducting region, i.e., in the order of 10^?6 to 10^?4 S cm^?1 that follow the Arrhenius equation. Nernst–Plank equation has been applied to determine some kinetic parameters such as self‐diffusion coefficient (D₀), energy of activation (E_a), and entropy of activation (ΔS*) for Mg(II), Ca(II), Sr(II), Ba(II), Ni(II), Cu(II), Mn(II), and Zn(II) exchange with H⁺ at different temperatures on this composite material. These results are useful for predicting the ion‐exchange process occurring on the surface of this cation‐exchanger. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Elastomeric composites based on ethylene–propylene–diene monomer rubber and conducting polymer-modified carbon black

Thermally stable elastomeric composites based on ethylene–propylene–diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via “in situ” deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300°C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5–10 phr depending on the formulation and electrical dc conductivity values in the range of 1 × 10⁻³ to 1 × 10⁻² S cm⁻¹ above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Melt processing of composites of PVDF and carbon black modified with conducting polymers

Conductive composites from poly(vinylidene fluoride) (PVDF) and a novel thermally stable conductive additive made via in situ deposition of polyaniline or polypyrrole on carbon black particles were produced by a melting process. Electrical conductivity in the order of 10^?2 S/cm could be achieved with low contents of the conductive filler. Thermogravimetric analysis (TGA) showed that there is no appreciable degradation of the composites at temperatures as high as 300°C. Moreover, the addition of the conducting polymer‐modified carbon black additive is advantageous to the melt processing of the composites, reducing the melt viscosity in comparison to the addition of pure carbon black. Composites containing the β‐phase of PVDF could be obtained via quenching from the melt, as indicated by X‐Ray diffraction analysis. The type and amount of the additive and the quenching rate influence the formation of β‐phase in the PVDF composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 553–557, 2004     

Synthesis of conducting polyaniline/TiO2 composite nanofibres by one‐step in situ polymerization method

Conducting polyaniline (PANI)/titanium dioxide (TiO₂) composite nanofibres with an average diameter of 80–100 nm were prepared by one‐step in situ polymerization method in the presence of anatase nano‐TiO₂ particles, and were characterized via Fourier‐transform infrared spectra, UV/vis spectra, wide‐angle X‐ray diffraction, thermogravimetric analysis, and transmission electron microscopy, as well as conductivity and cyclic voltammetry. The formation mechanism of PANI/TiO₂ composite nanofibres was also discussed. This composite contained ～ 65% conducting PANI by mass, with a conductivity of 1.42 S cm^?1 at 25°C, and the conductivity of control PANI was 2.4 S cm^?1 at 25°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2007