Enhanced Dielectric Constant for Efficient Electromagnetic Shielding Based on Carbon-Nanotube-Added Styrene Acrylic Emulsion Based Composite

An efficient electromagnetic shielding composite based on multiwalled carbon nanotubes (MWCNTs)-filled styrene acrylic emulsion-based polymer has been prepared in a water-based system. The MWCNTs were demonstrated to have an effect on the dielectric constants, which effectively enhance electromagnetic shielding efficiency (SE) of the composites. A low conductivity threshold of 0.23 wt% can be obtained. An EMI SE of ~28 dB was achieved for 20 wt% MWCNTs. The AC conductivity (σ _ac) of the composites, deduced from imaginary permittivity, was used to estimate the SE of the composites in X band (8.2–12.4 GHz), showing a good agreement with the measured results.     

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

The polypyrrole-coated multi-walled carbon nanotubes (MWCNTs) were prepared by in situ chemical oxidative polymerization of pyrrole on the surface of MWCNTs for the novel electromagnetic interference (EMI) shielding materials. The oxyfluorination treatment on MWCNTs introduced the hydrophilic functional groups resulting in well distribution and higher interfacial affinity between polypyrrole (PPy) and MWCNTs. The PPy phases formed on MWCNTs were observed by SEM. The thickness of PPy on the surface of MWCNTs decreased as increasing the hydrophilic groups on MWCNTs by the oxyfluorination treatment. The PPy-coated MWCNT composites showed the remarkable increases in permittivity, permeability, and EMI shielding efficiency (SE). The EMI SE of PPy-coated MWCNTs increased up about 28.6 dB mainly based on the absorption mechanism.     

Epoxy composite foams with excellent electromagnetic interference shielding and heat‐resistance performance

Epoxy composite foams with improved heat‐resistant property and efficient electromagnetic interference shielding effectiveness (EMI SE) were fabricated through a two‐step foaming technique. A sort of novel and untraditional expandable microspheres was adopted to reduce the density of prepared materials. A multiscale conductive network system composed of multiwalled carbon nanotubes (MWCNTs) and nickel‐plated carbon fibers (NiCFs) was introduced in these foams. Benefitting from the synergistic effect between NiCFs and MWCNTs, the multiscale epoxy foam with best comprehensive performance achieved a greatly enhanced T_g at 178.3 °C and an exceptional specific EMI SE ranging from 52.8 to 72.6 dB cm³ g^?1 in X band (8.2–12.4 GHz) at low filler loading. These properties are greatly better than original epoxy foam with a T_g of 157.8 °C and specific EMI SE of 1.0–6.4 dB cm³ g^?1. Their shielding mechanisms were discussed and the results showed that reflection is dominating. The effects of microspheres content, foaming temperature, NiCFs content, and length were investigated. In general, we provided a feasible, convenient and cost‐effective method to fabricate light‐weight, heat‐resistant thermosetting epoxy foams with sufficient EMI shielding performance which has a potential to be applied in aerospace or electronic devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46013.     

Thermoplastic polyvinyl alcohol/multiwalled carbon nanotube composites: Preparation,mechanical properties,thermal properties,and electromagnetic shielding effectiveness

This study uses the solution mixing method to combine plasticized polyvinyl alcohol (PVA) as a matrix, and multiwalled carbon nanotubes (MWCNTs) as reinforcement to form PVA/MWCNTs films. The films are then laminated and hot pressed to create PVA/MWCNTs composites. The control group of PVA/MWCNTs composites is made by incorporating the melt compounding method. Diverse properties of PVA/MWCNTs composites are then evaluated. For the experimental group, the incorporation of MWCNTs improves the glass transition temperature (T_g), crystallization temperature, T_c), and thermal stability of the composites. In addition, the test results indicate that composites containing 1.5 wt % of MWCNTs have the maximum tensile strength of 51.1 MPa, whereas composites containing 2 wt % MWCNTs have the optimal electrical conductivity of 2.4 S/cm, and electromagnetic shielding effectiveness (EMI SE) of ?31.41 dB. This study proves that the solution mixing method outperforms the melt compounding method in terms of mechanical properties, dispersion, melting and crystallization behaviors, thermal stability, and EMI SE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43474.     

Theoretical and experimental studies on EMI shielding mechanisms of multi-walled carbon nanotubes reinforced high performance composite nanofibers

Electrically conductive composite nanofibers of polyvinylpyrrolidone (PVP) filled with multi-walled carbon nanotubes (MWCNTs) were prepared by electrospinning process. The complex permittivity and electromagnetic interference shielding effectiveness (EMI SE) of all composite nanofibers were measured in the X band frequency range 8.2–12.4 GHz. The electrical conductivity, real and imaginary part of permittivity, and EMI shielding behaviors of the composite nanofibers were reported as function of MWCNTs concentration. Electrical conductivity of MWCNTs/PVP composite nanofiber followed power law model of percolation theory having a percolation threshold ?_c = 0.72 vol% (~1 wt.%) and exponent t = 1.71. The total EMI SE of MWCNTs/PVP composite nanofibers increased up to 42 dB mainly base on the absorption mechanism. The EMI SE measured from experiments was also compared with the approximate value calculated from theoretical model. The obtained theory results confirmed that the selected model presented acceptable performance for evaluating the involved parameters and prediction of the EMI SE of composite nanofibers. The ability of the theoretical model to predict the EMI shielding by reflection and absorption was found to be a function of the frequency, thickness, permittivity, and conductivity.     

Synergistic effect of multiwalled carbon nanotubes and an intumescent flame retardant: Toward an ideal electromagnetic interference shielding material with excellent flame retardancy

To shield undesirable electromagnetic waves caused by electronic devices and simultaneously resolve the flame safety of the electronic components, an electromagnetic interference (EMI) shielding material with excellent flame‐retardant properties is urgently needed. The synergistic effect of the intumescent flame retardant (IFR) and multiwalled carbon nanotubes (MWCNTs) for polystyrene (PS) nanocomposites prepared by melt blending was investigated. The results show that addition of certain amounts of IFRs facilitated the dispersion of MWCNTs in the PS matrix, and the percolation threshold of the MWCNTs in the PS matrix also decreased from 1.67 ± 0.05 to 1.29 ± 0.04 wt %. Moreover, the EMI shielding efficiencies (SEs) of the PS–MWCNT–IFR composites were consistently higher than those of the PS–MWCNT composites without the addition of the IFRs at the same MWCNT content; this indicated that the synergistic effect of the MWCNTs and IFRs effectively improved the EMI SE of the PS–MWCNT–IFR composites. Furthermore, the limiting oxygen index (LOI) testing results show that the LOI values of the PS–MWCNT composites were consistently higher than 27%; this indicated that the PS–MWCNT composites effectively met the needs of flame safety; this indicated that the PS–MWCNT–IFR composite is a novel and promising candidate for an ideal EMI shielding material with excellent flame‐retardant properties for today's electronic devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45088.     

5‐Sulfoisophthalic acid monolithium salt doped polypyrrole/multiwalled carbon nanotubes composites for EMI shielding application in X‐band (8.2–12.4 GHz)

This article describes the synthesis and characterization of highly conductive polypyrrole (PPy)/multiwalled carbon nanotube (MWCNT) composites prepared by in situ polymerization of pyrrole using 5‐sulfoisophthalic acid monolithium salt [lithio sulfoisophthalic acid (LiSiPA)] as dopant and ferric chloride as oxidant. Several samples were prepared by varying the amounts of MWCNTs ranging from 1 to 5 wt %. Scanning electron microscope and transmission electron microscope images clearly show a thick coating of PPy on surface of MWCNTs. The electrical conductivity of PPy increased with increasing amount of MWCNTs and maximum conductivity observed was 52 S/cm at a loading of 5 wt % of MWCNTs. Pure PPy prepared under similar conditions had a conductivity of 25 S/cm. Electromagnetic interference (EMI) shielding effectiveness (SE) also showed a similar trend and average EMI shielding of ?108 dB (3 mm) was observed for sample having 5 wt % MWCNT in the frequency range of 8.2–12.4 GHz (X‐band). The light weight and absorption dominated total SE of ?93 to ?108 dB of these composites indicate the usefulness of these materials for microwave shielding. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45370.     

Comparison of polyelectrolyte and sodium dodecyl benzene sulfonate as dispersants for multiwalled carbon nanotubes on cotton fabrics for electromagnetic interference shielding

Cotton fabrics with multiwalled carbon nanotubes (MWCNTs) dispersed by Nafion, a polyelectrolyte, and sodium dodecyl benzene sulfonate (SDBS), a surfactant, were prepared for electromagnetic interference (EMI) shielding. The fabrics were characterized by scanning electron microscopy and vector network analysis. The fabrics with the Nafion–MWCNT coating possessed a better shielding efficiency (SE) than those with the SDBS–MWCNT coating because of a more uniform dispersion of MWCNTs, which improved the electrical conductivity and EMI shielding properties. The maximum SE value of the fabric reached 11.48 dB, and the specific SE was 39.6 dB cm³/g. The reflectivity and absorptivity were calculated separately to determine the main mechanism of EMI shielding. The absorptivity was 68.6% at 12 GHz for the Nafion–MWCNT‐coated fabric; this showed that the dominant mechanism of EMI shielding for the treated fabrics was absorption. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40588.     

Effect of functionalization on the thermo-mechanical and electrical behavior of multi-wall carbon nanotube/epoxy composites

The effect of the functionalization of multi-wall carbon nanotubes (MWCNTs) on the structure, the mechanical and electrical properties of composites was investigated. Samples based on epoxy resin with different weight percentage of MWCNTs or COOH-functionalized carbon nanotubes (MWCNT–COOH) were prepared and characterized. Dynamic-mechanical thermal analysis shows that the storage modulus increases with the addition of MWCNTs, whereas a constant value or even a weak reduction was observed for functionalized nanotubes. Two phases were suggested in the composites with MWCNT–COOH, both by dynamic-mechanical properties and by water transport. Chemical functionalization of MWCNTs increases the compatibility with the epoxy matrix due to the formation of an interface with stronger interconnections. This, in turn, causes a significant decrease in the electrical conductivity of this type of composite with respect to the untreated MWCNTs which can be explained in terms of tunnelling resistance between interacting nanotubes.     

Direct functionalization with 3,5‐substituted benzoic acids of multiwalled carbon nanotube/epoxy composites

Directly functionalized multiwalled carbon nanotubes (MWCNTs) with benzene‐1,3,5‐tricarboxylic acid (BTC) and 3,5‐diaminobenzoic acid (DAB) were successfully accomplished with less structural damage as confirmed by XPS and FT‐Raman results. Their dispersibility and thermal stability were achieved after the functionalization. The functional groups on MWCNT surfaces can accelerate the curing reaction of epoxy composites remarkable inducing rather low exothermic peak temperature (T_p) and exothermic heat of reaction (ΔH). The values of activation energy (E_a) obtained from Kissinger and Ozawa methods obviously decreased with the introduction of MWCNTs, especially DAB‐MWCNTs. The dynamic mechanical properties notably enhanced with the incorporation of unmodified and functionalized MWCNTs. The crosslink density (ρ) increased and free volume fraction (f_g) decreased, resulting in dramatic increase of glass transition temperatures (T_g) and decrease of coefficient of thermal expansion. Additionally, epoxy composites exhibited low dielectric constant close to that of neat epoxy resin. From these remarkable properties, MWCNT/epoxy composites can be considered as a good candidate for high performance insulation materials. POLYM. ENG. SCI., 53:2194–2204, 2013. © 2013 Society of Plastics Engineers     

Rheological properties and fracture toughness of epoxy resin/multi‐walled carbon nanotube composites

Multi‐walled carbon nanotubes (MWCNTs), surface‐treated via chemical functionalization, i.e., oxidation and amidation, were used to reinforce diglycidylether of bisphenol F (DGEBF) epoxy resin. The effects of the functionalization on the dispersion stability, rheological properties, and fracture toughness of DGEBF/MWCNT composites were investigated. The dispersion homogeneity of the MWCNTs in the epoxy matrix improved after functionalization. In addition, isothermal rheology measurements revealed that the DGEBF/dodecyl amine‐functionalized MWCNT (D‐MWCNT) composite had a longer gel time and higher activation energy of cross‐linking than the DGEBF/acid‐treated MWCNT (A‐MWCNT) composite. The fracture toughness of the former was also significantly higher than that of the latter; this resulted from the relatively high dispersion stability of the D‐MWCNTs in the epoxy matrix, owing to the presence of alkyl groups on the D‐MWCNT surface. POLYM. ENG. SCI., 55:2676–2682, 2015. © 2015 Society of Plastics Engineers     

Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

Cure reaction of multi‐walled carbon nanotubes/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites: effect of carboxylic functionalization of MWCNTs

BACKGROUND: The aim of this work was to study, using differential scanning calorimetry, the effect of carboxylic functionalization of multi‐walled carbon nanotubes (MWCNTs) on the cure reaction of MWCNTs/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites. This is important for the practical design, analysis and optimization of novel materials processing. RESULTS: Comparing the influence of non‐functionalized MWCNTs and carboxyl‐functionalized MWCNTs, it was found that, at the initial curing stage, both MWCNTs act as catalyst and COOH functionalization of MWCNTs has a catalytic effect on the curing process. Then, at the later curing stage, non‐functionalized MWCNTs prevent the occurrence of vitrification, whereas COOH functionalization of MWCNTs promotes vitrification. Non‐functionalized MWCNTs decrease the degree of curing, as evidenced by lower total heat of reaction and lower glass transition temperatures of nanocomposites compared to neat epoxy; however, COOH functionalization of MWCNTs increases the degree of curing. CONCLUSION: For the development of composites, COOH functionalization of MWCNTs could bring a positive influence to the composite process. Its acceleration of cure could help shorten pre‐cure time or lower pre‐treatment temperature, and its effect of promoting vitrification could help shorten post‐cure time or lower post‐treatment temperature. Copyright © 2009 Society of Chemical Industry     

Multiwalled carbon nanotubes–BaTiO3/silica composites with high complex permittivity and improved electromagnetic interference shielding at elevated temperature

Composites with silica matrix and mixed filler of multiwalled carbon nanotubes (MWCNTs) and BaTiO₃ powder were fabricated. Excellent uniform dispersion of MWCNTs can be obtained using a two-step mixing method. Both of the real and imaginary parts of complex permittivity increased with increasing MWCNT content and measured temperature. The electromagnetic interference (EMI) shielding results showed that the absorption mechanism is the main contribution to the total EMI shielding effectiveness (SE). Compared with the EMI SE resulting from reflection, the absorption showed more dependence on the MWCNT content, measured temperature and frequency. The total EMI SE is greater than 20 dB at 25 °C and 50 dB at 600 °C in the whole frequency range of 12.4–18 GHz with a 1.5 mm composite thickness, which suggests that the MWCNT–BaTiO₃/silica composites could be good candidates for the EMI shielding materials in the measured frequency and temperature region.     

Physical properties of phenol-anchored multiwall carbon nanotube/epoxy nanocomposite

Surface functionalization of multiwall carbon nanotubes (MWCNTs) was carried out by introducing a ylide group containing anchored phenol structures. Epoxy nanocomposites filled with modified and pristine carbon nanotubes were prepared, and their mechanical, electrical, and thermal properties were evaluated. Mechanical properties such as tensile strengths and Young’s moduli of the epoxy nanocomposites increased significantly with the addition of the modified MWCNTs compared to the pristine MWCNTs, due to the strong interaction between the modified MWCNTs and the epoxy matrix. Scanning electron microscopy of the fractured epoxy systems revealed that the functionalized MWCNTs were finely dispersed in the matrix, as opposed to the pristine carbon nanotubes. The epoxy/functionalized MWCNT nanocomposite had a lower surface electrical resistance than the epoxy/pristine MWCNT nanocomposite, confirming the effect of functionalization.     

Flexible poly(styrene-b-(ethylene-co-butylene)-b-styrene) nanocomposites for electromagnetic interference shielding

In this report, multiwalled carbon nanotubes (CNT) embedded poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) microspheres (CNT/SEBS) were prepared by solvent evaporation method. Reduced graphene oxide (rGO) nanosheets were used to cover the surface of CNT/SEBS microspheres. The CNT/SEBS/rGO nanocomposites with special segregated conductive network were fabricated by hot pressing these as-prepared complex microspheres. The morphology, electrical percolation threshold, electrical conductivity, and electromagnetic interference (EMI) shielding effectiveness (SE) of CNT/SEBS/rGO composites were characterized. The shielding mechanisms were discussed in detail. Analysis of electrical conductive performance shows that the electrical percolation threshold of rGO is 0.22 vol %. Results of EMI shielding test confirmed the synergistic effect between CNT and rGO. The EMI SE of the composite filled by 2.1 vol % CNT and 3.35 vol % rGO can achieve 26 dB in 8.2− 12.4 GHz (X band), which exceeds the basic requirement for commercial application (20 dB). Its reflectance coefficient (19–41%) indicates that the most part of incident electromagnetic (EM) wave energy is attenuated through absorption mechanism. This kind of absorptive EMI shielding material can be applied without serious secondary EM radiation pollution problems. The effects of filler content, molding temperature on EMI SE, and shielding mechanism were also investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48542.     

Effect of silane structure on the properties of silanized multiwalled carbon nanotube-epoxy nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were functionalized with aminosilanes via an aqueous deposition route. The size and morphology of siloxane oligomers grafted to the MWCNTs was tuned by varying the silane functionality and concentration and their effect on the properties of a filled epoxy system was investigated. The siloxane structure was found to profoundly affect the thermo-mechanical behavior of composites reinforced with the silanized MWCNTs. Well-defined siloxane brushes increased the epoxy T_g by up to 19 °C and significantly altered the network relaxation dynamics, while irregular, siloxane networks grafted to the MWCNTs had little effect. The addition of both types of silanized MWCNTs elicited improvements in the strength of the nanocomposites, but only the well-defined siloxane brushes engendered dramatic improvements in toughness. Because the silanization reaction is simple, rapid, and performed under aqueous conditions, it is also an industrially attractive functionalization route.     

A comparative study on the properties of the different amino‐functionalized multiwall carbon nanotubes reinforced epoxy resin composites

Multiwall carbon nanotubes (MWCNTs) were amino‐functionalized by 1,2‐ethylenediamine (EDA)' triethylenetetramine (TETA), and dodecylamine (DDA), and investigated by fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and thermogravimetric analysis (TGA). The dispersion of the DDA functionalized MWCNT in DMF is better than that of the MWCNT functionalized by the EDA and the TETA. Carbon nanotubes reinforced epoxy resin composites were prepared, and the effect of the amino‐functionalization on the properties of the composites was investigated by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), and TGA. The composites reinforced by the MWCNTs demonstrate improvement in various mechanical properties. The increase of T_g of the composites with the addition of amino‐functionalized MWCNT compared to the T_g of the composites with the addition of unfunctionalized MWCNT was due to the chemical combination and the physical entanglements between amino group from modified MWNTs and epoxy group from the epoxy resin. The interfacial bonding between the epoxy and the amino group of the EDA and the TETA‐modified MWCNT is more important than the well dispersion of DDA‐modified MWCNT in the composites for the improvement of the mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of amino‐functionalization of multi‐walled carbon nanotubes on the dispersion with epoxy resin matrix

Amino‐functionalization of multiwalled carbon nanotubes (MWCNTs) was carried out by grafting triethylenetetramine (TETA) on the surfaces of MWCNTs through the acid–thionyl chloride way. The amino‐functionalized MWCNTs show improved compatibility with epoxy resin and, as a result, more homogenous dispersion in the matrix. The mechanical, optical, and thermal properties of the amino‐functionalized MWCNT/epoxy composites were also investigated. It was found that introducing the amino‐functionalized MWCNTs into epoxy resin greatly increased the charpy impact strength, glass transition temperature, and initial decomposing temperature of cured epoxy resin. In addition, introducing unfunctionalized MWCNTs into epoxy resin was found greatly depressing the light transmission properties, which would affirmatively confine the application of the MWCNTs/epoxy composites in the future, while much higher light transmittance than that of unfunctionalized MWCNTs/epoxy composites was found for amino‐functionalized MWCNTs/epoxy composites. SEM of the impact cross section and TEM of ultrathin film of the amino‐functionalized MWCNTs/epoxy composites showed that the amino‐functionalized MWCNTs were wetted well by epoxy matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 97–104, 2006     

Investigation of the electric conductivity and the electromagnetic interference shielding efficiency of SWCNTs/GNS/PAni nanocomposites

This work demonstrates the fabrications and characterizations of polyaniline (PAni) composites containing single-walled carbon nanotubes (SWCNTs), graphite nanosheets (GNS), or hybrid fillers (SWCNTs/GNS). The characterization of microstructure, examination of fracture surface morphologies, and measurement of electric conductivity and electromagnetic interference shielding efficiency (EMI SE) were performed. It was found that both the electric conductivity and the EMI SE increase with filler loading, and the nanocomposites filled with 1.0 wt.% SWCNTs/GNS possessed the highest electric conductivity of 16.2 S/cm and total EMI SE of 27.0 dB. The experimental results also show that absorption is the primary mechanism of EMI SE for all of the loadings and fillers.