Preparation of Nylon-6/flake graphite derivatives composites with antistatic property and thermal stability

Nylon-6/flake graphite (FG) composite, Nylon-6/graphene intercalation compounds (GIC) composite and Nylon-6/exfoliated graphite (EG) composite were prepared by FG, GIC, EG and caprolactam via in situ polymerization, and the volume resistivities of Nylon-6/flake graphite derivatives composites were also investigated. Meanwhile, the structure of Nylon-6/EG composite was characterized and the thermal stability of Nylon-6/EG composite was investigated as well. When the mass percents of FG, GIC and EG were 1%, 2–4% and 1%, the volume resistivities of flake graphite derivatives composites would reach 7.5 × 10⁶ Ω cm, 3.6 × 10⁸–1.4 × 10⁶ Ω cm and 2.3 × 10⁶ Ω cm. When the mass percent of EG increases from 0% to 9%, the thermal stability temperature of Nylon-6/EG composite would enhance from 70 to 196 °C. This shows that Nylon-6/flake graphite derivatives composites can have the antistatic property and thermal stability synchronously.     

Preparation and characterization of Nylon-6/exfoliated graphite composite via a combination method of in situ polymerization and thermal expansion

Nylon-6/exfoliated graphite (Nylon-6/EG) composite was prepared via a combination method of in situ polymerization and thermal expansion and characterized via scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Otherwise, the resistivity value of Nylon-6/EG composite was measured, and the volume resistivity value was calculated as well as. The characterization showed that Nylon-6/EG composite had the morphology of the graphite worm and was structured by EG and Nylon-6, which covered on the surface of EG. The result exhibited that the volume resistivity of Nylon-6/EG composite would decrease when the dosage of EG increased. When the mass percent of EG was 1%, the the volume resistivity value of Nylon-6/EG composite could reach 2.3 × 10⁶ Ω cm. This shows that the combination method not only is very effective and reliable but also can play an important role in preparing antistatic Nylon-6 composite.     

Synthesis of expanded graphite filled polyaniline composites and evaluation of their electrical and electrochemical properties

A series of conducting polyaniline/expanded graphite (PA/EG) composite was synthesized by in situ polymerization of aniline in acid medium followed by the addition of expanded graphite in various proportions (1, 2 and 3 wt%). The synthesized samples were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, ultraviolet–visible absorption, X-ray diffraction and by electrical conductivity measurements. The dc electrical conductivities of the composites were dramatically increased compared with pure polyaniline and found to be 0.50 × 10² S/cm to 6.11 × 10² S/cm. The PA/EG composites showed a reversible electrochemical response up to 150th repeated cycles as revealed by the cyclic voltametry study.     

Polyaniline–sodium montmorillonite clay nanocomposites: effect of clay concentration on thermal, structural, and electrical properties

A simple and facile method was used to synthesize polyaniline (PANI) nanocomposites with sodium montmorillonite clay (Na⁺-MMT) using in situ intercalative oxidative polymerization. Aniline was admixed with Na⁺-MMT at various concentrations, keeping the aniline monomer in the reaction mixture constant. The intercalation of PANI into the clay layers was confirmed by X-ray diffraction studies in conjugation with electron microscope techniques and FTIR spectra, particularly by the narrowing of the Si–O stretching vibration band confirmed the interaction between PANI and the clay. The employed route offers the possibility to improve the thermal properties with simultaneously controlled electrical conductivity. Thermal studies show an improved thermal stability of the nanocomposites relative to the pure PANI. Depending on the loading of the clay, the room temperature conductivity values of these nanocomposites varied between 2.0 × 10⁻⁴ and 7.4 × 10⁻⁴ S cm⁻¹, with the maximum at 44 wt% PANI concentration. The decrease of electrical conductivity at high PANI concentration was ascribed to the decrease of the structural ordering of PANI in the nanocomposite.     

MWNTs/PANI composite materials prepared by in-situ chemical oxidative polymerization for supercapacitor electrode

Multi-walled carbon nanotubes (MWNTs)/polyaniline (PANI) composite materials were prepared by in-situ chemical oxidative polymerization of an aniline solution containing well-dispersed MWNTs. The supercapacitive behaviors of these composite materials were investigated with cyclic voltammetry (CV), charge–discharge tests, and ac impedance spectroscopy, respectively. The composites based on the charge-transfer complex between well-dispersed MWNTs and PANI matrixes show much higher specific capacitance, better thermal stability, lower resistance, and were more promising for applications in supercapacitors than a pure PANI electrode. The highest specific capacitance value of 224 Fg⁻¹ was obtained for the MWNTs/PANI composite materials containing MWNTs of 0.8 wt%. The improvement mechanisms of the capacitance of the composite materials were also discussed in detail.     

Lightweight glass/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>-polyaniline composite hollow spheres with conductive and magnetic properties

Lightweight composite hollow spheres with conductive and magnetic properties were prepared by using Hollow Glass Spheres (HGS) as substrate. The morphology, composition, conductive, and magnetic properties of the resultant products were characterized by SEM, EDX, XRD, FTIR spectra, conductivity measurement, and vibrating-sample magnetometry. Polyaniline (PANI) were in situ polymerized on HGS with increasing ratios of PANI to HGS, resulting in the enhanced conductivity of HGS/PANI composites from 1.3 × 10⁻² S/cm to 4.4 × 10⁻² S/cm. Lightweight glass/Fe₃O₄-PANI composite hollow spheres (HGS/Fe₃O₄-PANI) with conductivity of 5.4 × 10⁻³ S/cm and magnetization of 9.25 emu/g were prepared by deposition of Fe₃O₄ nanoparticles onto HGS via electrostatic adsorption first, and then polymerization of aniline onto HGS/Fe₃O₄. The glass/PANI-Fe₃O₄ composite hollow spheres (HGS/PANI-Fe₃O₄) composed of Fe₃O₄ as the outmost layer and PANI as the inner layer were prepared for comparison. The conductivity and magnetization of HGS/PANI-Fe₃O₄ were 1.1 × 10⁻⁴ S/cm and 2.61 emu/g, respectively.     

Enhancing the thermoelectric performance by defect structures induced in p-type polypyrrole-polyaniline nanocomposite for room-temperature thermoelectric applications

Organic thermoelectric materials mainly conducting polymers are green materials that can convert heat energy into electrical energy and vice versa at room temperature. In the present work, we investigated the thermoelectric properties of polymer nanocomposite of polypyrrole (PPy) and polyaniline (PANI) (PPy/PANI) by varying the pyrrole: aniline monomer ratios (60:40, 50:50, and 40:60). The PPy/PANI composite is prepared by in-situ chemical polymerization of PPy on PANI dispersion. It has been observed that the combination of two conducting polymers has enhanced the electrical and thermal properties in the PPy/PANI composite due to the strong π–π stacking and H-bonding interaction between the conjugated structure of PPy and conjugated structure of PANI. The maximum electrical conductivity of 14.7 S m^?1 was obtained for composite with high pyrrole content, whereas the maximum Seebeck coefficient of 29.5 μV K^?1 was obtained for composite with high aniline content at 366 K. Consequently, the PPy/PANI composite with pyrrole to aniline monomer ratio of 60:40 exhibits the optimal electrical conductivity, Seebeck coefficient, and high power factor. As a result, the maximum power factor of 2.24 nWm^?1 K^?2 was obtained for the PPy/PANI composite at 60:40 pyrrole to aniline monomer ratio, which is 29 times and 65.8 times higher than PPy (0.077 nWm^?1 K^?2) and PANI (0.034 nWm^?1 K^?2), respectively.

     

Polyaniline and polypyrrole modified conductive nanocomposites of polyfuran and polythiophene with montmorillonite clay

Nanocomposites of polyfuran (PF) and polythiophene (PTP) with montmorillonite clay (MMT) were prepared and modified by loading of polyaniline (PANI) and polypyrrole (PPY) moieties via polymerization of aniline (ANI) and pyrrole (PY) in aqueous dispersions of PF-MMT and PTP-MMT nanocomposites. Formation of PANI and PPY and their subsequent incorporation in the PF-MMT and PTP-MMT composites was confirmed by FTIR absorption studies. X-ray diffraction (XRD) patterns of PANI and PPY modified PF-MMT and PTP-MMT composites showed that PF-MMT and PTP-MMT intercalates were still present in the modified composites. Scanning electron microscopic analysis revealed distinctive morphological patterns of the various composite particles. The dc conductivity values of PANI and PPY modified PF-MMT and PTP-MMT composites were in the order of 10⁻² S/cm in either system – a value much improved compared to the same for both of the unmodified PF-MMT (10⁻⁷ S/cm) and PTP-MMT (10⁻⁵ S/cm) nanocomposites respectively.     

HClO4–graphite intercalation compound and its thermally exfoliated graphite

The aims of this work are to synthesize the HClO₄–graphite intercalation compound (GIC) by chemical method and analyze the effects of processing parameters on the exfoliated volume (EV) of HClO₄–GIC and in the meantime, characterize the structural characteristics of HClO₄–GIC and its exfoliated graphite by using X-ray diffraction. The experimental results show that the optimum condition for preparing the HClO₄–GIC with the maximum EV of 540 cm³/g is that the intercalating reaction temperature, time, the thermally exfoliating temperature and the ratio between natural flake graphite, HClO₄ and HNO₃ are 373 K, 15 min, 1173 K and 1/4/0.15, respectively. The HClO₄–GIC synthesized through the optimum processing condition has EV of 360 cm³/g at 473 K and the natural flake graphite also can be intercalated by HClO₄ at low temperature 258 K in the system.     

A three-dimensional nanostructured PANI/MnOx porous microsphere and its capacitive performance

Three-dimensional nanostructured polyaniline (PANI) and manganese oxide (MnO _x ) composite porous microspheres were prepared by oxidizing aniline with KMnO₄ under interfacial chemical synthesis with 4-amino-thiophenol (4-ATP) as the structure-directing agent on the Au substrate. Surface morphology and chemical composition of PANI/MnO _x microsphere were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermo gravimetric-differential thermal analysis, and Fourier transform infrared spectrum. The result displayed that concentration of KMnO₄ played a key role in forming the 3D nanostructured porous microspheres. To obtain the regular shapes and uniform sizes of the porous microspheres, the optimal concentration of oxidant was 0.15 mol L⁻¹. The electrochemistry performances of PANI/MnO _x microsphere were determined by cyclic voltammograms, electrochemical impedance spectroscopy, and galvanostatic charge–discharge. The specific capacitance of the 3D nanostructured PANI–MnO _x porous microspheres exhibited a maximum value of 828 F g⁻¹ at current density of 2 mA cm⁻² over a potential range of 0.0–0.9 V versus SCE. It has improved 365 and 88 % comparing with that of PANI (178 F g⁻¹) and MnO _x (440 F g⁻¹) obtained at the similar condition. The charge–discharge tests showed the PANI/MnO _x microsphere possessed a good cycling stability. It maintained about 84.2 % of the initial capacitance after 1000 cycles at a current density of 2.0 mA cm⁻².     

Microwave adsorption of core–shell structured Sr(MnTi)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>12−2<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>19</Subscript>/PANI composites

Polyaniline polymer-coated MnTi-substituted strontium hexaferrite (Sr(MnTi) _x Fe_12−2x O₁₉/PANI, x = 1.0, 1.5, 2.0) composites were synthesized by the oxidative chemical polymerization of aniline in the presence of ammonium peroxydisulfate. The structure and morphologies of the products were characterized by X-ray diffraction, FT-IR, TGA, SEM, and TEM. In the magnetization for the Sr(MnTi) _x Fe_12−2x O₁₉/PANI composites, it was found that the saturation magnetization (M _s) and coercivity (H _c) decreased after polyaniline coating. The composite under an applied magnetic field exhibited hysteretic loops of ferromagnetic behavior, such as high saturation magnetization (M _s = 12.1–1.9 emu/g) and coercivity (H _c = 0.919–0.084 kG). The composite specimens of core–shell Sr(MnTi) _x Fe_12−2x O₁₉/PANI and thermal plastic resin had a band-width microwave absorption due to the reflection losses from −15 to −35 dB at frequencies between 18 and 40 GHz as observed by a high-frequency network analyzer.     

Conductive polymer preparation under extreme or non-classical conditions

Polyaniline (PANI) emeraldine salt form and PANI/silver composites have been synthesized by sonochemical and ionizing radiation methods. These composite materials were obtained through sonication and γ irradiation of an aqueous solution of aniline and silver nitrate, in room temperature, respectively. The mechanisms suggested to explain the formation of these products are based on the fact that both methods produce hydroxyl radical ^•OH and hydrogen radical ^•H, where hydroxyl radical ^•OH acts as an oxidizing agent in the polymerization process of aniline monomer; and hydrogen radical ^•H, as a reducing agent for silver ions. Spectroscopic, X-ray, and SEM measures show that PANI and silver nano particles of 40 nm average diameter are produced with ultrasonic methods, whereas silver nano particles of 60 nm average, and fibrillar, highly network morphology for PANI with 60 nm fibrillar diameter average are obtained using γ radiation).     

High performance cellulose acetate propionate composites reinforced with exfoliated graphene

This paper deals with the preparation, structural characterization, and physical performances of composites composed of biomass-based cellulose acetate propionate (CAP) and exfoliated graphene (EG). As a reinforcing nanofiller, EG is thus prepared by an oxidation/thermal expansion process of natural graphite flakes and it is characterized to consist of disordered graphene platelets. Structural features, thermal stability, mechanical modulus, and electrical resistivity of CAP/EG composites are investigated as a function of EG content. SEM and X-ray diffraction data demonstrate that graphene platelets of EG are well dispersed and exfoliated in the CAP matrix for the composites with up to ～1 wt.% EG, although they are partially aggregated in the composites with higher EG contents above ～3 wt.%. Thermo-oxidative stability of CAP/EG composites under active oxygen gas condition is improved substantially due to the gas barrier effect of graphene platelets of EG dispersed in the CAP matrix. Dynamic mechanical modulus of the composites is also enhanced significantly with increasing the EG content. This mechanical enhancement of CAP/EG composites is analyzed by adopting the Halpin–Tsai model. The electrical volume resistivity of CAP/EG composites prepared by melt-compounding is decreased dramatically from ～10¹⁵ to ～10⁶ Ω cm by forming the electrical conduction path at a certain EG content between 5 and 7 wt.%.     

High performance cellulose acetate propionate composites reinforced with exfoliated graphene

This paper deals with the preparation, structural characterization, and physical performances of composites composed of biomass-based cellulose acetate propionate (CAP) and exfoliated graphene (EG). As a reinforcing nanofiller, EG is thus prepared by an oxidation/thermal expansion process of natural graphite flakes and it is characterized to consist of disordered graphene platelets. Structural features, thermal stability, mechanical modulus, and electrical resistivity of CAP/EG composites are investigated as a function of EG content. SEM and X-ray diffraction data demonstrate that graphene platelets of EG are well dispersed and exfoliated in the CAP matrix for the composites with up to ∼1 wt.% EG, although they are partially aggregated in the composites with higher EG contents above ∼3 wt.%. Thermo-oxidative stability of CAP/EG composites under active oxygen gas condition is improved substantially due to the gas barrier effect of graphene platelets of EG dispersed in the CAP matrix. Dynamic mechanical modulus of the composites is also enhanced significantly with increasing the EG content. This mechanical enhancement of CAP/EG composites is analyzed by adopting the Halpin–Tsai model. The electrical volume resistivity of CAP/EG composites prepared by melt-compounding is decreased dramatically from ∼10¹⁵ to ∼10⁶ Ω cm by forming the electrical conduction path at a certain EG content between 5 and 7 wt.%.     

The preparation and morphology characteristics of exfoliated graphite derived from HClO4-graphite intercalation compounds

Natural flake graphite (NFG) and perchloric acid (PA) were used as host material and intercalating agent, respectively, to synthesize graphite intercalation compound (GIC) through chemical method in the binary HClO₄-graphite system. The HClO₄-GIC was exfoliated above 200 °C to produce exfoliated graphite (EG). The exfoliating ability of HClO₄-GIC was characterized through its exfoliated volume (EV), i.e. the apparent volume of EG of per unit weight. The effect of some technological parameters on the EV was discussed in detail. The HClO₄-GIC prepared under the condition: the intercalating reaction temperature, time and the mass ratio of PA to NFG being 120 °C, 30 min and 5/1, respectively, has an outstandingly exfoliating ability at low temperature (200 °C) and its EV can attain 360 cm³/g. In addition, the morphology characteristics of EG were characterized by scanning electron microscope.     

高导电聚苯胺/纳米石墨微片复合材料的结构与性能

以天然可膨胀石墨(GN)为原材料,采用酸及快速热处理制备了膨胀石墨(EG),再将膨胀石墨置于超声波中制得了纳米石墨微片(NanoG),最后采用原位聚合法制备了聚苯胺/纳米石墨微片(PANI/NanoG)导电复合物。扫描电镜(SEM)显示纳米石墨微片长径为0.8μm～20μm,厚度为30nm～90nm。聚苯胺均匀覆盖在纳米石墨微片表面;透射电镜(TEM)揭示了纳米石墨微片的片层分散在复合物中并形成了导电网络;电性能测试表明,当纳米石墨微片含量为0.5%(质量分数,下同)时,复合物电导率达到107.3S/cm,其渗滤阈值达到0.1%,纳米石墨微片独特的结构(宽度/厚度的高比值)及在聚苯胺中的分散造就了复合物良好的导电性能。     

Novel surfactant-stabilized graphene-polyaniline composite nanofiber for supercapacitor applications

In this work, we present a new synthesis method for surfactant stabilized graphene (SSG) combined with polyaniline nanofiber (PANI-Nf) and apply the composite material as supercapacitor (SC) electrodes by screen-printing technique. Surfactant stabilized graphene polyaniline nanofiber composite (PANI-SSG) was synthesized by electrolytic exfoliation of graphite and subsequent interfacial polymerization. Firstly, graphite was electrolytically exfoliated in an electrolyte containing anionic surfactant. Next, ammonium peroxydisulfate initiator and hydrochloric acid were added to the graphene dispersion to form the aqueous phase for interfacial polymerization of polyaniline nanofiber. This dispersion was then added to the water-insoluble solvent phase containing aniline monomer. The polymerization only occurred at the interface of the two immiscible phases leading to polyaniline nanofiber decorated graphene structures. Characterizations by scanning electron microscopy, transmission electron microscopy, atomic force microscopy and Raman spectroscopy suggested nanocomposite formation with intermolecular π-π bonding of graphene with polyaniline nanofibers. Pastes of the materials were screen printed on stainless steel current collectors and tested for SC performance by cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD) measurements with 2 M H₂SO₄ electrolyte using a home-built two-electrode test-cell. CV results showed redox peaks of polyaniline with wide cyclic loop, indicating large pseudocapacitance of the nanocomposite. From GCD measurement, a high specific capacitance of 690 Fg⁻¹ at 1 Ag⁻¹ was achieved. Therefore, PANI-SSG nano-composite prepared by electrolytic exfoliation and interfacial polymerization is a promising candidate for SC applications.     

Dielectric relaxation and ac conductivity of polyaniline–zinc ferrite composite

In situ polymerization of aniline is carried out in the presence of zinc ferrite to synthesize polyaniline/ZnFe₂O₄ composites (PANI/ZnFe₂O₄) by chemical oxidation method. The composite has been synthesized with various compositions (10, 20, 30, 40 and 50 wt.%) of zinc ferrite in PANI. From the infrared spectroscopy (FTIR) studies on polyaniline/ZnFe₂O₄ composites, the peak at 1140 cm^?1 is considered to be measure of the degree of electron delocalization. The surface morphology of these composites is studied with scanning electron micrograph (SEM). The ac conductivity and dielectric properties are studied in the frequency range from 10² to 10⁶ Hz. The results obtained for these composites are of scientific and technological interest.     

Synthesis and characterization of polyaniline nanorods/Ce(OH)3-Pr2O3/montmorillonite composites through reverse micelle template

Polyaniline (PANI) nanorods/Ce(OH)₃-Pr₂O₃/montmorillonite (MMT) nanocomposites were synthesized via in situ polymerization of aniline monomer through reverse micelle template (RMT) in the presence of montmorillonite and Ce(OH)₃, Pr₂O₃. In the experiment, sulphosalicylic acid was used as dopant, aniline was designated as oil phase and the aqueous solution comprising Ce³⁺ and Pr³⁺ as water phase. The nanocomposites were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) analysis, Fourier transform infrared (FT-IR) spectroscopy and thermogravimetry-differential thermal analysis (TG-DTA). The results showed that PANI nanorods were synthesized in the interlayer spaces of MMT with uniform spherical rare earth nanoparticles. The thermal stability of the nanocomposites prepared was enhanced drastically compared with pure polyaniline.