Polymerization and characterization of high conductivity and good adhension polypyrrole films for electromagnetic interference shielding

<正>Polypyrrole(PPy) shows a favorable application in the electromagnetic interference(EMI) shielding due to its good electrical conductivity and outstanding air stability.Conducting PPy films with high conductivity and good adhesion were successfully polymerized on the surface of insulating epoxy resin substrates using chemical polymerization.The factors affecting the properties of PPy films,such as the surface morphology,adhesion between PPy film and substrate,electrical conductivity,EMI shielding effectiveness(SE),were investigated.The adhesion was improved significantly through a three-step surface pretreatment of epoxy resin substrates including removing impurities,roughening,and surface modification with silane coupling agent.An enhancement in the conductivity of PPy films of about one order of magnitude was achieved by adding dopant in FeCl_3 solution.The higher the conductivity,the better the shielding effectiveness.Taking sodium p-toluenesulfonate doped PPy film as example,EMI SE was in the practically useful range of about 30 dB over a wide frequency range from 30 MHz to 1500 MHz.The PPy film samples were characterized by scanning electron microscopy (SEM),infrared spectra(IR),X-ray photoelectron spectroscopy(XPS) and the flange coaxial transmission device.The fourpoint probe method was used to measure conductivity of PPy films.     

Multi-layered graphene-Fe3O4/poly (vinylidene fluoride) hybrid composite films for high-efficient electromagnetic shielding

A flexible and multi-layered graphene nanosheets (GNSs)-Fe₃O₄/poly (vinylidene fluoride) hybrid composite film with high-efficient electromagnetic interference (EMI) shielding was fabricated via a facile layer-by-layer coating. The well-designed multi-layered and hybrid electromagnetic fillers endow the prepared film with good surface impedance matching and prominent internal multiple absorption, which forms “absorb-reflect-reabsorb” electromagnetic transmission pattern and results in highly efficient electromagnetic shielding effectiveness (EMI SE). The resultant composite film exhibits an exceptional EMI SE of 52.0 dB at a thickness of 0.3 mm. What is more important is that the prepared film exhibits excellent flexibility and EMI stability, and the retention rate of efficient EMI SE is high as 91.9% after 1000 bending-release cycles. This study provides a feasible strategy for designing high-efficient EMI shielding film with excellent flexibility and ultra-thin thickness that suitable for next-generation intelligent protection devices.     

Polyaniline/thermoplastic polyurethane blends: Preparation and evaluation of electrical conductivity

Conducting polymer blends whose undiluted components have different properties are promising materials for specific applications and have attracted interest in recent years. The aim of this study was to obtain and evaluate the electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid (PAni.DBSA)/polyurethane thermoplastic (TPU) blends. The PAni.DBSA was synthesized from DBSA-aniline (DBSAn) salt through an emulsion polymerization in tetrahydrofurane (THF) or in the presence of polyurethane thermoplastic solution, resulting in pure PAni.DBSA or PAni.DBSA/TPU blends. Blends of PAni.DBSA/TPU were also prepared through casting, at room temperature, after dissolving both components in THF as a common solvent. The insulator-conductor transition was very sharp and the percolation threshold was lower than 2.7 wt% of PAni.DBSA. The electrical conductivity of PAni.DBSA/TPU blends, prepared by both methods, reached maximum values at a PAni.DBSA concentration of 40 wt%, close to the value observed for the undiluted conducting polymer. However, for a PAni.DBSA content lower than 30 wt%, the electrical conductivity was dependent on the blend preparation method. Blends were characterized by infrared spectroscopy, thermogravimetric analysis (TG) and optical microscopy. The electrical conducting characteristics of the PAni.DBSA/TPU blends prepared using different procedures indicate a high potential for their successful application in electrical processes.     

Recent progress in MXene and graphene based nanocomposites for microwave absorption and electromagnetic interference shielding

There is widespread use of telecommunication and microwave technology in modern society, and raised the electromagnetic interference (EMI) issue to alarming situation due to apprehensive demand and growth of 5G technology undesirably disturbing the human health. The two dimensional (2D) materials including graphene and MXenes are already been used for variety of electronic devices due to their exceptional electrical, mechanical, optical, chemical, and thermal properties. MXene is composed of metal carbides, in which mainly metals are the building blocks for dielectrics, semiconductors, or semimetals. However, the strong interfaces with electromagnetic waves (EM) are variable from terahertz (THz) to gigahertz (GHz) frequency levels and are widely used in EMI and Microwave absorption (MA) for mobile networks and communication technologies. The use of different organic materials with metal, organic, inorganic fillers, polymers nanocomposite and MXene as a novel material has been studied to address the recent advancement and challenges in the microwave absorption mechanism of 2D materials and their nanocomposites. In this concern, various techniques and materials has been reported for the improvement of shielding effectiveness (SE), and theoretical aspects of EMI shielding performance, as well stability of 2D materials particularly MXene, graphene and its nanocomposites. Consequently, various materials including polymers, conducting polymers, and metal–organic frameworks (MOF) have also been discussed by introducing various strategies for improved MA and control of EMI shieling. Here in this comprehensive review, we summarized the recent developments on material synthesis and fabrication of MXene based nanocomposites for EMI shielding and MA. This research work is a comprehensive review majorly focuses on the fundamentals of EMI/MA.  The recent developments and challenges of the MXene and graphene based various structures with different polymeric composites are described in a broader perspective.     

Advancement in cellulose-based multifunctional high conductive PNIPAAm/PPy hydrogel/cotton composites for EMI shielding

Exploitation of cotton fabric as electromagnetic interference (EMI) shielding substrates have attracted a growing interest due to their desirable low carbon footprint, economic feasibility, and sustainability. Herein, a facile strategy was proposed for preparing a cellulose-based multifunctional PNIPAAm/PPy hydrogel/cotton (PPHC) EMI shielding composites with simultaneous high-efficient electro-photo-thermal conversion and comfort regulation functions. The PPHC was fabricated via in situ polymerization conductive PPy hydrogel on cotton substrate followed by deposition of PNIPAAm. Benefiting from the unique interconnected three-dimensional networked conductive structure of PPy hydrogel, the obtained PPHC composites exhibited high conductivity (15 mS/cm), and EMI shielding effectiveness (EMI SE?~?40 dB) in the frequency of 8.2–12.3 GHz. Moreover, the PNIPAAm coating endowed the composite fabrics with adjustable wettability performance in response to external temperature, leading to excellent comfort regulation performance. This work provided feasible avenue toward low cost and sustainability cotton-based EMI shielding composites with efficient EMI shielding and comfort regulation performance.

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Significantly enhanced electromagnetic interference shielding effectiveness of montmorillonite nanoclay and copper oxide nanoparticles based polyvinylchloride nanocomposites

In the present study, montmorillonite (MMT) nanoclay and copper oxide (CuO) nanoparticles (NPs) reinforced polyvinylchloride (PVC) based flexible nanocomposite films were prepared via solvent casting technique. Using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Scanning electron microscopy (SEM) and thermo-gravimetric analysis (TGA), the structural, morphological and thermal properties of PVC/MMT/CuO nanocomposite films with various loadings of CuO NPs and MMT were investigated. These studies suggested that by the addition of dual nanofillers in the polymer matrix some structural modifications occurred owing to the homogenous dispersion of MMT and CuO NPs within the PVC matrix. The TGA results reveal that the addition of CuO NPs and MMT considerably improved the thermal stability of the nanocomposites. The EMI shielding effectiveness (SE) of nanocomposites was examined in the X-band (8–12 GHz) and Ku-band (12–18 GHz) frequency regions. The EMI SE values were found to be −30 dB (X-band) and −35 dB (Ku-band) for nanocomposites containing 0.3 wt% of CuO NPs and 4.7 wt% of MMT respectively while the shielding was found to be absorption dominant. These results emphasize that PVC/MMT/CuO nanocomposite films can be used as a potential EMI shielding material.     

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.     

Synergistic effect of double percolated co‐supportive MWCNT‐CB conductive network for high‐performance EMI shielding application

The recent development in telecommunication technology has led electromagnetic interference (EMI) to a serious threat to both electronic devices and living beings. In this work, we designed a highly efficient EMI shielding material by taking advantage of both carbonaceous hybrid filler and double percolation phenomenon. Here, a flexible, lightweight microwave absorbing conductive polymer composite was fabricated by employing poly (ethylene‐co‐methyl acrylate) and ethylene octene copolymer (EMA/EOC) binary blend as the matrix and multiwall carbon nanotube carbon black (MWCNT/CB) hybrid filler as the conductive moiety. We investigated the effect of MWCNT content in the hybrid composite on mechanical, thermomechanical, electrical, and shielding efficiency. A total EMI shielding efficiency of ?37.4 dB in the X band region was attained with 20 wt% hybrid filler containing 50 wt% MWCNT along with promising mechanical properties.     

Electromagnetic interference shielding by using conductive polypyrrole and metal compound coated on fabrics

Electromagnetic interference (EMI) shielding materials of complex type of conductive polypyrrole (PPy) as an intrinsically conducting polymer and silver‐palladium (AgPd) metal compound coated on woven or non‐woven fabrics are synthesized. From dc conductivity and SEM photographs of PPy/fabric complexes, we discuss charge transport mechanism and the homogeneity of coating on the fabrics. The EMI shielding efficiency of PPy/fabric and AgPd/fabric complexes is in the range of 8 ～ 80 dB depending on the conductivity and the additional Ag vacuum evaporation. The highest EMI shielding efficiency of PPy/fabric complexes vacuum‐evaporated by Ag is ～80 dB, indicating potential materials for military uses. We propose that PPy/fabrics are excellent RF and microwave absorber because of the relatively high absorbance and low reflectance of the materials. Copyright © 2002 John Wiley & Sons, Ltd.     

Electrically conductive carbon nanofiber/polyethylene composite: effect of melt mixing conditions

The effect of melt mixing conditions on the morphological, rheological, electrical, electromagnetic interference (EMI) shielding effectiveness (SE), and tensile properties of 7.5 vol% vapor grown carbon nanofiber (VGCNF)/polyethylene composites were investigated. 7.5 vol% VGCNF was used because such loading is required to obtain a composite with satisfactory EMI SE. The composites were compounded by melt mixing and the parts were prepared by hot‐compression molding. The dispersion and distribution of nanofibers were enhanced by increasing the mixing energy, i.e. mixing time and/or rotation speed. The influence of mixing energy on the electrical and EMI SE properties was found to be a function of rotation speed, i.e. shear stress. For composites compounded at 20 rpm, increasing the mixing energy from 70 to 2300 J/ml decreased the EMI SE from 29.5 to 23.9 dB. However, for composites prepared at 100 rpm, increasing the mixing energy from 600 to 1700 J/ml decreased the EMI SE from 25.4 to 18.6 dB. No considerable influence on the yield stress, Young's modulus, and strain at break were found for different processing conditions. Copyright © 2009 John Wiley & Sons, Ltd.     

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     

Mechanical properties,thermal stability,sound absorption,and flame retardancy of rigid PU foam composites containing a fire‐retarding agent: Effect of magnesium hydroxide and aluminum hydroxide

Isocyanate, polyether polyol, a flame retardant (10 wt%), and aluminum hydroxide/magnesium hydroxide (0, 5, 10, 15, and 20 wt%) are used to form the rigid polyurethane (PU) foam, while nylon nonwoven fabrics and a polyester aluminum foil are combined to serve as the panel. The rigid PU foam and panel are combined to form the rigid foam composites. The cell structure, compressive stress, combustion resistance, thermal stability, sound absorption, and electromagnetic interference shielding effectiveness (EMI SE) of the rigid foam composites are evaluated, examining the effects of using aluminum hydroxide and magnesium hydroxide. Compared with magnesium hydroxide, aluminum hydroxide exhibits superior performance to the rigid foam composites. When aluminum hydroxide is 20 wt%, the rigid foam composite has an optimal density of 0.153 g/cm³, an average cell size of 0.2466 mm, a maximum compressive stress of 546.44 Kpa, an optimal limiting oxygen index (LOI) of 29.5%, an optimal EMI SE of 40 dB, and excellent thermal stability and sound absorption.     

Conducting polystyrene/polyaniline blend through template-assisted emulsion polymerization

Electrically conducting polystyrene (PS)/polyaniline blends have been prepared through a one-step “anilinium-surfactant template”-assisted emulsion polymerization at room temperature. The self-assembled cylindrical An⁺PDPSA^? micelle formed inside the PS matrix can act as a structure directing template cum dopant. Morphological observation under scanning electron microscopic studies revealed that during the progress of polymerization, the initially formed nanostructured conducting polyaniline was changed into cubic/hexagonal/lamellar particles and finally transformed into a percolated structure inside the PS matrix. Blend was further characterized by UV-Vis spectroscopy, FTIR spectroscopy, X-ray diffraction, electrical conductivity, thermal stability, dielectric property, rheological property, and electromagnetic shielding efficiency. The key finding of this work is that the conductive blend prepared through micelle-guided polymerization exhibited superior electrical conductivity (9.6 S/m) with low percolation threshold concentration (5 wt%), excellent thermal stability, electromagnetic interference (EMI) SE of 1–10 dB which makes it a promising candidate for EMI shielding and antistatic discharge matrix for the encapsulation of microelectronic devices.     

Asymmetric Ni/PVC films for high-performance electromagnetic interference shielding

A novel asymmetric Ni/PVC film has been developed by solution casting method. The structure, electrical conductivity, electromagnetic interference(EMI) shielding, and impact resistance were investigated. The results showed that the Ni particles were asymmetrically distributed along the thickness direction in the film. The top surface resistivity increased with film thickness, while the bottom surface exhibited the different trend. EMI shielding effectiveness(SE) depended on formation of closed packed conductive Ni network, which was influenced by both Ni content and film thickness. A linear relationship was observed between EMI SE and film thickness. The films with lower Ni content showed the faster increasing rate of EMI SE with film thickness. Some of the films show appreciably high EMI SE( 40 d B), indicating the promising application in EMI shielding field. Moreover, the films exhibit different impact performance under different impacting directions. All the experimental facts demonstrate that the asymmetric structure endows the film achieving high-performance EMI shielding function.     

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.     

Electromagnetic-Interference-Shielding Effectiveness of Lyocell-Based Carbon Fabrics Carbonized at Various Temperatures

Lyocell is a biodegradable filament yarn obtained by directly dissolving cellulose in a mixture of N-methylmorpholine-N-oxide and a non-toxic solvent. Therefore, herein, lyocell fabrics were employed as eco-friendly carbon-precursor substitutes for use as electromagnetic interference (EMI) shielding materials. First, a lyocell fabric treated with polyacrylamide via electron beam irradiation reported in a previous study to increase carbon yields and tensile strengths was carbonized by heating to 900, 1100, and 1300 °C. The carbonization transformed the fabric into a graphitic crystalline structure, and its electrical conductivity and EMI shielding effectiveness (SE) were enhanced despite the absence of metals. For a single sheet, the electrical conductivities of the lyocell-based carbon fabric samples at the different carbonization temperatures were 3.57, 5.96, and 8.91 S m⁻¹, leading to an EMI SE of approximately 18, 35, and 82 dB at 1.5–3.0 GHz, respectively. For three sheets of fabric carbonized at 1300 °C, the electrical conductivity was 10.80 S m⁻¹, resulting in an excellent EMI SE of approximately 105 dB. Generally, EM radiation is reduced by 99.9999% in instances when the EMI SE was over 60 dB. The EMI SE of the three lyocell-based carbon fabric sheets obtained at 1100 °C and that of all the sheets of the sample obtained at 1300 °C exceeded approximately 60 dB.     

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.     

Effects of diameter and surface area of electrospun nanocomposite fibers on electromagnetic interference shielding

The effects of variation in average diameter and surface area of nanocomposite fibers on electromagnetic interference (EMI) shielding of multi-walled carbon nanotubes (MWCNTs)/polyvinylpyrrolidone (PVP) fibers were investigated in this paper. The EMI shielding effectiveness of electrospun nanocomposite fibers were measured in the X-band frequency range 8.2–12.4 GHz. The electrical conductivity and EMI shielding behaviors of the nanocomposite fibers were reported as function of average diameter and surface area of MWCNTs/PVP nanocomposite fibers. The electrical conductivity measurements demonstrate using thinner nanocomposite fibers results in a lower limit of electrical resistivity, better electrical conductivity performance. The EMI shielding efficiency of thinner nanocomposite fibers increased up to 42 dB. The EMI shielding data for MWCNTs/PVP nanocomposite fibers with various average diameter and surface area showed that absorption was the major shielding mechanism and reflection was the secondary shielding mechanism. It can be related to higher specific surface area of thinner electrospun MWCNTs/PVP nanocomposite fibers that means more surface area for radiative scatter and absorption leading to higher EMI shielding performance.     

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.     

Multifunctional waterproof MXene-coated wood with high electromagnetic shielding performance

Increasing electromagnetic pollution calls for electromagnetic interference (EMI) shielding materials, especially sustainable, lightweight, and environmentally stable, biomass-based materials. MXene-coated wood (M/wood) is prepared by simply spraying MXene sheets on the wood surface. Varying this spray coating manipulates the shielding performance and its application to different wood species. The M/wood exhibits high electrical conductivity (sheet resistance is only 0.65 Ω/sq) with an excellent EMI shielding effectiveness of 31.1 dB at 8.2?~?12.4 GHz and is also fire retardant. Furthermore, waterborne acrylic resin (WA) is coated on M/wood to enhance environmental stability. The WA coating improves EMI shielding performance stability after water-soaking and drying testing and prevents the peeling of MXene from wood. These satisfactory properties of WA-M/wood and the facile manufacturing approach promote the feasibility of wood-based EMI shielding materials.

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