Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

Superior mechanical and electrical properties of multiwall carbon nanotube reinforced acrylonitrile butadiene styrene high performance composites

In-house synthesized multiwall carbon nanotubes (MWCNTs) have been dispersed in acrylonitrile butadiene styrene (ABS) using a micro twin-screw extruder with back flow channel. The electrical and mechanical properties of MWCNTs in ABS with different wt% have been studied. Incorporation of only 3 wt. % MWCNTs in ABS leads to significant enhancement in the tensile strength (up to 69.4 MPa) which was equivalent to 29% increase over pure ABS. The effect of MWCNTs on the structural behaviour of ABS under tensile loading showed a ductile to brittle transition with increase concentration of MWCNTs. The results of enhanced mechanical properties were well supported by micro Raman spectroscopic and scanning electron microscopic studies. In addition to the mechanical properties, electrical conductivity of these composites increased from 10⁻¹² to 10⁻⁵ Scm⁻¹ showing an improvement of ∼7 orders of magnitude. Due to significant improvement in the electrical conductivity, EMI shielding effectiveness of the composites is achieved up to −39 dB for 10 wt. % loaded MWCNTs/ABS indicating the usefulness of this material for EMI shielding in the Ku-band. The mechanism of improvement in EMI shielding effectiveness is discussed by resolving their contribution in absorption and reflection loss. This material can be used as high-strength EMI shielding material.     

Effects of hybrid fillers on the electromagnetic interference shielding effectiveness of polyamide 6/conductive filler composites

The effects of hybrid conductive fillers on the electrical conductivity and electromagnetic interference shielding effectiveness (EMI SE) of polyamide 6 (PA6)/conductive filler composites were investigated. Nickel-coated carbon fiber (NCCF) was used as the main filler and multi-walled carbon nanotube (MWCNT), nickel-coated graphite, carbon black, and titanium dioxide (TiO₂) were used as the second fillers in this study. From the results of morphological studies of the PA6/NCCF/second filler composites, NCCF easily formed an electrical pathway since it has a high aspect ratio and random orientation, and the second fillers seemed to disperse evenly in the PA6 matrix. The electrical conductivity and EMI SE of the PA6/NCCF composites were increased with the increase of NCCF content. Among the second fillers used in this study, TiO₂ appeared to be the most effective second filler with regard to increasing the EMI SE and electrical conductivity of the PA6/NCCF composite. This was probably because TiO₂ has a high dielectric constant with dominant dipolar polarization, consequently leading to greater shielding effectiveness due to the absorption of electromagnetic waves. From the above results of EMI SE and electrical conductivity, it was suggested that the TiO₂ produced a synergistic effect when it was hybridized with the NCCF of the PA6/NCCF/TiO₂ composites.     

Elastomer foam nanocomposites for electromagnetic dissipation and shielding applications

A novel elastomer foamed nanocomposite has been developed with high electromagnetic dissipation and shielding properties. This light weight foamed fluorocarbon incorporates multi-walled carbon nanotubes at low loading concentrations to achieve levels of conductivity and energy shielding that surpass the requirements for electromagnetic static discharge (ESD) and electromagnetic interference (EMI) shielding. Foaming the elastomer reduces that weight by 30% with minimal impact on ESD or EMI characteristics. The percolation threshold is at about 2% carbon nanotubes and the saturation conductivity occurs at 8% carbon nanotubes by weight. Combining the good electrical properties with the flexibility and fluid resistance of fluorocarbon yields a very versatile yet light weight material for a variety of ESD and EMI applications.     

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.     

Highly conducting poly(methyl methacrylate)/carbon nanotubes composites: Investigation on their thermal, dynamic-mechanical, electrical and dielectric properties

Nanocomposites of poly(methyl methacrylate) (PMMA) containing various multi-walled carbon nanotubes (MWCNT) contents were prepared using melt mixing. Several techniques were employed to study the influence of the MWCNT addition on the thermal, mechanical, electrical and dielectric properties of the PMMA matrix. The electrical percolation threshold (p_c) was found to be 0.5 vol.% by performing AC and DC conductivity measurements. Significantly high conductivity levels (σ_dc) were achieved: σ_dc exceeds 10⁻² S/cm already at 1.1 vol.%, the criterion for EMI shielding (σ_dc > 10⁻¹ S/cm) is fulfilled at 2.9 vol.%, and the highest loaded sample (5.2 vol.%) gave a maximum value of 0.5 S/cm. Dielectric relaxation spectroscopy measurements in broad frequency (10⁻¹−10⁶ Hz) and temperature ranges (−150 to 170 °C) indicated weak polymer-filler interactions, in consistency with differential scanning calorimetry and dynamic-mechanical analysis findings. Weak polymer-filler interactions and absence of crystallinity facilitate the achievement of high conductivity levels in the nanocomposites.     

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.     

The effect of geometric factor of carbon nanofillers on the electrical conductivity and electromagnetic interference shielding properties of poly(trimethylene terephthalate) composites: a comparative study

In this study, the effects of filler geometry on the electrical conductivity and electromagnetic interference (EMI) shielding properties of poly(trimethylene terephthalate) (PTT) composites filled with graphene nanosheets (GNSs), carbon nanotubes (CNTs), and GNS–CNT hybrid nanofillers have been investigated. The GNSs, CNTs, and hybrid GNS–CNT were well dispersed in the PTT matrix using a simple coagulation process. GNSs were prepared from graphene oxide (GO) through hydrazine reduction, and thermal reduction of GO at two different temperatures of 1050 and 1500 °C. PTT filled with different aspect ratios and oxygen functional groups of GNS were also prepared in order to compare the electrical conductivity and EMI shielding properties. The aspect ratios of GNSs and CNTs were estimated by using an ellipsoid model. Percolation scaling laws were applied to the magnitudes of conductivity to reveal the percolation network and filler dispersion. The percolation exponent of the PTT/GNS composites was larger than that of the PTT/CNT composites. The percolated filler–filler network at which the percolation exponent changed was correlated with the filler geometric structure. GNS–CNT hybrid nanofillers formed a complex double brush structure in the PTT/GNS–CNT composites. The geometric structure, aspect ratio, and intrinsic conductivity of carbon nanofillers affected the electrical percolation threshold and EMI shielding efficiency of the composites.     

Processing of graphene nanoribbon based hybrid composite for electromagnetic shielding

The advent of graphene heralded by the recent studies on carbon based conducting polymer composites has been a motivation for the use of graphene as an electromagnetic interference (EMI) shielding material. One of the variants of graphene, graphene nanoribbon (GNR) shows remarkably different properties from graphene. The EMI shielding effectiveness of the composite material mainly depends on fillers’ intrinsic conductivity, dielectric constant and aspect ratio. We have synthesized graphene nanoribbon (GNR) – Polyaniline (PANI) – epoxy composite film for effective shielding material in the X-band frequency range of 8.2–12.4 (GHz). We have performed detailed studies of the EMI shielding effect and the performance of the composite and found that the composite shows ∼−40 dB shielding which is sufficient to shield more than 95% of the EM waves in X Band. We checked the shielding effectiveness of the composite film by varying the GNR percentage and the thickness of the film. The strength properties of the synthesized composited were also studied with a aim to have a material having both high strength and EMI shielding properties.     

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.     

The effects of carbon nanotubes on mechanical and thermal properties of woven glass fibre reinforced polyamide-6 nanocomposites

This paper presents a preliminary investigation on the effects of incorporating carbon nanotubes (CNT) into polyamide-6 (PA6) on mechanical, thermal properties and fire performance of woven glass reinforced CNT/PA6 nanocomposite laminates. The samples were characterized by tensile and flexural tests, thermal gravimetric analysis (TGA), heat distortion temperature (HDT) measurements, thermal conductivity and cone calorimeter tests. Incorporation of up to 2 wt% CNT in CNT/PA6/GF laminates improved the flexural stress of the laminates up to 36%, the thermal conductivity by approximately 42% and the ignition time and peak HRR time was delayed by approximately 31% and 118%, respectively.     

Highly strong and conductive carbon nanotube/cellulose composite paper

Carbon nanotube (CNT)/cellulose composite materials were fabricated in a paper making process optimized for a CNT network to form on the cellulose fibers. The measured electric conductivity was from 0.05 to 671 S/m for 0.5–16.7 wt.% CNT content, higher than that for other polymer composites. The real permittivities were the highest in the microwave region. The unique CNT network structure is thought to be the reason for these high conductivity and permittivity values. Compared to other carbon materials, our carbon CNT/cellulose composite material had improved parameters without decreased mechanical strength. The near-field electromagnetic shielding effectiveness (EMI SE) measured by a microstrip line method depended on the sheet conductivity and qualitatively matched the results of electromagnetic field simulations using a finite-difference time-domain simulator. A high near-field EMI SE of 50-dB was achieved in the 5–10 GHz frequency region with 4.8 wt.% composite paper. The far-field EMI SE was measured by a free space method. Fairly good agreement was obtained between the measured and calculated results. Approximately 10 wt.% CNT is required to achieve composite paper with 20-dB far-field EMI SE.     

In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites

Electrically conductive and thermally stable polyamide 6 (PA 6) nanocomposites were prepared through one-step in situ polymerization of ε-caprolactam monomer in the presence of electrically insulating and thermally unstable graphene oxide (GO) nanosheets. These nanocomposites show a low percolation threshold of ∼0.41 vol.% and high electrical conductivity of ∼0.028 S/m with only ∼1.64 vol.% of GO. Thermogravimetric analysis and X-ray photoelectron spectroscopy results of GO before and after thermal treatment at the polymerization temperature indicate that GO was reduced in situ during the polymerization process. X-ray diffraction patterns and scanning electron microscopy observation confirm the exfoliation of the reduced graphene oxide (RGO) in the PA 6 matrix. The low percolation threshold and high electrical conductivity are attributed to the large aspect ratio, high specific surface area and uniform dispersion of the RGO nanosheets in the matrix. In addition, although GO has a poor thermal stability, its PA 6 nanocomposite is thermally stable with a satisfactory thermal stability similar to those of neat PA 6 and PA 6/graphene nanocomposite. Such a one-step in situ polymerization and thermal reduction method shows significant potential for the mass production of electrically conductive polymer/RGO nanocomposites.     

Synergetic effect of conducting polymer composites reinforced E-glass fabric for the control of electromagnetic radiations

The use of fibril materials as substrate for reinforcing polymers has wide industrial applications. In this article, we discuss polyaniline and polypyrrole as conducting polymers to provide electronic conductivity in E-glass fabric reinforced conducting composite with varied degree of composition and conductivity using industrially important polymers polymethylmethacrylate and polyvinyl chloride as a host matrix. Aromatic sulphonic acids such as PXSA, OXSA, PSA, PDSA, RDSA, OCPSA and MCSA were used as a dopant. The influence of the aromatic ring substituents in these dopants over the conductivity and processibility due to various interactions has been studied. The study shows that due to bulk nature of conductivity, shielding effectiveness (SE) increases with increase in conductivity and thickness of a composite. The test samples were characterized by conductivity and electromagnetic shielding effectiveness (EMI SE). The electromagnetic shielding effectiveness was measured by co-axial transmission line method in the frequency range of 0.01–1000 MHz. These composites with both side shielded by polypyrrole offered a uniform shielding effectiveness of 69 dB.     

Self-assemblies of linearly aligned diamond fillers in polysiloxane/diamond composite films with enhanced thermal conductivity

The relocation of diamond fillers was performed in polysiloxane-based composite films under different electric fields. The microscale diamond filler particles were dispersed by sonication in a prepolymer mixture of polysiloxane, followed by high-speed mixing. The homogeneous suspension was cast onto a polyamide spacer of microscale thickness and subjected to three different electric fields: AC, DC, and switched DC, before the mixture became cross-linked. Analysis revealed that self-assemblies of linearly aligned diamond fillers (LADFs) were fabricated in the composite film, connecting the film planes as bridges with different thicknesses depending on the applied electric field. Composites with assemblies of LADFs exhibited enhanced thermal conductivity and electrical insulation, and are attractive for application as thermal interface materials in the semiconductor industry.     

Influence of small scale melt mixing conditions on electrical resistivity of carbon nanotube-polyamide composites

Polyamide 6 (PA6) and polyamide 6.6 (PA66) were filled with multiwalled carbon nanotubes (MWNT) using small scale melt mixing under variation of processing conditions, including temperature, rotation speed, and mixing time. In PA66 an electrical percolation threshold of 1 wt% MWNT was found which is lower than that of PA6 at 2.5–4 wt%. In both cases mixing conditions influenced strongly the dispersion and distribution of CNT and the electrical volume resistivity, whereas crystallisation behaviour was only slightly changed. With increasing mixing energy input remaining agglomerates were less in number and smaller, leading to better dispersion. On the other hand, in samples containing 5 wt% MWNT in PA6 electrical volume resistivity showed a minimum at a quite low energy input and then increased considerably with further input of mixing energy. This increase may be related to MWNT breaking during mixing and encapsulation of MWNT by the polyamide chains.     

Investigation of thermal conductivity and dielectric properties of LDPE-matrix composites filled with hybrid filler of hollow glass microspheres and nitride particles

The hybrid filler of hollow glass microspheres (HGM) and nitride particles was filled into low-density polyethylene (LDPE) matrix via powder mixing and then hot pressing technology to obtain the composites with higher thermal conductivity as well as lower dielectric constant (D_k) and loss (D_f). The effects of surface modification of nitride particles and HGMs as well as volume ratio between them on the thermal conductivity and dielectric properties at 1 MHz of the composites were first investigated. The results indicate that the surface modification of the filler has a beneficial effect on thermal conductivity and dielectric properties of the composites due to the good interfacial adhesion between the filler and matrix. An optimal volume ratio of nitride particles to HGMs of 1:1 is determined on the basis of overall performance of the composites. The thermal conductivity as well as dielectric properties at 1 MHz and microwave frequency of the composites made from surface-modified fillers with the optimal nitride to HGM volume ratio were investigated as a function of the total volume fraction of hybrid filler. It is found that the thermal conductivity increases with filler volume fraction, and it is mainly related to the type of nitride particle other than HGM. The D_k values at 1 MHz and microwave frequency show an increasing trend with filler volume fraction and depend largely on the types of both nitride particles and HGMs. The D_f values at 1 MHz or quality factor (Q × f) at microwave frequency show an increasing or decreasing trend with filler volume fraction and also depend on the types of both nitride particle and HGM. Finally, optimal type of HGM and nitride particles as well as corresponding thermal conductivity and dielectric properties is obtained. SEM observations show that the hybrid filler particles are agglomerated around the LDPE matrix particles, and within the agglomerates the smaller-sized nitride particles in the hybrid filler can easily form thermally conductive networks to make the composites with high thermal conductivity. At the same time, the increase of the value D_k of the composites is restricted due to the presence of HGMs.     

Synergy in hybrid polymer/nanocarbon composites. A review

The aim of this review article is to report the most recent developments in the understanding of and beliefs about the properties of polymer hybrid composites that are reinforced with various combinations of nanometer-sized carbon and mineral fillers. The discussions are primarily focused on an analysis and comparison of the electrical, thermal, and mechanical properties. It is shown that the introduction of a mixed (hybrid) system of filler nanoparticles into polymer matrices enhances the macro- and microproperties of the composites as a result of the synergistic interactions between the fillers and the simultaneous creation of a unique filler network in the polymer. The synergy of various types of carbon nanofillers and combinations of nanocarbon materials with inorganic fillers manifests itself as modifications of most of the properties of hybrid polymer composites relative to the properties of a polymer system containing a single filler. The reinforcing effect is related to the structure and particle geometry of the hybrid fillers, the interactions between the fillers, the concentrations and the processing methods.The existence of synergy between different types of carbon nanofillers, as well as with mineral fillers, shows great potential and could significantly increase applications of carbon-based nanomaterials.     

Development of high performance EMI shielding material from EVA,NBR, and their blends: effect of carbon black structure

The conductive composites were prepared using two different types of conductive black (Conductex and Printex XE2) filled in matrices like EVA and NBR and their different blends. The electromagnetic interference shielding effectiveness (EMI SE) of all composites was measured in the X band frequency range 8–12 GHz. Both conductivity and EMI SE increase with filler loading. However, Printex black shows higher conductivity and better EMI SE at the same loading compared to Conductex black, and this can be used as a material having high EMI shielding effectiveness value. The conductivity of different blends with same filler loading generally found to increase slightly with the increase in NBR concentration. However, EMI SE has some dependency on blend composition. EMI SE increases linearly with thickness of the sample. EMI SE versus conductivity yields two master curves for two different fillers. EMI SE depends on formation of closed packed conductive network in insulating matrix, and Printex black is better than Conductex black in this respect. Some of the composites show appreciably high EMI SE (>45 dB).     

Nanoparticles with various surface modifications as functionalized cross-linking agents for composite resin materials

The performance of epoxy resins used for carbon fibre reinforced plastics can be significantly improved by the incorporation of nanoparticles. It is well known that the effect of material altering depends on many factors as filler material, particle distribution, particle size and shape. This paper investigates the hypothesis that particle surface modifications lead to a further improvement of the mechanical properties. Results of nanocomposites filled with four different surface modified boehmite particles are presented. The material was tested with different filler contents and analysed for chemical bonding, viscosity, thermal properties and bending performance. Surprising results show a strong influence of the surface modification on the viscosity, but no significant changes in the other material characteristics. The change of filler content in contrast has an influence on all tested performances of the nanocomposites. The results show a contrary effect of network interruption due to sterical hindrance by the particles and reinforcement due to the stiff ceramic fillers. For different filler contents these two effects have a varying influence on the material characteristics. From these results a model for the mechanism of the particle reinforcement in thermosets is concluded, which helps to understand the effectiveness of nanoparticles as reinforcement of epoxy resins.