Synthesis and characterization of composites of polyaniline and polyurethane‐modified epoxy

A toughened, semiconductive polyaniline/polyurethane (PANI/PU)‐epoxy nanocomposite was prepared using a conductive polymer, PANI, and a PU prepolymer‐modified diglycidyl ether of bisphenol A (DGEBA) epoxy. The formation of a nanostructure was confirmed by Fourier transform infrared spectroscopy and SEM. The mechanical properties of the composites were evaluated and compared with those of the corresponding matrix. The improvement in impact strength of the composites (especially in the PANI/PU(PPG2000)‐epoxy system) was explained after fracture surface analysis using SEM. DSC and TGA studies indicated that the thermal properties of these composites were comparable to those of DGEBA epoxy. A conductivity in the range 10^?9–10^?3 S cm^?1 was obtained, depending on the testing frequency (10³–10⁷ Hz) and the PANI content incorporated. Copyright © 2006 Society of Chemical Industry     

Electrically conductive composites based on epoxy resin containing polyaniline–DBSA‐ and polyaniline–DBSA‐coated glass fibers

Four kinds of polyaniline (PANI)‐coated glass fibers (GF–PANI) combined with bulk PANI particles were synthesized. GF–PANI fillers containing different PANI contents were incorporated into an epoxy–anhydride system. The best conductivity behavior of the epoxy/GF–PANI composites was obtained with a GF–PANI filler containing 80% PANI. Such a composite shows the lowest percolation threshold at about 20% GF–PANI or 16% PANI (glass fiber‐free basis). The PANI‐coated glass fibers act as conductive bridges, interconnecting PANI particles in the epoxy matrix, thus contributing to the improvement of the conductivity of the composite and the lower percolation threshold, compared with that of a epoxy/PANI–powder composite. Particularly, the presence of glass fibers significantly improves the mechanical properties, for example, the modulus and strength of the conductive epoxy composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1329–1334, 2004     

High Thermal Conductivity Nanocomposites Based on Conductive Polyaniline Nanowire Arrays on Boron Nitride

With the development of soft electronics, conductive composites are garnering an increasing amount of attention. The electrical conductivity, thermal conductivity, and electrical stability of conductive composites are all very important. In particular, the thermal conductivity of conductive composites is critical to the stability of their conductive properties. However, little is reported on thermal management in conductive systems. Herein, sufficiently hydroxylated boron nitride nanosheets (BN‐OH)@polyaniline (PANI) composite nanosheets with a high thermal conductivity and outstanding conductance stability are reported. PANI nanowire arrays are aligned vertically on BN‐OH. This well‐ordered nanostructure provides the means to form a good conductive and thermally conductive path. Notably, the composite through‐plane thermal conductivity is 2.1 W m^?1 K^?1(≈1000% that of pure PANI) and that the resistivity of the composite is 1.38 Ω cm. Importantly, the resistivity of the composite remains unchanged after 1 h of work. The results show that this composite has prospective applications for use in soft electronics.     

Nano‐SiO2/PMMA‐PU composite particles with core‐shell structure via emulsion polymerization and their application in epoxy resin

A novel method of nano‐SiO₂/poly(methyl methacrylate)(PMMA)‐polyurethane(PU) composite particles modifying epoxy resin is reported. The composite particles with the obvious core‐shell structure were prepared by emulsion polymerization of PMMA and PU prepolymer on the surface of nano‐SiO₂. The diameter of the composite particles was 50–100 nm with dark core SiO₂ (30–60 nm) and light shell polymer of PMMA and PU (20–30 nm); moreover, PU was well distributed in PMMA with about 10 nm diameter. After nano‐SiO₂ was encapsulated by PMMA and PU, the Si content on the surface decreased rapidly to 2.08% and the N content introduced by PU was about 1.27%. The ratio of polymer to original nano‐SiO₂ (f_p), the grafting ratio of polymer to original nano‐SiO₂ (f_r) and the efficiency grafting ratio of polymer (f_e) were, respectively, about 116.7%, 104.4%, and 89.5%. The as‐prepared composite particles were an effective toughness agent to modify epoxy resin, and the impact strength of the modified epoxy resin increased to 46.64 kJ m^?2 from 19.12 kJ m^?2 of the neat epoxy resin. This research may enrich the field of inorganic nanoparticles with important advances toward the modification for polymer composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41919.     

Polyether and polyester polyol based glycidyl-terminated polyurethane modified epoxy resins: Mechanical properties and morphology

A glycidyl-terminated polyurethane prepolymer was synthesized and used to enhance the properties of epoxy resins. Some properties of glycidyl-terminated PU/epoxy with polyether based (PPG) and polyester based (PBA) glycidyl-terminated PU were investigated in this research. The polyether based glycidyl-terminated PU(PPG) modified epoxy resin proved to be superior to conventional epoxy resins in improved impact strength and fracture energy, but not tensile strength, tensile modulus, flexural strength and flexural modulus. On the other hand, the polyester based glycidyl-terminated PU(PBA) modified epoxy resin had increased mechanical properties while showing slight variation of impact strength and fracture energy. Different mechanisms for this behaviour are advanced in this paper.     

Preparation and performance of PANI–PVA composite film doped with HCl

The polyaniline (PANI)–poly (vinyl alcohol) (PVA) composite film doped with HCl was prepared by adopting PVA as matrix. Effects of PVA content and film drying temperature on properties of HCl–PANI–PVA composite film were studied. A comparison was made for tensile strength, elasticity, conductivity and thermal stability of PVA, HCl–PANI or HCl–PANI–PVA. PVA film presented the highest tensile strength and elasticity (150.8?MPa and 300.0%), but its conductivity was the lowest. The conductivity of HCl–PANI–PVA was the highest (1500?S?m^?1), and tensile strength and elasticity of HCl–PANI–PVA were higher than those of HCl–PANI. The order of their thermal stability is PVA?>?HCl–PANI?>?HCl–PANI–PVA before 260°C, and the order of their thermal stability is HCl–PANI?>?HCl–PANI–PVA?>?PVA after 260°C. At the same time, the structure and conductive mechanism of composite materials were characterised and analysed through infrared and scanning electron microscopy (SEM).     

聚醚型聚氨酯增强增韧环氧树脂的研究

用聚丙二醇(PPG400,PPG1000)与异佛尔酮二异氰酸酯(IPDI)反应制备了聚氨酯(PU)预聚体,然后通过与环氧树脂(EP)的加成反应和环氧树脂的固化反应将聚氨酯引入环氧固化物网络,并研究了两种聚醚型聚氨酯对环氧树脂的改性效果。结果发现,聚氨酯的引入不但起到了增韧的作用,而且使体系的强度有了很大的提高。随聚氨酯用量增大,PU/EP材料拉伸强度、弯曲强度、冲击强度均先增大后减小,过多的聚氨酯用量导致其不能接人环氧固化物网络;分子链较短的PPG400型聚氨酯的改性效果优于PPG1000,PU与EP的质量之比的最佳值为15%～20%;1,4-丁二醇/三羟甲基丙烷的引入能够使体系中聚氨酯分子链增长并交联成网状,但并不能进一步提高PU/EP材料的强度和韧性。     

Control of Conductive and Mechanical Performances of Poly(Amide‐Imide) Composite Films Utilizing Synergistic Effect of Polyaniline and Multi‐Walled Carbon Nanotube

Functionalized multi‐walled carbon nanotubes (FMWCNTs) have been incorporated into binary composites of poly(amide‐imide) (PAI) and polyaniline (PANI) to improve their conductive and mechanical performances. The conductivity of PAI/PANI/FMWCNTs ternary composites significantly increased from 10^?3 to 8.3 S m^?1 with increasing the weight ratio of FMWCNTs from 0 to 10 wt%, which is much higher than that of the sum of PAI/PANI and PAI/FMWCNTs binary composites. The enhanced conductivity is mainly ascribed to be the more intensive conductive percolating network formed in the PAI/PANI/FMWCNTs ternary composites due to the hydrogen bond interaction among PAI, PANI and FMWCNTs. On the other hand, the tensile strength has been improved by 40% from 25 to 35 MPa. The self‐extinguishing property and phase transition of the ternary films have also been investigated by thermal gravimetric analysis and differential scanning calorimetry, respectively. It is found that the weight ratio of FMWCNTs and the special morphology are the two important factors that induce such unusual properties. POLYM. ENG. SCI., 59:E224–E230, 2019. © 2018 Society of Plastics Engineers     

Polyaniline-Coated Short Nylon Fiber/Natural Rubber Conducting Composite

Natural rubber-Polyaniline (PANI)-Polyaniline coated short nylon-6 fiber (PANI-N6) composites were prepared by mechanical mixing and its cure characteristics, filler dispersion, mechanical properties, conductivity and thermal stability were evaluated. PANI was synthesized by chemical oxidative polymerization of aniline in presence of hydrochloric acid. PANI-N6 was prepared by in situ polymerization of aniline in the presence of short nylon-6 fiber. The composite showed higher tensile strength, tear strength and modulus values and lower elongation at break. The DC electrical conductivity and the thermal stability of the composites increased with PANI and PANI-N6 concentration. The highest conductivity obtained was 1.99 × 10^?6 S/cm.     

Photo‐induced protonation and conductivity of polyaniline/poly(ethylene glycol) and polyaniline/[poly(ethylene glycol)‐grafted polyaniline] composites

Composites of polyaniline in its emeraldine base form (PANI‐EB) and photo‐acid generators (PAG) show an increase in conductivity upon photo‐irradiation due to the protonation of PANI‐EB. Such materials may be utilized to fabricate conducting patterns by photo‐irradiation. However, the conductivity obtained by direct irradiation of PANI‐EB/PAG composites was normally quite low (<10^?3 S/cm) due to aggregation of highly loaded PAG. In this work, poly(ethylene glycol) (PEG), which is a proton transfer polymer, was added to PANI‐EB/PAG. Results showed that addition of low M_w (550) PEG significantly enhance the photo‐induced conductivity. Conductivities as high as 10^?1–10⁰ S/cm were observed after photo‐irradiation. This conductivity is comparable to that of PANI‐salt synthesized by oxidizing aniline in the presence of an acid. High M_w (8000) PEG is much less effective than PEG 550, which is attributed to its lower compatibility with PANI. PEG‐grafted PANI (N‐PEG‐PANI) was also studied as an additive. Composites of PANI‐EB and N‐PEG‐PANI showed conductivity as high as 10² S/cm after treatment with HCl vapor. The photo‐induced conductivity of the N‐PEG‐PANI/PANI‐EB/PAG composite reached 10^?2–10^?1 S/cm. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Interpenetrating polymer networks of bismaleimide and polyether polyurethane–crosslinked epoxy

In this work, we prepared the interpenetrating polymer networks of bismaleimide and polyether-type polyurethane(polyoxypropylene)–crosslinked epoxy (BMI/PU(PPG)–EP IPNs) by employing the simultaneous bulk polymerization technique. The polyurethane (PU)–crosslinked epoxy was identified via infrared (IR) spectra analysis. Also investigated herein were the mechanical properties, including tensile strength, Izod impact strength, and fracture energy (G_IC) of the IPNs with various BMI contents in PU–crosslinked epoxy matrix. In addition, differential scanning calorimetry (DSC) analysis and the thermogravimetric analysis (TGA) were performed to examine the thermal properties of the BMI/PU(PPG)–EP IPNs. In addition, morphology and dynamic mechanical analysis (DMA) of the BMI/PU(PPG)–EP IPNs were also studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2635–2645, 1998     

Water‐dispersible nanocomposites of polyaniline and montmorillonite

The polymerization of aniline (ANI) in aqueous medium in the presence of (NH₄)₂S₂O₈ and montmorillonite (MMT) resulted in the formation of a nanocomposite (PANI–MMT). The inclusion of PANI in the composite was confirmed by FTIR studies. The extent of PANI loading in the composite increased with ANI concentration at a fixed oxidant/MMT amount and with the oxidant amount at a fixed ANI and MMT weight, but decreased with an MMT amount at a fixed ANI and oxidant level. TGA revealed a higher stability for the PANI–MMT composite relative to PANI and confirmed a PANI loading of ca. 51% in the composite. The conductivity increased in all the cases. XRD analysis revealed no expansion of the d₀₀₁ spacing at 9.8 Å, implying no intercalation of PANI within the MMT layers. Scanning electron micrography studies revealed interesting morphological features for the composites. Transmission electron micrography analysis revealed distinctive features and confirmed the formation of PANI–MMT composite particles of diameters in the 300‐ to 400‐nm range. These composites could be obtained as stable colloids in the presence of poly (N‐vinyl pyrrolidone) under selective conditions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2948–2956, 2000     

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     

Thermal and mechanical properties of poly(urethane‐imide)/epoxy/silica hybrids

Improving properties of polyurethane (PU) elastomers have drawn much attention. To extend the properties of the modified PU composite, here a new method via the reaction of poly(urethane‐imide) diacid (PUI) and silane‐modified epoxy resin (diglycidyl ether of bisphenol A) was developed to prepare crosslinked poly (urethane‐ imide)/epoxy/silica (PUI/epoxy/SiO₂) hybrids with enhanced thermal stability. PUI was synthesized from the reaction of trimellitic anhydride with isocyanate‐terminated PU prepolymer, which was prepared from reaction of polytetramethylene ether glycol and 4,4′‐diphenylmethane diisocyanate. Thermal and mechanical properties of the PUI/epoxy/SiO₂ hybrids were investigated to study the effect of incorporating in situ SiO₂ from silane‐modified epoxy resin. All experimental data indicated that the properties of PUI/epoxy/SiO₂ hybrids, such as thermal stability, mechanical properties, were improved due to the existence of epoxy resin and SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of dopant and oxidant on the electrochemical properties of polyaniline/graphite nanoplate composites

Optimizing the synthesis parameters of polyaniline/graphite nanoplate (PANI/GNP) composite is essential to the final electrochemical performance. Herein, the electrochemical properties of PANI/GNP composites, prepared by in situ chemical polymerization using varying amounts of different oxidants, with or without the addition of 4‐dodecylbenzenesulfonic acid (DBSA) as dopant, were investigated. Cyclic voltammetric results suggested that a stoichiometric amount of the oxidant iron chloride (FeCl₃) was beneficial to the electrochemical properties of the composites. The use of ammonium persulfate (APS) instead of FeCl₃ as oxidant largely increased the actual PANI content, conductivity and specific capacitance of the PANI/GNP composites. The dopant DBSA increased the conductivity of the PANI/GNP composites but did not show a positive effect on the electrochemical behavior. The cyclic voltammograms of the PANI/GNP composites indicated that the pseudocapacitance of PANI contributes more than the electrical double‐layer capacitance of GNP to the capacitance of the composites, while the presence of GNP plays an essential role in the rate capability of the composites. In this study, PANI/GNP (1:1) composite synthesized with an APS to aniline molar ratio of 1 showed a balanced combination of high specific capacitance (180.5 F g^?1 at 20 mV s^?1) and good rate capability (78% retention at 100 mV s^?1). © 2018 Society of Chemical Industry     

Polyaniline–13X zeolite composite‐supported platinum electrocatalysts for direct methanol fuel cell applications

We successfully synthesized 13X zeolite using a hydrothermal method. Then, composites of polyaniline (PANI) with 13X zeolite and PANI–13X with platinum were prepared by chemical oxidative polymerization and chemical reduction, respectively. Field emission scanning electron microscopy, X‐ray diffraction, Raman spectroscopy and Brunauer–Emmett–Teller techniques were used to characterize the PANI–Pt and PANI–Pt–13X composites. Further, the electrocatalytic activity towards methanol oxidation of the synthesized catalysts was explored using cyclic voltammetry in 1 mol L^?1 CH₃OH + 0.5 mol L^?1 H₂SO₄ solution. From the obtained results, PANI–Pt–13X shows superior performance compared to PANI–Pt towards methanol oxidation and electrical conductivity. Hence, the 13X zeolite‐incorporated PANI–Pt composite could be an efficient catalyst for direct methanol fuel cell applications. © 2019 Society of Chemical Industry     

Doping effects of cerium ion on structure and electrochemical properties of polyaniline

Polyaniline (PANI)/Ce³⁺ and PANI/Ce⁴⁺ composites were successfully prepared by in situ polymerization in an aqueous solution of poly(2‐acrylamido‐2‐methylpropane sulfonic acid) and characterized by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, X‐ray photoelectron spectroscopy, SEM, TEM and electrochemical methods. The results showed that the PANI/Ce ion composites had a high degree of sphericity, high electrical conductivity and good electrochemical performance. The conductivity of PANI/Ce(NO₃)₃ reaches a maximum of 46.76 S cm^?1 at 20 wt% of Ce(NO₃)₃. It is increased by 377% by comparison with that of pure PANI. In particular, the polarization results showed that the corrosion current density (0.47 µA cm^?2) and the inhibition efficiency (97%) of PANI/Ce(NO₃)₃ were better than the results for PANI and PANI/Ce(SO₄)₂ composite. This suggested that the PANI/Ce(NO₃)₃ composite has promising applications in conductive materials, anticorrosion coatings and other related fields. © 2017 Society of Chemical Industry     

Molecular composites obtained by polyaniline synthesis in the presence of p‐octasulfonated calixarene macrocycle

Polyaniline (PANI) molecular composites were synthesized by chemical oxidative polymerization of the aniline and aniline dimer, N‐phenyl‐1,4‐phenylendiamine, in the presence of a macrocycle, calix[8]arene p‐octasulfonic acid (C8S), using ammonium peroxidisulfate as oxidant. The macrocycle has acted both as acid dopant and surfactant to obtain processable PANI‐ES. The PANI/calix[8]arene p‐octasulfonic acid composite was also obtained by a simple doping of PANI emeraldine base form with calix[8]arene sulfonic acid. The structure of materials was confirmed by Fourier transform infrared, UV–vis and nuclear magnetic resonance spectroscopy. All synthesized composite materials are amorphous and soluble in chloroform, dimethylsulfoxide, NMP, showing excellent solution‐processing properties combined with electrical conductivity. Cyclic voltammetry evidenced a good electroactivity for the composite films. Dielectric properties (dielectric constant and dielectric losses) were determined and are comparable with those of other PANI/ionic acid polymer composites. Preliminary studies have evidenced a high dielectric constant (10⁴ at 100 Hz) and electrical conductivity of 6 × 10^?3 S/cm for PANI composites. From sulfur elemental analysis of the PANI/calixarene, it results that the content in macrocycle is ～30% (weight). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Experimental investigation and numerical simulation of granite powder filled polymer composites for wind turbine blade: A comparative analysis

This paper describes the mechanical, thermo‐mechanical, and thermal behavior of unfilled E‐glass fiber (10–50 wt%) reinforced polymer (GFRP) composites and granite powder filled (8–24 wt%) GFRP composite in different weight percentages, respectively. The void fraction of unfilled glass epoxy composite is decreased from 7.71% to 3.17% with the increase in fiber loading from 10 to 50 wt%. However, void fraction for granite powder filled GFRP composites show reverse in trend. The granite powder addition in glass‐epoxy composites show significant improvement in hardness (37–47 Hv), impact strength (31.56–37.2 kJ/m²), and stress intensity factor (by 14.29% for crack length of 5 mm) of the composites. The thermo‐mechanical analyses also show strong correlation with the mechanical performance of the composites. The minimum difference of 0.17 GPa in storage and flexural moduli are observed for unfilled 20 wt% glass epoxy composite; whereas, maximum difference of 0.71 GPa is recorded for unfilled 50 wt% glass epoxy composite. Moreover, the numerical and experimentally measured thermal conductivity of unfilled and granite powder filled epoxy composites are within the lower and upper bound values. Hence, a successful attempt is presented for mechanical analysis of full scale model by finite element analysis. The results show that finite element analysis predicted reasonably actual stress value and tip deflection of wind turbine blade. POLYM. COMPOS., 38:1335–1352, 2017. © 2015 Society of Plastics Engineers     

聚氨酯改性环氧树脂胶粘剂的制备及性能研究

由端-NCO基聚氨酯(PU)预聚物与环氧树脂反应,制备了PU接枝改性环氧树脂。着重探讨了PU预聚物的含量、活性稀释剂的含量和异氰酸酯结构等因素,对改性环氧树脂的粘度和粘接性能的影响。实验结果表明,该改性环氧树脂的粘度随着PU预聚物含量的增加而逐渐增大,随着活性稀释剂含量的增加而逐渐降低,而且在相同的条件下,用不同的二异氰酸酯改性环氧树脂的粘度大小次序为:IPDI型>MDI型>TDI型;该改性环氧树脂在PU预聚物含量为20%时,对铝片/铝片的剪切强度最大(7.82 MPa);在PU预聚物含量为10%时,对铁片/铁片的剪切强度最大(11.70 MPa),而且TDI型和IPDI型改性环氧树脂的粘接性能明显好于MDI型改性环氧树脂。