Segregated reduced graphene oxide polymer composite as a high performance electromagnetic interference shield

Herein, we report the synthesis of a graphene/polymer composite via a facile and straightforward approach for electromagnetic interference (EMI) shielding applications. Polystyrene (PS) beads were added in graphene oxide (GO)/water solution followed by the addition of hydroiodic acid (HI) for in situ reduction of GO. The composite solution (rGO/PS) was filtered, hot compressed and tested for EMI shielding and dielectric measurements. A 2-mm thick segregated rGO/PS sample with 10 wt% filler loading delivered a high EMI shielding effectiveness (SE) of 29.7 dB and an AC electrical conductivity of 21.8 S m^?1, which is well above the commercial requirement for EMI shielding applications. For comparison with the segregated rGO/PS composite, a control polymer composite sample utilizing a thermally reduced graphene oxide was synthesized by following a conventional coagulation approach. The as-synthesized conventional rGO/PS yield an EMI SE of 14.2 dB and electrical conductivity of 12.5 S m^?1. The high EMI shielding of segregated rGO/PS is attributed to the better filler-to-filler contact among graphene layers surrounded by PS beads and also to the better reduction and preservation of graphene structure during reduction process that makes the low temperature chemically reduced segregated rGO/PS approach a viable route compared to high temperature thermally reduced conventional rGO/PS approach.     

高导电聚苯胺薄膜的制备及其电磁屏蔽性能的研究

随着电器制品、电子器件的商用、军事用和科学应用的迅速增长 ,产生了亟待解决的电磁干扰 (也称作电磁环境污染 )问题 ,电磁干扰屏蔽日益受到关注 .本文从聚苯胺掺杂工艺角度出发 ,通过改变掺杂剂用量和溶剂种类 ,制备出高导电的聚苯胺薄膜 ,并对其电磁屏蔽特性进行了初步的测试与理论分析 ,将屏蔽效能的实测结果与理论计算值进行了比较     

Effect of oxyfluorination on electromagnetic interference shielding of polyaniline-coated multi-walled carbon nanotubes

Highly conducting polyaniline (PANi)-coated multi-walled carbon nanotubes (MWCNTs) were prepared by in situ polymerization method for electromagnetic interference shielding. The thickness of the PANi coatings was controlled by the oxyfluorination treatment on the multi-walled carbon nanotubes and analyzed with both SEM and TEM. The oxyfluorination with higher oxygen content produced more hydrophilic functional groups on the surface of multi-walled carbon nanotubes. The functional groups led to the well distribution and coating of PANi on the multi-walled carbon nanotubes resulting in the higher interfacial affinity between them. The uniform coating of PANi on MWCNTs by controlling the oxyfluorination conditions also played a crucial role in increasing the electrical conductivity of nanocomposites. The improved interfacial affinity resulted in the higher electromagnetic interference (EMI) SE of 47.03?dB based on the synergistic combination of the conductive components. The EMI shielding mechanism of PANi on MWCNTs suggested that EMI was mainly shielded by adsorption to avoid secondary EMI.     

EMI shielding and microwave absorption behavior of Au‐MWCNT/polyaniline nanocomposites

Electrically conducting Au‐multiwalled carbon nanotube/polyaniline (Au‐MWCNT/PANi) nanocomposites were synthesized by two different ways: (1) by direct mixing of MWCNT/PANi and Au nanoparticles (Au‐MWCNT/PANi‐1) and (2) by in situ polymerization of aniline in the presence of both MWCNTs and Au nanoparticles (Au‐MWCNT/PANi‐2). The higher electrical conductivity of Au‐MWCNT/PANi‐2 compared with the other samples (PANi, MWCNT/PANi, Au‐MWCNT/PANi‐1) is supported by the red shifts of the UV‐vis bands (polaron/bipolaron), the high value of the –NH+= stretch peak (Fourier transform infrared spectroscopy studies), the high % crystallinity (X‐ray diffraction analysis) and more uniform dispersion of the Au NPs in the material. The performance of the samples in electromagnetic interference (EMI) shielding and microwave absorption was studied in the X‐band (8–12 GHz). For all the samples, absorption was the dominant factor contributing toward the EMI shielding. Au‐MWCNT/PANi‐2 showed the best performance with a total shielding effectiveness of ?16 dB [averaged over the X‐band (GHz)] and a minimum reflection loss of ?56.5 dB. The higher dielectric properties resulting from the heterogeneities because of the presence of nanofillers and the high electrical conductivity lead to the increased EMI shielding and microwave absorption. The results show the significance of both Au nanoparticles and method of synthesis on the EMI shielding performance of MWCNT/PANi composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Current trends in spinel based modified polymer composite materials for electromagnetic shielding

The present article deals with current trends in spinel based modified polymer composite materials for applications in the field of electromagnetic shielding. The interaction between the various spinel based materials and polymers is an emerging field of studies among various researchers. The thermal stability, electrical conductivity, the bonding between the metal ferrites and the polymer plays an important role in the interaction of electromagnetic radiation. These properties also effect the mechanism of the EM waves for the shielding applications. Considering these all properties, polyaniline appears to be an suitable polymer for electromagnetic shielding applications. Polyaniline composites not only reinforced the properties of spinel materials but also enhanced the dielectric properties of the composite material. When carbon based materials such as graphene, graphene oxide and CNT was added along with spinel material in polyaniline based composite, they accelerate the electrical properties and enhances the shielding applications. In this paper the various synthesis methods, fabrication methods of polyaniline, and the properties of polyaniline based composites have been discussed. In addition, the various salient features and futuristic challenges of polyaniline based composite materials for EMI shielding applications were attempted to make a well equipped material for radar absorption.     

Antistatic applications of conducting polyaniline

A method is described to impart flexibility and mechanical strength to conducting polyaniline by polymerizing aniline on fabrics and on cellulose papers. The study indicates that these conducting fabrics offer 16–18 dB of shielding effectiveness for the control of electromagnetic interference (EMI) up to a frequency of 10³ MHz.     

Intrinsically conducting polymers for electromagnetic interference shielding

This paper summarizes and reviews the research on electromagnetic interference (EMI) shielding with intrinsically conducting polymers (ICPs), mainly polyaniline (PANI) and polypyrrole (PPY), and their composites in various frequency ranges. ICPs are new alternative candidates for EMI shielding applications due to their lightweight, corrosion resistance, ease of processing, and tunable conductivities as compared with typical metals. More importantly, the dominant shielding characteristic of absorption other than that of reflection for metals render ICPs more promising materials in applications requiring not only high EMI shielding effectiveness but also shielding by absorption, such as in stealth technology. Copyright © 2005 John Wiley & Sons, Ltd.     

Electromagnetic interference shielding effectiveness and microwave absorption properties of thermoplastic polyurethane/montmorillonite‐polypyrrole nanocomposites

In this work, thermoplastic polyurethane‐filled montmorillonite‐polypyrrole (TPU/Mt‐PPy) was prepared through melt mixing process for using in electromagnetic shielding applications. The effect of conducting filler content and type, sample thickness, and X‐band frequency range on the electromagnetic interference shielding effectiveness (EMI SE) and EMI attenuation mechanism was investigated. A comparative study of electrical and microwave absorption properties of TPU/Mt‐PPy nanocomposites and TPU/PPy blends was also reported. The total EMI SE average and electrical conductivity of all Mt‐PPy.Cl or Mt‐PPy.DBSA nanocomposites are higher than those found for TPU/PPy.Cl and TPU/PPy.DBSA blends. This behavior was attributed to the higher aspect ratio and better dispersion of the nanostructured Mt‐PPy when compared with neat PPy. Moreover, the presence of Mt‐PPy into TPU matrix increases absorption loss (SE_A) mechanism, contributing to increase EMI SE. The total EMI SE values of nanocomposites containing 30 wt% of Mt‐PPy.DBSA with 2 and 5 mm thickness were approximately 16.6 and approximately 36.5 dB, respectively, corresponding to the total EMI of 98% (75% by absorption) and 99.9% (88% by absorption). These results highlight that the nanocomposites studied are promising materials for electromagnetic shielding applications.     

Polarons radical polymerization

Polystyrene has been typically prepared with radical polymerization by benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN). In this report, polymerization of styrene was carried out by radical cations of polyaniline (PANI). Polarons of conducting polymers are consisting of radical cations. The polarons bear electrical conduction as a charge carrier. We employ the polarons as an initiator for radical polymerization. Polymerization of styrene and acrylonitrile by the polarons was conducted to explore new possibility of conducting polymers. Fourier‐transfer infrared absorption (FTIR) spectroscopy measurements for the resultant polymers obtained with polarons of polyaniline indicates that the polystyrene thus synthesized grows from polyaniline. The qualitative solubility, average molecular weight, and thermal stability are comparable to that of polystyrene obtained by the common method with BPO. Radical polymerization by polarons may provide a new avenue for radical polymerizations through application of conducting polymer. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 805–811     

Microstructure,electrical, and electromagnetic interference shielding properties of carbon nanotube/acrylonitrile–butadiene–styrene nanocomposites

Processing, electrical, and electromagnetic interference (EMI) shielding behaviors of carbon nanotube (CNT)/acrylonitrile–butadiene–styrene (ABS) nanocomposites were studied as function of CNT concentration. The nanocomposites were prepared by melt mixing followed by compression molding. The selective and good level of dispersion of CNT in the styrene–acrylonitrile section of the ABS polymer was found to create conductive networks in the ABS matrix at a nanofiller loading of 0.75 wt %. At this nanofiller loading, the nanocomposite electrical conductivity was 10^?5 S/m. This conductivity makes the nanocomposite suitable for electrostatic discharge protection applications. The EMI shielding effectiveness of the nanocomposites increased with the increase in nanofiller concentration. In the 100–1500 MHz frequency range, 1.1 mm thick plates made of ABS nanocomposite filled with 5 wt % CNT exhibit an EMI shielding effectiveness of 24 dB. At this shielding level, the nanocomposite is suitable for a broad range of applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Facile Fabrication of PBS/CNTs Nanocomposite Foam for Electromagnetic Interference Shielding

In order to reduce the pollutants of environment and electromagnetic waves, environment friendly polymer foams with outstanding electromagnetic interference shielding are imminently required. In this paper, a kind of electromagnetic shielding, biodegradable nanocomposite foam was fabricated by blending poly (butylene succinate) (PBS) with carbon nanotubes (CNTs) followed by foaming with supercritical CO₂. The crystallization temperature and melting temperature of PBS/CNTs nanocomposites with 4 wt % of CNTs increased remarkably by 6 °C and 3.1 °C compared with that of pure PBS and a double crystal melting peak of various PBS samples appeared in DSC curves. Increasing the CNT content from 0 to 4 wt % leads to an increase of approximately 3 orders of magnitude in storage modulus and nearly 9 orders of magnitude in enhancement of electrical properties. Furthermore, CNTs endowed PBS nanocomposite foam with adjustable electromagnetic interference (EMI) shielding property, giving a specific EMI shielding effectiveness of 28.5 dB cm³/g. This study provides a promising methodology for preparing biodegradable, lightweight PBS/CNTs foam with outstanding electromagnetic shielding properties.     

Electrically conductive composite prepared by template polymerization of pyrrole into a complexed polymer

Electrically conducting polymer composite films have been synthesized by the exposure of poly(4-vinylpyridine) complexed with cupric ions to pyrrole and water vapor. To immobilize a stoichiometric amount of the oxidant inside the polymer matrix, the ratio of poly(4-vinylpyridine)/cupric ion = 1.8 was chosen. Polypyrrole was formed in this tailored structure by a template polymerization process. Opaque polymer composite films with electrical conductivity up to 60 (Ω cm)^?1 have been obtained by this method, However, slightly colored transparent composite thin films with a conductivity as high as 50 (Ω cm)^?1 were also produced. The electrically conducting polymer composite films and the metal-polymer complex have been characterized by XPS and IR spectroscopy, elemental analysis, EDX, and scanning electron microscopy. The polymerization process was also followed by use of a quartz crystal microbalance. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of red mud/polyaniline composites: Electrical properties and thermal stability

New types of conducting composites using red mud as an inorganic substrate and polyaniline as the conducting phase were prepared. Red mud/polyaniline (RM/PANI) composites were synthesized in acidic aqueous solution by the chemical oxidative polymerization of aniline using ammonium peroxydisulfate as the oxidant. The composites exhibit conductivities in the 0.42-5.2 S cm⁻¹ range, depending on the amount of polyaniline. They were characterized by infrared and UV-vis spectroscopy, scanning electron microscopy and X-ray diffraction. The IR and X-ray results show that PANI is deposited on the RM surface. The composites have a globular structure and the PANI globules synthesized on the surface of RM are smaller than those prepared under the same conditions without the substrate. Thermogravimetric analysis was used for investigation of the thermal stability of the composites. The thermal stability of the conductivity of RM/PANI composites was studied by ageing at 125 °C, the conductivity being measured in situ during this process.     

Solidification of non-halogen fire-retardant liquids by encapsulation within porous uniform PDVB microspheres for preparation of fire-retardant polymeric blends

Polystyrene/polydivinyl benzene (PS/PDVB) composite microspheres of narrow size distribution were prepared by a single-step swelling process of uniform PS microspheres with DVB and benzoyl peroxide, followed by polymerization of DVB within the microspheres. Dissolution of the PS template resulted in porous uniformly sized PDVB microspheres. New, solid, non-halogenated, fire-retardant composite microspheres of narrow size distribution were prepared by encapsulation of resorcinol bis (diphenyl phosphate) (RDP) within the pores of the PDVB microspheres. The encapsulation was performed by two different methods as follows: (1) vacuum and (2) heat/cool cycles. The loading capacity of the RDP into the PDVB particles was elucidated. PS/PDVB-RDP blends were prepared by mixing PS with the PDVB-RDP microspheres. Thermogravimetric analysis (TGA) illustrated that the thermal stability of the PS increases as the content (10–40 %) of the PDVB-RDP increased. Polycarbonate/poly(acrylonitrile-butadiene-styrene)/PDVB-RDP (PC/ABS/PDVB-RDP) blends were prepared by melting PC/ABS together with the PDVB-RDP microspheres at 250 °C and then pelleting it in an injection molding machine at 250 °C and 40 t. The improved thermal stability of the PC/ABS by blending it with PDVB-RDP was demonstrated by a vertical burn test on PC/ABS/PDVB-RDP bones.     

Effect of cellulose nanofibers on induced polymerization of aniline and formation of nanostructured conducting composite

Cellulose nanofibers (CNFs), derived from the most abundant and renewable biopolymer, are known as natural one-dimensional nanomaterials because of their high aspect ratio. CNFs also are rich in hydroxyl groups, offering opportunities for functionalization toward development of high-value nanostructured composites. Herein, CNFs were extracted from poplar wood powder by chemical pretreatment combined with high-intensity ultrasonication, and then coated with polyaniline (PANI) through in situ polymerization. The PANI-coated CNFs formed nanostructured frameworks around PANI, thereby conferring the CNF/PANI composite with stability and higher charge transport. The optimum PANI content to achieve maximum conductivity of CNF/PANI composites was determined. The morphology, crystall structure, chemical composition, and conductivity of the samples were characterized by transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and four-point probe method, respectivily. Our results demonstrated that CNFs can be effective as a template for a flexible and stable conducting polymer to form higher-order nanostructures.     

Conducting polyaniline/nano-zinc phosphate composite as a pigment for corrosion protection of low-carbon steel

Zinc phosphate (Zn₃(PO₄)₂) nanocrystals were synthesized and used for making conducting polyaniline/nano-zinc phosphate composite by chemical oxidative method. The product was characterized by UV–visible absorption spectroscopy. The crystal structure, morphology and thermal stability of the product were studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermo gravimetric analysis, respectively. The epoxy-based paint containing conducting polyaniline/nano-zinc phosphate composite pigment was applied on low-carbon steel samples. Corrosion protection performance of the painted low-carbon steel samples in 3.5 mass % sodium chloride solution was evaluated using electrochemical technique. Transmission electron microscopic image revealed the formation of core shell structure of the composite. Composite was found to be more thermally stable than the conducting polyaniline. The corrosion rate of conducting polyaniline/nano-zinc phosphate-painted low-carbon steel was found to be 5.1 × 10^?4 mm per year, about 34 times lower than that of unpainted low-carbon steel and 10 times lower than that of epoxy nano-zinc phosphate paint-coated steel. The study reveals the possibility of using conducting polyaniline/nano-zinc phosphate as a pigment for corrosion protection.     

Thermomechanical behaviors and dielectric properties of polyaniline‐doped para‐toluene sulfonic acid/epoxy resin composites

Composites based on conductive organic/inorganic fillers dispersed in insulating matrix have been widely investigated because of their widespread applications such as electromagnetic shielding, electrostatic discharge, and sensors. In this context, novel composite materials based on epoxy resin matrix charged with polyaniline (PANI)‐doped para‐toluene sulfonic acid were elaborated. Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy were used to check the structure and the morphology of the samples. Viscoelastic behavior and thermal stability of the composites were explored by dynamic mechanical thermal analysis and thermogravimetric analysis. It was shown that the PANI particles exhibited a partial crystalline structure and were homogeneously dispersed in epoxy matrix. Consequently, this structure affected the thermal stability and viscoelastic properties of the composites. Furthermore, the dielectric and electrical properties were investigated up to 1 MHz. Measurements of dielectric properties revealed that with loading fillers in matrix, the dielectric parameters increased to high values at low frequency then decreased at values around 40 and 32 of real and imaginary parts, respectively, at 1 MHz with 15% of PANI content. Copyright © 2011 John Wiley & Sons, Ltd.     

Self-sustaining hybrid electrode prepared from polyaniline,carbon nanotubes,and carbon fibers: morphological,structural, and electrochemical analyses

The self-sustaining hybrid electrode was prepared via chemical polymerization of aniline in acid medium containing dispersed carbon nanotubes (CNT), using carbon fiber (CF) as conducting substrate. The ternary composites called PAni/CNT/CF were characterized in order to evaluate their morphologies, structures, and thermal properties. The influence of the polyaniline (PAni) layer in the ternary composite properties was studied considering different deposition times on CF samples (30, 60, and 90 min). The ternary composite morphologies were observed by scanning electron microscopy while thermal structural analyses were obtained using thermogravimetric measurements. The structural features were analyzed by Raman scattering spectroscopy and Fourier transform infrared spectroscopy (FTIR). The possible interactions between PAni and CNT were discussed on the basis of Raman and FTIR spectra. These spectroscopic analyses also confirmed that the PAni present in the composite is in the emeraldine (ES) salt form. Furthermore, the ternary composites were also evaluated by electrochemical measurements such as cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) techniques. The results showed good charge storage capacity for ternary composites, in particular, for PAni/CNT/CF obtained with 90 min of deposition time, which exhibited specific capacitance of around 500 F g^?1. Therefore, this electrode was selected to build a prototype of type I supercapacitor. This device presented specific capacitance of around 143 F g^?1 after 3200 charge/discharge cycles.     

Thermal analysis of polyaniline poly(N-vinylpyrrolidone)-stabilized dispersions

The polyaniline dispersions stabilized with poly(N-vinylpyrrolidone) (PANI/PVP) were synthesized by oxidative polymerization with different mass ratios of PANI and PVP and different molar concentrations of the components in the polymerization mixture. The composite powders prepared from colloidal PANI/PVP dispersions were characterized by thermogravimetry and differential thermal analysis. The change in the ratio of PANI and PVP as well as the starting molar concentrations of aniline hydrochloride and oxidant has influence on the resulting properties of the dispersions. Concerning the doping, the results show that PANI/PVP powders are stable up to approximately 160 °C. Degradation of polymer chains starts at temperatures above 250 °C. The PANI/PVP composite powders with lower content of PANI exhibit slightly higher thermal stability. Further, colloidal PANI/PVP dispersions were screen-printed on aluminum foil for infrared spectroscopic characterization and on poly(ethylene terephthalate) foil for electrical measurements. The sheet resistance of printed layers measured by two-point probe was of the order of tens to thousands of kΩ sq^?1. The influence of both the change in the composition and the drying temperature is discussed.     

Lightweight electromagnetic shields using optimized polyaniline composites in the microwave band

A genetic algorithm (GA) was used to optimize a multilayer electromagnetic shield of polyaniline (PANI)–polyurethane (PU) conducting composites in the microwave band. First, the electronic properties of freestanding films with different mass fractions of polyaniline were studied. A very low percolation threshold (0.2%) was found, with a maximum of conductivity of 10⁴ S/m. Second, the electromagnetic shielding effectiveness of the films were investigated in the X and Ku bands (8.2–18 GHz), showing an attenuation increase of 1–40 dB with the mass fraction of polyaniline in the blends. Then, the electromagnetic shielding properties of multi‐layered PAni–PU composites were investigated in order to obtain an attenuation superior to 40 or 80 dB, depending on the application. To improve the performances of the electromagnetic shields, three‐layered PAni–PU composites were made, using an optimization method. The intrinsic physical parameters of the composites were used as a database for the optimization calculation. The optimization results showed that materials with a thickness of <500 µm could answer many industrial or military shielding applications. As the electronic properties can be tuned easily with the mass fraction of polyaniline in the blends, conducting multi‐layered composite materials can be made following the results of the optimization. Their electromagnetic shielding effectiveness was measured, showing good agreement between the measurements and modeling. These results demonstrated that the genetic algorithm allows us to conceive lightweight and high performance electromagnetic shields using intrinsically conducting polymers. The mass per unit of surface of the shield was <200 g/m², giving potential applications in the aeronautics domain. Copyright © 2007 John Wiley & Sons, Ltd.