Polypyrrole/polyacrylonitrile composite films: Dielectric, spectrophotometric and morphologic characterization

Spectrophotometric, morphologic and dielectric properties of polyacrylonitrile (PAN) composite films in the presence of pyrrole derivatives were reported in this paper. The composite films were fabricated by oxidative polymerization of pyrrole (Py), N-methyl pyrrole (NMPy) and N-phenyl pyrrole (NPhPy) by cerium(IV) on polyacrylonitrile matrix. The effect of temperature on the dielectric properties was studied in the frequency range from 0.05 Hz up to 10 MHz and in the temperature range from 0 °C up to 250 °C. Conductivity was increased with temperature due to increase of the mobility of charge carriers in the composite films. By increasing the temperature, the dipoles become free and respond to the applied electric field in composite structure; thus, the polarization and dielectric constant increases. PNPhPy-PAN composite films exhibited the highest dielectric constant, AC conductivity and tan delta.     

Characterization of conductive poly(acrylonitrile-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate) composites: Matrix polymerization of pyrrole derivatives

In this study, poly(acrylonitrile-co-vinyl acetate) (P(AN-co-VAc)) composite films were prepared by chemical polymerization of pyrrole(Py), N-methyl pyrrole (NMPy) and N-phenyl pyrrole (NPhPy) with cerium(IV) [Ce(IV)] on P(AN-co-VAc) matrix. An increase was observed in the absorbances of CN ring stretching vibration (1451 cm⁻¹) by introducing pyrrole (Py) derivatives on P(AN-co-VAc) matrix. The nitrile (CN) and carbonyl (C=O) groups played a significant role on the interactions with cationic sites of Py derivatives. Conductivity was increased in the presence of carbonyl (C=O) groups due to their additional negative charges on P(AN-co-VAc) matrix compared to PAN. Poly(N-Phenyl Pyrrole) (PNPhPy) exhibited higher dielectric constant and AC conductivity in the frequency range between the 10⁻²–10⁷ Hz. The TGA results exhibited shifts of peak to higher temperatures by the presence of Py derivatives by increasing the weight loss %.     

Structural investigation of anionic functional poly(vinyl alcohol) doped polypyrrole nanospheres

This article reports on a facile route for the preparation of polypyrrole nanospheres with improved water solubility, ordering and conductivity in the presence of a polyelectrolyte, such as phosphorylated polyvinyl alcohol. The phosphorylated polyvinyl alcohol (PPVA) was used as both the stabilizer and the dopant in the chemical oxidative polymerization of pyrrole. The resulting PPVA doped polypyrrole (PPy) nanocomposites (PPy-PPVA) were characterized with FTIR, TGA, SEM and AFM techniques. The electrical conductivity of polymer was measured by four-point probe method. Our observation and results suggest a plausible formation mechanism of PPy nanospheres, PPVA micelle might have functioned as ‘template’ during the polymerization of pyrrole monomers, meanwhile, the PPy chains doped with phosphate group. It was found that the size decreased and their dispersion stability in water increased with the increasing feeding ratio of PPVA. The conductivity of PPy with different morphologies was also measured and compared. When the PPVA: pyrrole feeding ratio ranged from 20 to 50 wt%, the PPy-PPVA nanoparticles showed spherical shape with excellent uniformity, good electrical conductivity (up to 33.1 S·cm^?1), and weakly temperature dependent conductivity. It’s worth mentioning that the PPy-PPVA nanocomposite prepared in high PPVA feeding ratio has been well-dispersed for more than 24 months, which indicates its significant dispersion stability.     

Properties and performance of polypyrrole (PPy)-coated silk fibers

Different silk substrates in form of spun silk tops, nonwoven web, yarn, and fabric were coated with electrically conducting doped polypyrrole (PPy) by in situ oxidative polymerization from an aqueous solution of pyrrole (Py) at room temperature using FeCl₃ as catalyst. PPy-coated silk materials were characterized by optical (OM) and scanning electron (SEM) microscopy, FT-IR spectroscopy, and thermal analysis (DSC, TG). OM and SEM showed that PPy completely coated the surface of individual silk fibers and that the polymerization process occurred only at the fiber surface and not in the bulk. Dendrite-like aggregates of PPy adhered to the fiber surface, with the exception of the sample first polymerized in the form of tops and then spun into yarn using conventional industrial machines. FT-IR (ATR mode) showed a mixed spectral pattern with bands typical of silk and PPy overlapping over the entire wavenumbers range. DSC and TG showed that PPy-coated silk fibers attained a significantly higher thermal stability owing to the protective effect of the PPy layer against thermal degradation. The mechanical properties of silk fibers remained unchanged upon polymerization of Py. The different PPy-coated silk materials displayed excellent electrical properties. After exposition to atmospheric oxygen for two years a residual conductivity of 10–20 % was recorded. The conductivity decreased sharply under the conditions of domestic washing with water, while it remained essentially unchanged upon dry cleaning. Abrasion tests caused a limited increase of resistance. PPy-coated silk tops were successfully spun into yarn either pure or in blend with untreated silk fibers. The resulting yarns maintained good electrical properties.     

Decay of electrical conductivity in p-toluene sulfonate doped polypyrrole films

Long term performance of conductivity of p-toluene sulfonic acid (pTSA) doped electrochemically synthesized polypyrrole (PPy) films was estimated from accelerated aging studies between 80 °C and 120 °C. Conductivity decay experiments indicated that overall aging behavior of PPy films deviated from first order kinetics at prolonged aging times at elevated temperatures. However, an approximate value for the activation energy of the conductivity decay of PPy was calculated as E=47.4 kJ/mol, enabling an estimate of a rate constant of k=8.35×10⁻⁶/min at 20 °C. The rate of decrease of conductivity was not only temperature dependent but also influenced by the dopant concentration. A concentration of 0.005 M pTSA in the electrolyte resulted in a conductive film and when this film was exposed to 120 °C for a period of 40 h, the conductivity decayed to about 1/20 of its original value. The concentration of pTSA was increased to 0.05 mol/l and when the resulting film was aged in the same way, it showed a decrease in the conductivity to about 1/3 of its original value. Both microwave transmission and dc conductivity data revealed that highly doped films were considerably more electrically stable than lightly doped films. The dopant had a preserving effect on the electrical properties of PPy.     

Microstructures and electrical properties of composite films based on carbon nanotube and para-aramid containing cyano side group

We report the microstructures and electrical properties of poly(2-cyano-1,4-phenylene terephthalamide) (cyPPTA)-based composite films including pristine multi-walled carbon nanotube (MWCNT) of 0.3-10.0 wt%, which were manufactured by ultrasonication-based solution mixing and casting techniques. FT-IR spectra of the composite films revealed the existence of specific interaction between cyPPTA and MWCNT. Accordingly, the pristine MWCNTs were found to be dispersed uniformly in the cyPPTA matrix, as confirmed by TEM images. The electrical resistivity of the composite films decreased considerably from ~10¹⁰ Ω cm to ~10⁰ Ω cm with the increase of the MWCNT content by forming a conductive percolation threshold at ~0.525 wt%. The composite films with 3.0-10.0 wt% MWCNT contents, which have sufficiently low electrical resistivity of ~10²-10⁰ Ω cm, exhibited excellent electric heating performance by attaining high maximum temperatures and electric power efficiency under given applied voltages of 10-100 V. Since the thermal decomposition of the composite films took place at 520-600 °C under air atmosphere, cyPPTA/MWCNT composite films could be used for high performance electric heating, antistatic, and EMI shielding materials.     

Synthesis and electropolymerization of 9-tosyl-9<Emphasis Type="Italic">H</Emphasis>-carbazole,electrochemical impedance spectroscopic study and circuit modelling

This work reports on the newly synthesized 9-tosyl-9H-carbazole (TsCz) monomer. Capacitive properties of the electrochemically grown homopolymer, poly(TsCz) film on carbon fibre microelectrode (CFME), are characterised by cyclic voltammetry (CV), Fourier transform infrared reflectance-attenuated total reflection spectroscopy (FTIR-ATR), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Different monomer concentrations (1, 3 and 10 mM) were used for electrodeposition in 0.1 M sodium perchlorate (NaClO₄)/acetonitrile (ACN) solution. The capacitive behaviour of modified CFMEs was defined via Nyquist, Bode-magnitude and Bode-phase plots. An equivalent electrical circuit R(CR)(QR)(CR) for different concentrations of poly(TsCz)/CFME was proposed and experimental data were simulated to obtain the numerical values of the circuit components. The Nyquist plot for poly(TsCz) shows the highest specific capacitance (50.0 mF cm⁻²) at frequency of 0.01 Hz in the initial monomer concentration of 10 mM.     

Functionalized multi-walled carbon nanotubes with hyperbranched aromatic polyamide for poly(methyl methacrylate) composites

Multi-walled carbon nanotubes (MWCNTs) were functionalized with hyperbranched aromatic polyamide (HAP) by in situ polymerization and by the AB ₂ approach to enhance the mechanical properties of poly(methylmethacrylate) (PMMA) composites. Various concentrations of HAP-functionalized MWCNTs (HAP-f-MWCNTs) were used to prepare HAP-f-MWCNT-reinforced PMMA composite films. The covalent attachment of HAP to the MWCNTs, as achieved by in situ functionalization, resulted in effective dispersion of the MWCNTs in the PMMA matrix, thus enhancing the mechanical and thermal properties of the composite films. The breaking stress of the composites increased largely with the HAP-f-MWCNT loading.     

Improvement of mechanical and electrical properties of poly(ethylene glycol) and cyanoresin based polymer electrolytes

Ionic conductivity and mechanical properties of a mixed polymer matrix consisting of poly(ethylene glycol) (PEG) and cyanoresin type M (CRM) with various lithium salts and plasticizer were examined. The CRM used was a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) with a molar ratio of 1:1, mixed plasticizer was ethylene carbonate (EC) and propylene carbonate (PC) at a volume ratio of 1:1. The conductive behavior of polymer electrolytes in the temperature range of 298∼338 K was investigated. The PEG/LiClO₄ complexes exhibited the highest ionic conductivity of ∼10⁻⁵ S/cm at 25°C with the salt concentration of 1.5 M. In addition, the plasticized PEG/LiClO₄ complexes exhibited improvement of ionic conductivity. However, their complexes showed decreased mechanical properties. The improvement of ionic conductivity and mechanical properties could be obtained from the polymer electrolytes by using CRM. The highest ionic conductivity of PEG/CRM/LiClO₄/(EC-PC) was 5.33×10⁻⁴ S/cm at 25°C.     

Preparation and characterization of electro-conductive rotor yarn by in situ chemical polymerization of pyrrole

This work describes a novel method for preparing electro-conductive rotor yarns by in situ oxidative chemical polymerization of pyrrole. The effects of different process parameters on electrical resistivity of the yarn were studied by using Box-Behnken response surface design. The concentration of monomer, polymerization time and polymerization temperature were found to influence the electrical resistivity of the yarn. It was observed that electrical resistivity of the yarn increased linearly with increase of measuring length of it. Whereas the effects of yarn twist and tensile strain found to had negative correlation with electrical resistivity of electro-conductive rotor yarns. Microscopic image analysis showed that there was uniform distribution of PPy polymer on the surface of cotton fibres and FTIR analysis depicted possible chemical interaction between polypyrrole and cellulose.     

Copolymerization of benzyl methacrylate and a methacrylate bearing benzophenoxy and hydroxyl side groups: Monomer reactivity ratios,thermal studies and dielectric measurements

Statistical copolymers of 2-hydroxy-3-benzophenoxy propyl methacrylate (HBPPMA) and benzyl methacrylate (BzMA) in different feed ratios were synthesized by free radical copolymerization method at 60 °C in presence of AIBN initiator. The compositions of copolymer were estimated from ¹H-NMR technique. The monomer reactivity ratios of HBPPMA and BzMA were calculated as r₁ (r_HBPPMA)=0.51±0.076 and r₂ (r_BzMA)=1.07±0.140 for Kelen-Tüdos method, and was estimated as r₁=0.37±0.0006 and r₂=0.64±0.0485 according to Fineman Ross equation. The average values estimated from the two methods showed that monomer reactivity ratio of benzyl methacrylate was a slightly high in comparison to HBPPMA. The copolymer system showed an azeotropic point, which is equal to M _BzMA =m _BzMA =0.43. DSC measurements showed that the T_g’s of poly(HBPPMA) and poly(BzMA) were 84 °C and 73 °C, respectively. The T_g in the copolymer system decreased with increase in benzyl methacrylate content. The decomposition temperature of poly(BzMA) and poly(HBPPMA) occurs in a single stage at about 207 °C and 260 °C, respectively. Those of HBPPMA-BzMA copolymer systems are between decomposition temperatures of two homopolymers. The dielectric constant, dielectric loss factor and electrical conductivity were investigated depend on the frequency of the copolymers. The highest dielectric constants depending on all the studied frequencies were recorded for the poly(HBPPMA) and the copolymer containing the highest HBPPMA unit. The dielectric constant for P(HBPPMA) and P(BzMA) at 1 kHz are 6.56 and 3.22, respectively. Also, those of copolymer systems were estimated between these two values. Similarly, poly(HBPPMA) and copolymers, which are prepared under the same conditions show the dissipation factor and conductivity as well.     

Enhanced thermal conductivity for PVDF composites with a hybrid functionalized graphene sheet-nanodiamond filler

A new thermal conductive poly(vinylidene fluoride) (PVDF) composite has been developed via a hybrid functionalized graphene sheets (FGS)-nanodiamonds (NDs) filler by a simple solution method. The PVDF composite showed different thermal conductivities at different proportion of hybrid filler. The thermal conductivity of the composite was up to 0.66 W/m·K for a mixture containing 45 wt% hybrid filler, which is about 2-fold increment in comparison to the PVDF martrix. The PVDF composites consisting of 20 wt% hybrid FGS/ND filler at the weight ratio of 1:3 shows the best thermal stability. The electrical conductivity of composites was increased from 5.1×10^?15 S cm^?1 (neat PVDF) to 7.1×10^?7 S cm^?1 of the PVDF composite with 10 wt% hybrid filler.     

Mechanical properties,morphology and dynamic mechanical properties of LGF/TPU/SAN composites

A series of the long glass fiber reinforced thermoplastic polyurethane elastomers and poly (styrene-acrylonitrile) (LGF/TPU/SAN) composites with different contents of long glass fiber were prepared by using self-designed impregnation device. Dynamic mechanical properties of TPU/SAN matrix reinforced with 10, 20 and 30 % by weight long glass fibers have been investigated by using dynamic mechanical thermal analysis (DMA). The results indicated that the content of long glass fiber and scanning frequency had some influence on dynamic mechanical properties and glass transition of LGF/TPU/SAN composites. In addition, the Arrhenius relationship has been used to calculate the activation energy of a-transition of the LGF/TPU/SAN composites. SEM demonstrates the relatively good dispersion of the long glass fiber in the TPU/SAN matrix. In addition, Effects of the content of long glass fiber on mechanical properties of the LGF/TPU/SAN composites are investigated.     

Electrodeposition of homogeneous and adherent polypyrrole/Na<Superscript>+</Superscript>-cloisite nanocomposite on iron electrodes

In this work homogeneous and adherent nanocomposite of polypyrrole (PPY) with Na⁺-Cloisite nanoclays was successfully prepared by insitu electropolymerization of pyrrole monomer in the presence of Na⁺-Cloisite nanoclays. Formation of nanocomposite and incorporation of nanoclays in polypyrrole matrix was endorsed and characterized by FTIR spectroscopy studies, X-ray diffraction (XRD) pattern and scanning electron microscopy (SEM). The X-ray difraction patterns showed that PPY was intercalated between clay layers in the order of nanoscale. The morphology of the resulted nanocomposite was studied by scanning electron micrograph (SEM). Cyclic voltammetry experiments were carried out in different electrolytes and showed that nanocomposite is electroactive, while conductivity of the nanocomposite derived from four point probe technique indicated that the resulted nanocomposite is conductive. The anticorrosive properties of a thin layer coating of PPY/Na⁺-Cloisite nanocomposite on iron coupons was evaluated and compared with pure polypyrrole coating. According to the results in various corrosive environments PPY/Na⁺-Cloisite nanocomposite has enhanced corrosion protection effect in comparison to pure polypyrrole coating. It was observed that the corrosion protection effect was due to the dispersion of nanoclays in polymer matrix, which results in the increase in the corrosion potential and decrease in corrosion current and corrosion rate.     

Conductive cotton fabrics for heat generation prepared by mist polymerization

Cotton fabrics were coated with conducting polypyrrole (PPy) by mist polymerization derived from aqueous solution of pyrrole (Py) with ferric chloride (FeCl₃) as oxidant. The polymerization conditions, such as the reaction time and the concentrations of monomer and oxidant, were systematically investigated. The prepared PPy-coated fabrics could keep their temperature at about 24–44 °C when charged by a fixed DC voltage of 1–3 V. The results indicate that these PPy-coated fabrics can be used potentially as heating pads and integrated into the apparel to make the wearer warm enough using a portable battery. Furthermore, such fabrics are more comfortable than the conventional heating pads due to their flexibility and breathability.     

Facile In-situ Polymerization of Thermotropic Liquid Crystalline Polymers as Thermally Conductive Matrix Materials

Although thermally conductive composites that can efficiently dissipate the heat generated from electronic devices are in high demand, most neat polymers used as matrix materials are problematic because they have poor thermal conductivities. The low thermal conductivity of polymeric materials is caused by structural defects; therefore, it can be improved by increasing the orientational regularity of the polymer chains. Here, main-chain liquid crystalline polymers (LCPs) were designed and synthesized to investigate the effects of liquid crystallinity-induced structural regularity on the thermal conductivity of the polymers. In addition, an in-situ polymerization method was devised for commercial applicability, and the thermal conductivity of the obtained polymer was compared to that of a conventionally polymerized polymer having the same structure. The designed polymers exhibited thermotropic liquid crystalline characteristics, and the polymer with longer spacers between the rigid segments showed relatively higher thermal conductivity exceeding 0.5 W·m^-1· K^-1 after sample preparation by injection molding. In addition, X-ray diffraction analysis revealed that the differences in the thermal conductivity, depending on the molding temperature during specimen preparation, were caused by variations in chain orientation within the same polymer. Based on the obtained results, it was concluded that LCPs are strong candidate matrix materials for thermally conductive composites; the suggested in-situ polymerization method could be applied practically to the polymerization of polyester-type LCPs.     

Optimization of molecular structure of polythiophene-graft-PMMA for effective compatibilization of SAN/MWCNT composite with superior mechanical properties

A new compatibilizer, P3HT-g-PMMA with controlled graft density and degree of polymerization of PMMA graft, has been synthesized for preparation of poly(styrene-co-acrylonitrile) (SAN)/multi-walled carbon nanotube (MWCNT) composites with superior mechanical properties. Fluorescence emission and Raman spectra reveal that the π-π interaction between polythiophene backbone of the compatibilizer and the surface of MWCNT is more effective as the graft density of PMMA in the compatibilizer is decreased while the degree of polymerization of PMMA is increased. Since FE-SEM observation also shows that the use of compatibilizer with higher degree of polymerization of PMMA graft yields well-dispersed MWCNTs in composites, it is concluded that the compatibilizer with lower graft density and higher degree of polymerization of PMMA graft is the most effective for reinforcing SAN with MWCNT.     

The preparation and characterization of conductive poly(ethylene terephthalate)/polyaniline composite fibers using benzoyl peroxide

Conductive polyaniline (PAn)/poly(ethylene terephthalate) (PET) composite fibers were prepared by chemical polymerization of aniline in the presence of PET fibers using benzoyl peroxide (Bz₂O₂) in organic solvent/aqueous hydrochloric acid mixtures. The effects of polymerization conditions such as organic solvent/water ratio, oxidant, aniline and hydrochloric acid concentrations and temperature were investigated on the amount of PAn deposited on PET fiber and the electrical surface resistance of composite fibers. The maximum PAn content and the lowest electrical surface resistance of composite fibers were observed at HCl concentrations of 0.5 mol L⁻¹. The properties of PAn/PET composite fibers such as density, diameter, tensile strength and breaking elongation were also investigated in comparison with those of pure PET. Characterization of conductive composite fibers was carried out by FTIR, TGA, SEM techniques, surface resistance measurements, and cross section images taken by optical microscope.     

Morphology and properties of polyacrylonitrile/single wall carbon nanotube composite films

Composite films were prepared by casting the solution of polyacrylonitrile (PAN) and single wall nanotube (SWNT) in DMF subsequent to sonication. The SWNTs in the films are well dispersed as ropes with 20–30 nm thickness. Moreover, AFM surface image of the composite film displays an interwoven fibrous structure of nanotubes which may give rise to conductive passways and lead to high conductivity. The polarized Raman spectroscopy is an ideal characterization technique for identification and the orientation study of SWNT. The well-defined G-peak intensity at 1580 cm⁻¹ shows a dependency on the draw ratio under cross-Nicol. The degree of nanotube orientation in the drawn film was measurable from the sine curve obtained by rotating the drawn film on the plane of cross-Nicol of polarized Raman microscope. The threshold loading of SWNT for electrical conductivity in PAN is found to be lower than 1 wt% in the composite film. The electrical conductivity of the SWNT/PAN composite film decreased with increasing of draw ratio due to the collapse of the interwoven fibrous network of the nanotubes with uniaxial orientation.     

Improved compressive strength of poly(p-phenylene benzobisoxazole) copolymer fiber containing multi-functional comonomer

Multi-functional comonomer from pentaerythritol (PE) and terephthaloyl chloride (TPC) was synthesized and used for polymerization of poly(p-phenylene benzobisoxazole) (PBO) copolymer. PBO copolymer fibers were prepared from PBO copolymers using a dry-jet wet spinning. The tensile strength of PBO copolymer fibers was higher than that of PBO, and showed 42 % increase at 0.5 mol% loading of comonomer. The tensile modulus of PBO copolymer fiber at 0.5 mol% loading showed 192 % increase compared to PBO fiber. The compressive strength of PBO copolymer fiber had values between 0.46 GPa and 0.6 GPa with the comonomer content. 64-114 % increase in compressive strength of PBO copolymer fibers was observed compared to PBO fiber.