Development of electromagnetic shielding materials from the conductive blends of polyaniline and polyaniline-clay nanocomposite-EVA: Preparation and properties

Electromagnetic interference shielding composite materials were developed from the conductive blends of nanostructured polyaniline (PANI) and polyaniline-clay nanocomposite (PANICN) with ethylene vinyl acetate (EVA) as host matrix. Electrically conducting nanostructured PANI and PANICNs were prepared using amphiphilic dopants, 3-pentadecyl phenol 4-sulphonic acid (3-PDPSA) derived from cashew nut shell liquid, a low cost renewable resource based product and dodecyl benzene sulfonic acid (DBSA). Effects of type and quantity of conductive fillers on the electrical conductivity, mechanical properties, thermal stability, morphology and electromagnetic shielding efficiency were investigated. The presence of exfoliated nanoclay and interaction between the conductive filler–host matrix in conductive films containing PANICNs manifested from the measurement on rheological property. Films with conductive filler (～15% loading) showed a shielding effectiveness of ～40–80 dB at 8 GHz which makes these conducting composites potential candidate for the encapsulation as EMI shielding materials for electronic devices.     

Effect of silver incorporation into PVDF-barium titanate composites for EMI shielding applications

Composites of polyvinylidene fluoride (PVDF) with micron and nano sized BaTiO₃ powders were developed for electromagnetic interference (EMI) shielding applications in the X band. PVDF-nano BaTiO₃ composites show better shielding property compared to PVDF-micron sized BaTiO₃ composites. The composite of PVDF with 40 vol% of nano BaTiO₃ showed the best EMI shielding effectiveness and is about 9 dB. The contributions from reflection and absorption to the total EMI shielding effectiveness is same for the PVDF-BaTiO₃ composites. Addition of small amount of silver particles improved the shielding properties of these composites due to the increased conductivity. An EMI shielding effectiveness of about 26 dB is obtained in the measured frequency range for the PVDF-20 vol% nano BaTiO₃-10 vol% Ag composite of thickness 1.2 mm. Novel three phase composite combining the advantages of metal, nano ceramic and polymer is obtained with the potential for effective EMI shielding applications.     

New electromagnetic wave shielding effectiveness at microwave frequency of polyvinyl chloride reinforced graphite/copper nanoparticles

A novel functional nanoconducting composite from polyvinyl chloride reinforced graphite–copper nanoparticles (PVC/GCu) was fabricated in order to produce a material suitable for electromagnetic interference (EMI) shielding applications. The microstructure of the nanocomposites was investigated by means of scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The thermal stability of the nanocomposites could improved with the incorporation of GCu nanoparticles. The electrical conductivity increases with increasing GCu content within composites. The percolation threshold of composites is low of about 2 wt.%. Hall-effect studies indicate that increase in GCu content in the composites causes increase in carrier concentration, mobility of the carriers and the composites behave as n-type semiconductor. The nanocomposites showed a high dielectric constant and a high dissipation factor in the frequency range of 1–20 GHz which makes it useful in charge storing and decoupling capacitors applications. The EMI shielding effectiveness (SE) of the PVC/GCu nanocomposites was tested over a frequency range of 1–20 GHz, and 22–70 dB shielding efficiency was obtained for the composites, suggesting that they may be used as an effective lightweight EMI shielding material in aerospace and radar evasion applications.     

Low temperature charge transport and microwave absorption of carbon coated iron nanoparticles–polymer composite films

In this paper, the low temperature electrical conductivity and microwave absorption properties of carbon coated iron nanoparticles–polyvinyl chloride composite films are investigated for different filler fractions. The filler particles are prepared by the pyrolysis of ferrocene at 980 °C and embedded in polyvinyl chloride matrix. The high resolution transmission electron micrographs of the filler material have shown a 5 nm thin layer graphitic carbon covering over iron particles. The room temperature electrical conductivity of the composite film changes by 10 orders of magnitude with the increase of filler concentration. A percolation threshold of 2.2 and an electromagnetic interference shielding efficiency (EMI SE) of ～18.6 dB in 26.5–40 GHz range are observed for 50 wt% loading. The charge transport follows three dimensional variable range hopping conduction.     

MWNT/PEG grafted nanocomposites and an analysis of their EMI shielding properties

EMI shielding films made from carbon nanotube grafted with organic polymers at a low cost have been developed. MWCNTs exhibit desirable electrical properties for EMI shielding films. In this study, PEG was employed by urethane bonding to increase the processability and dispersibility of the MWCNTs. The molecular weight of PEG was 200 and 2000, and their EMI shielding films were fabricated by addition of UV-curing photoinitiator. The EMI shielding property was measured, and they show proper EMI reflectance and shielding effectiveness. Especially, when 4.0 wt% of MWCNTs were added to PEG with a molecular weight of 200 g/mol, it exhibited the maximum EMI SE value was ?22.9 dB at 4.14 GHz, while the average EMI SE value which was ?20.53 dB.     

Electromagnetic interference shielding of composites consisting of a polyester matrix and carbon nanotube-coated fiber reinforcement

We investigated the electromagnetic interference shielding effectiveness (EMI SE) of composites consisting of an unsaturated polyester matrix containing woven glass or carbon fibers that had been coated with multiwalled carbon nanotubes (MWCNTs). Composite panels consisting of fiber fabrics with various combinations of fabric type and stacking sequence were fabricated. Their EMI SE was measured in the frequency range of 30 MHz–1.5 GHz. The underlying physics governing the EMI shielding mechanisms of the materials, namely, absorption, reflection, and multiple reflections, was investigated and used in analytical models to predict the EMI SE. Simulation and experimental results showed that the contributions of reflection and absorption to EMI shielding is enhanced by sufficient impedance mismatching, while multiple reflections have a negative effect. For a given amount of MWCNTs in the glass-fiber–reinforced composite, coating the outermost, instead of intermediate, glass fiber plies with MWCNTs was found to maximize the conductivity and SE.     

Designing of carbon nanotube/polymer composites using melt recirculation approach: Effect of aspect ratio on mechanical,electrical and EMI shielding response

The paper describes the effect of aspect ratio of multiwall carbon nanotubes (MCNTs) on the electrical, mechanical and electromagnetic properties of polypropylene random copolymer (PPC). Long and short MCNTs with aspect ratio of ~ 1356–1937 and ~ 158 respectively were melt-blended with PPC in a micro twin screw extruder with melt recirculation that allow the formation of composites having ~ 15 wt.% MCNTs. The good dispersion was confirmed by scanning electron microscopy and observation of electrical conductivity at low percolation threshold (0.45 and 1.07 wt.% for l- & s-MCNT/PPC composite respectively) and improvement of modulus and strength. The 15 wt.% l-MCNTs and s-MCNT loaded composites show 52% and 60% improvement in modulus respectively and 20% & 18% improvement in strength over neat PPC. The electromagnetic interference (EMI) shielding response (in 8.2–12.4 GHz frequency range) revealed that l-MCNT based PPC composites display better shielding at lower loading (up to 4 wt.%) while s-MCNT show better attenuation at higher loadings. The realization shielding effectiveness value of − 27 dB (> 99% attenuation) respectively for l-MCNT composites: and − 37 dB (> 99.9% attenuation) for s-MCNTs composites at 15 wt.% reflect their potential for making light weight and structurally strong EMI shields.     

Reduced graphene oxide deposited carbon fiber reinforced polymer composites for electromagnetic interference shielding

Reduced graphene oxide deposited carbon fiber (rGO-CF) was prepared by introducing GO onto CF surface through electrophoretic deposition method, following by reducing the GO sheets on CF with NaBH₄ solution. The rGO-CF was found to be more effective than CF to improve the electromagnetic interference (EMI) shielding property of unsaturated polyester (UP) based composites. With 0.75% mass fraction of rGO-CF, the shielding effectiveness of the composite reached 37.8 dB at the frequency range of 8.2–12.4 GHz (x-band), which had 16.3% increase than that of CF/UP composite (32.5 dB) in the same fiber mass fraction. The results suggest that rGO-CF is a good candidate for the use as a light-weight EMI shielding material.     

Short shaped copper fibers in an epoxy matrix: Their role in a multifunctional composite

Previous research indicates that short shaped copper fibers improve the fracture and impact toughness of brittle thermoset polymer matrix composites. This paper investigates the potential multifunctional ability of these same shaped copper fibers by determining their electromagnetic interference (EMI) shielding effectiveness (SE). Fiber shapes were selected based on previous single fiber pullout experiments where they displayed high toughness. The two fiber diameters tested were: 0.325 and 0.162 mm. Fiber shapes used in the experiments were: straight, flat end-impacted, rippled, and acid roughened. A SE of greater than 45 dB at 1.0 GHz was attained in epoxy that contained 15 vol% of 0.162 mm diameter shaped fibers. Composites with 15 vol% of the 0.325 mm diameter shaped fibers showed poor SE, less than 20 dB. Experimental results indicate that besides improving the fracture and impact toughness of a thermoset polymer matrix, short shaped copper fibers can also significantly improve the SE and electrical conductivity of the composite, resulting in a multifunctional material. This increase in SE and electrical conductivity can be attributed to: shape effects that increase the skin volume, surface discontinuities which increase the amount of electromagnetic (EM) wave scattering, and the fiber count which determines the number of conducting paths.     

Synthesis of conducting ferromagnetic nanocomposite with improved microwave absorption properties

The present paper reports the synthesis of polyaromatic amine–ferromagnetic composite with nanosize TiO₂ (～70–90 nm) and γ-Fe₂O₃ (～10–15 nm) particles via in situ emulsion polymerization. Magnetic and conductivity studies demonstrate that the conducting ferromagnetic composite possesses saturation magnetization (M_S) value of 26.9 emu g^?1 and conductivity of the order of 0.46 S cm^?1, which are measured by vibrating sample magnetometer and four-probe technique, respectively. It is observed that the presence of the nanosized γ-Fe₂O₃ in the polyaniline–TiO₂ matrix affects the electromagnetic shielding property of the composite. Polyaniline–TiO₂–γ-Fe₂O₃ nanocomposite has shown better shielding effectiveness due to absorption (SE_A ～ 45 dB) than the polyaniline-γ-Fe₂O₃ (SE_A ～ 8.8 dB) and polyaniline–TiO₂ (SE_A ～ 22.4 dB) nanocomposite. The polymer composites were further characterized by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) technique.     

Investigation of electrical conductivity and electromagnetic shielding effectiveness of polyaniline composite

With the increasing of electromagnetic pollution and the widely use of commercial and military products, there is an increasing interest in electromagnetic interference (EMI) shielding. This paper mainly aims at electrical conductivity and EMI shielding effectiveness (SE) of the conducting composites made from silicone rubber (SR) with different loading levels of HCl-doped polyaniline (PAN-HCl) in the low frequency range from 3 to 1500 MHz. The result indicates that SE of the composites increase and the volume resistivity decrease with increasing mass ratio loading of PAN-HCl in the SR. The measured SE of the composites are from 16 to 19.3 dB at 100 mass ratio loading of the PAN-HCl and the volume resistivity decrease nine orders of magnitude compared with that of the emeraldine base form of PAN (PAN-EB) composites.     

High-temperature dielectric and electromagnetic interference shielding properties of SiCf/SiC composites using Ti3SiC2 as inert filler

Ti₃SiC₂ filler has been introduced into SiC_f/SiC composites by precursor infiltration and pyrolysis (PIP) process to optimize the dielectric properties for electromagnetic interference (EMI) shielding applications in the temperatures of 25–600 °C at 8.2–12.4 GHz. Results indicate that the flexural strength of SiC_f/SiC composites is improved from 217 MPa to 295 MPa after incorporating the filler. Both the complex permittivity and tan δ of the composites show obvious temperature-dependent behavior and increase with the increasing temperatures. The absorption, reflection and total shielding effectiveness of the composites with Ti₃SiC₂ filler are enhanced from 13 dB, 7 dB and 20 dB to 24 dB, 21 dB and 45 dB respectively with the temperatures increase from 25 °C to 600 °C. The mechanisms for the corresponding enhancements are also proposed. The superior absorption shielding effectiveness is the dominant EMI shielding mechanism. The optimized EMI shielding properties suggest their potentials for the future shielding applications at temperatures from 25 °C to 600 °C.     

Segregated poly(vinylidene fluoride)/MWCNTs composites for high-performance electromagnetic interference shielding

Conductive polymer composites (CPCs) that contain a segregated structure have attracted significant attentions because of their promising for fulfilling low filler contents with high electromagnetic interference (EMI) properties. In the present study, segregated poly(vinylidene fluoride) (PVDF)/multi-walled carbon nanotubes (MWCNTs) composites were successfully prepared by mechanical mixing and hot compaction. The PVDF/MWCNTs samples with 7 wt% filler content possess high electrical conductivities and high EMI shielding effectiveness (SE), reaching 0.06 S cm⁻¹ and 30.89 dB (in the X-band frequency region), much higher than lots of reported results for CNT-based composites. And the EMI SE greatly increased across the frequency range as the sample thickness was improved from 0.6 to 3.0 mm. The EMI shielding mechanisms were also investigated and the results demonstrated absorption dominating shielding mechanism in this segregated material. This effective preparation method is simple, low-cost, and environmentally-friendly and has potential industrial applications in the future.     

Synthesis and properties of sandwiched films of epoxy resin and graphene/cellulose nanowhiskers paper

Graphene (GN)-based composite paper containing 10 wt.% cellulose nanowhiskers (CNWs) exhibiting a tensile strength of 31.3 MPa and electrical conductivity of 16 800 S/m was prepared by ultrasonicating commercial GN powders in aqueous CNWs suspension. GN/CNWs freestanding paper was applied to prepare the sandwiched films by dip coating method. The sandwiched films showed enhanced tensile strength by over two times higher than the neat resins. The moduli of the sandwiched films were around 300 times of the pure resins due to the high content of GN/CNWs paper. The glass transition temperature of the sandwiched films increased from 51.2 °C to 57.1 °C for pure epoxy (E888) and SF (E888), and 49.8 °C to 64.8 °C for pure epoxy (650) and SF (650), respectively. The bare conductive GN/CNWs paper was well protected by the epoxy resin coating, which is promising in the application as anti-static materials, electromagnetic interference (EMI) shielding materials.     

Effect of heat treatment on electromagnetic shielding effectiveness of ZK60 magnesium alloy

Electromagnetic interference (EMI) shielding capacity of ZK60 magnesium alloy in different heat treatment conditions was investigated in the testing frequency range of 30–1500 MHz. EMI shielding effectiveness (SE) was measured by coaxial cable method at ambient temperature. Experimental results indicate that solid solution treatment enhances the SE of as-extruded ZK60 alloy at low frequency, while has an inverse effect on the SE at high frequency. Artificial aging treatment following solid solution improves shielding capacity obviously, moreover the SE value of the alloy increase gradually with increasing amount of second phase precipitates. Solution treatment at 400 °C for 5 h plus artificial aging at 170 °C for 25 h is determined as the optimum heat treatment condition. In this condition, a high shielding effectiveness of 62–75 dB has been attained in the alloy, which is greatly higher than the value in extruded state. The above-mentioned observations were analyzed in terms of microstructural variation, especially solid solution and precipitation of alloying elements in ZK60 alloy in details.     

Graphene foam/carbon nanotube/poly(dimethyl siloxane) composites for exceptional microwave shielding

Highly porous poly(dimethyl siloxane) (PDMS) composites containing cellular-structured microscale graphene foams (GFs) and conductive nanoscale carbon nanotubes (CNTs) are fabricated. The unique three-dimensional, multi-scale hybrid composites with inherent percolation and a high porosity of 90.8% present a remarkable electromagnetic interference shielding effectiveness (EMI SE) of ∼75 dB, a 200% enhancement against 25 dB of the composites made from GFs alone with the same graphene content and porosity. The corresponding specific EMI SE measured against the composite density is 833 dB cm³/g. These values are among the highest for all carbon filler/polymer composites reported thus far. Significant synergy arises from the hybrid reinforcement structure of the composites: the GFs drive the incident microwaves to be attenuated by dissipation of the currents induced by electromagnetic fields, while the CNTs greatly enhance the dissipation of surface currents by expanding the conductive networks and introducing numerous interfaces with the matrix.     

Structure and properties of melt-processed PVDF/PMMA/polyaniline blends

Ternary blends composed of the matrix polymer poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) with different proportions of thermally doped polyaniline (PAni) using an alkylated dopant (dodecylbenzenesulfonic acid) (DBSA) were prepared by melt mixing. The effectiveness of these blends was compared with the corresponding binary blends of PVDF or PMMA with PAni–DBSA complex. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) measurements, thermal analysis by differential scanning calorimetry (DSC) and morphological studies by optical microscopy and scanning electron microscopy (SEM) were carried out to characterize the blends in light of the interactions between their components and on the resulting electrical conductivity. Though a notable dispersion of PAni–DBSA in the PMMA matrix was incurred along with better conductivity with respect to PVDF/PAni–DBSA and PVDF/PMMA/PAni–DBSA blends, the thin films based on PMMA/PAni–DBSA were found to be fragile in nature. However, the presence of PMMA in the ternary blends of PVDF/PMMA/PAni–DBSA provided improved dispersion of PAni–DBSA in the PVDF/PMMA host matrix as compared to PVDF/PAni–DBSA binary blends. An enhancement in the conductivity by about two orders of magnitude at >5 wt% PAni–DBSA was witnessed in the ternary blends than that of PVDF/PAni–DBSA binary blends. Thin films made of ternary blends of PVDF/PMMA/PAni–DBSA also offered superior mechanical properties and flexibility than that of PMMA/PAni–DBSA binary blends due to the contribution of PVDF in the blend.     

Polyaniline–MWCNT nanocomposites for microwave absorption and EMI shielding

Highly conducting polyaniline (PANI)–multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by in situ polymerization. The FTIR and XRD show systematic shifting of the characteristic bands and peaks of PANI, with the increase in MWCNT phase, suggesting significant interaction between the phases. The SEM and TEM pictures show thick and uniform coating of PANI over surface of individual MWCNT. Based on observed morphological features in SEM, the probable formation mechanism of these composites has been proposed. The electrical conductivity of PANI–MWCNT composite (19.7 S cm^?1) was even better than MWCNT (19.1 S cm^?1) or PANI (2.0 S cm^?1). This can be ascribed to the synergistic effect of two complementing phases (i.e. PANI and MWCNT). The absorption dominated total shielding effectiveness (SE) of ?27.5 to ?39.2 dB of these composites indicates the usefulness of these materials for microwave shielding in the Ku-band (12.4–18.0 GHz). These PANI coated MWCNTs with large aspect ratio are also proposed as hybrid conductive fillers in various thermoplastic matrices, for making structurally strong microwave shields.     

Thermal and electrical properties of magnetite filled polymers

By the addition of metal-oxide particles to plastics the electrical and thermal conductivity of polymers can be increased significantly. Such particle filled polymers can substitute metals and metal oxides in applications like radio frequency interference shielding. Furthermore, particle filled polymers with higher thermal conductivity than unfilled ones become more and more important in applications with decreasing geometric dimensions and increasing output of power, like in computer chips.Therefore, thermal and electrical properties of polypropylene and polyamide with metal-oxide particle filler (magnetite, Fe₃O₄) are investigated. Different particle sizes of magnetite and types of additives were added in various proportions to a standard polypropylene and polyamide in an extrusion process. Samples were prepared by injection molding to investigate thermal and electrical properties systematically.The thermal conductivity increases from 0.22 to 0.93 W/(m K) for a filler content of 44 vol% of magnetite, whereas the electrical resistivity decreases more than seven orders of magnitude from an insulator (0% of magnetite) to 10 kΩ m (47 vol% of magnetite).The experimental results of thermal and electrical conductivity were correlated to the amount and particle sizes of magnetite filler. Electrical resistivity shows a significant drop at the theoretical percolation threshold (∼0.33) and for filler contents exceeding 33 vol% the magnetite particles have point contacts and are surrounded by the polymer matrix.     

Effect of aluminum oxide doping on the structural,electrical, and optical properties of zinc oxide (AOZO) nanofibers synthesized by electrospinning

Zinc oxide nanofibers doped with aluminum oxide were prepared by sol–gel processing and electrospinning techniques using polyvinylpyrrolidone (PVP), zinc acetate and aluminum acetate as precursors. The resulting nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV–Vis spectroscopy, and current–voltage (I–V) properties. The nanofibers had diameters in the range of 60–150 nm. The incorporation of aluminum oxide resulted in a decrease in the crystallite sizes of the zinc oxide nanofibers. Aluminum oxide doped zinc oxide (AOZO) nanofibers exhibited lower bandgap energies compared to undoped zinc oxide nanofibers. However, as the aluminum content (Al/(Al + Zn) × 100%) was increased from 1.70 at.% to 3.20 at.% in the electrospinning solution, the bandgap energy increased resulting in lower conductivity. The electrical conductivity of the AOZO samples was found to depend on the amount of aluminum dopant in the matrix as reflected in the changes in oxidation state elucidated from XPS data. Electrospinning was found to be a productive, simple, and easy method for tuning the bandgap energy and conductivity of zinc oxide semiconducting nanofibers.