Highly electrically and thermally conductive silicon carbide-graphene composites with yttria and scandia additives

Dense silicon carbide/graphene nanoplatelets (GNPs) and silicon carbide/graphene oxide (GO) composites with 1 vol.% equimolar Y₂O₃–Sc₂O₃ sintering additives were sintered at 2000 °C in nitrogen atmosphere by rapid hot-pressing technique. The sintered composites were further annealed in gas pressure sintering (GPS) furnace at 1800 °C for 6 h in overpressure of nitrogen (3 MPa). The effects of types and amount of graphene, orientation of graphene sheets, as well as the influence of annealing on microstructure and functional properties of prepared composites were investigated. SiC-graphene composite materials exhibit anisotropic electrical as well as thermal conductivity due to the alignment of graphene platelets as a consequence of applied high uniaxial pressure (50 MPa) during sintering. The electrical conductivity of annealed sample with 10 wt.% of GNPs oriented parallel to the measuring direction increased significantly up to 118 S·cm⁻¹. Similarly, the thermal conductivity of composites was very sensitive to the orientation of GNPs. In direction perpendicular to the GNPs the thermal conductivity decreased with increasing amount of graphene from 180 W·m⁻¹ K⁻¹ to 70 W·m⁻¹ K⁻¹, mainly due to the scattering of phonons on the graphene – SiC interface. In parallel direction to GNPs the thermal conductivity varied from 130 W·m⁻¹ K⁻¹ up to 238 W·m⁻¹ K⁻¹ for composites with 1 wt.% of GO and 5 wt.% of GNPs after annealing. In this case both the microstructure and composition of SiC matrix and the good thermal conductivity of GNPs improved the thermal conductivity of composites.     

Economical conductive graphite-filled polymer composites via adjustable segregated structures: Construction,low percolation threshold,and positive temperature coefficient effect

The economical graphite-filled thermoplastic urethane/ultra-high molecular weight polyethylene (TPU/UHMWPE) composites with the segregated structure were constructed by the combination of mechanical crushing and melt blending method. The low percolation threshold of 1.89 wt% graphite in the adjustable segregated composites was obtained and high electrical conductivity was about 10⁻¹ S m⁻¹ at 10 wt% graphite loadings owing to the formation of three-dimensional conductive networks. Moreover, when the graphite loadings were over the percolation threshold, the remarkable positive temperature coefficient (PTC) effect of electrical resistivity for TPU/UHMWPE-Graphite composites were achieved, originating from the combined thermal motion of TPU and UHMWPE. Meanwhile, the outstanding repeatability of PTC effects was obtained after 5-time cycles. Therefore, economical conductive polymer composites were still the promising field in the practical application of PTC materials.     

Multilayered ultrahigh molecular weight polyethylene/natural graphite/boron nitride composites with enhanced thermal conductivity and electrical insulation by hot compression

A scalable strategy to fabricate thermally conductive but electrically insulating polymer composites was urgently required in various applications including heat exchangers and electronic packages. In this work, multilayered ultrahigh molecular weight polyethylene (UHMWPE)/natural graphite (NG)/boron nitride (BN) composites were prepared by hot compressing the UHMWPE/NG layers and UHMWPE/BN layers alternately. Taking advantage of the internal properties of NG and BN fillers, the UHMWPE/NG layers played a decisive role in enhancing thermal conductivity (TC), while the UHMWPE/BN layers effectively blocked the electrically conductive pathways without affecting the thermal conductive pathways. The in-plane TC, electrical insulation, and heat spreading ability of multilayered UHMWPE/NG/BN composites increased with the increasing layer numbers. At the total fillers loading of 40 wt%, the in-plane TC of multilayered UHMWPE/NG/BN composites with nine layers was markedly improved to 6.319 Wm⁻¹ K⁻¹, outperforming UHMWPE/BN (4.735 Wm⁻¹ K⁻¹) and pure UHMWPE (0.305 Wm⁻¹ K⁻¹) by 33.45% and 1971.80%, respectively. Meanwhile, the UHMWPE/NG/BN composites still maintained an excellent electrically insulating property (volume resistance~5.40×10¹⁴ Ω cm ; breakdown voltage~1.52 kV/mm). Moreover, the multilayered UHMWPE/NG/BN composites also exhibited surpassing heat dissipation capability and mechanical properties. Our results provided an effective method to fabricate highly thermal conductive and electrical insulating composites.     

Poly(methyl methacrylate)-functionalized reduced graphene oxide-based core–shell structured beads for thermally conductive epoxy composites

Thermally conductive epoxy nanocomposite with core–shell structured filler beads has been prepared. The core represents plasma-treated poly(methyl methacrylate) bead, and the shell, amine-functionalized reduced graphene oxide (frGO) sheets. The negatively charged core and the positively charged shell form core–shell unified structure through electrostatic attraction and the conductive bridges are formed among neighboring filler particles in the composite mass. The epoxy composite prepared with these core–shell structured filler shows a thermal conductivity of 0.72 W m⁻¹ K⁻¹ for an overall frGO concentration of as low as 0.96 wt %. Pal model has been applied to evaluate the effective thermal conductivity of frGO sheets that have been realized in the epoxy composition. Assuming the maximum possible volume packing fraction of the spherical beads for random jamming to be equal to 0.63, the effective thermal conductivity has been estimated as 280 W m⁻¹ K⁻¹. Evaluation of the effective thermal conductivity is a step forward to in-depth study of real contribution of the highly conductive fillers in the polymer composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47377.     

A bio-based compatibilizer for improved interfacial compatibility in thermally conductive and electrically insulating graphite/high density poly(ethylene) composites

Graphite is a thermally conductive filler. However, when dispersed into high density poly(ethylene) (HDPE) resin, graphite particles tend to agglomerate and requires a compatibilizer to achieve desired thermal/physical properties. In this study, oleic acid (OA), a bio-based additive and polyethylene-polyamines (PEPA) were used to synthesize a new compatibilizer, PEPA-g-OA, containing numerous  NR₂ groups. The experimental results showed that PEPA-g-OA can significantly improve the compatibility between graphite particles and the HDPE matrix due to uniform dispersion of graphite in the HDPE matrix. When the graphite content was 25 wt%, the thermal conductivity of the composite recorded 1.2 W m⁻¹ K⁻¹ (three times that of neat HDPE) and the volume resistivity was 1.8 × 10⁹ Ω cm, indicating excellent electrical insulation. Compared to the composites with no graphite content, the properties of the composites with 25 wt% graphite content exhibited narrower melting and crystallization peaks, more stable mechanical properties, and higher ultraviolet aging resistance. Synthesized new bio-based compatibilizer and thermally conductive and electrically insulating composites developed in this study can be useful in different industrial fields for the preparation of the next generation composites.     

The effect of graphene nanoplatelets on the thermal and electrical properties of aluminum nitride ceramics

The thermal conductivity (κ) of AlN (2.9 wt.% of Y₂O₃) is studied as a function of the addition of multilayer graphene (from 0 to 10 vol.%). The κ values of these composites, fabricated by spark plasma sintering (SPS), are independently analyzed for the two characteristic directions defined by the GNPs orientation within the ceramic matrix; that is to say, perpendicular and parallel to the SPS pressing axis. Conversely to other ceramic/graphene systems, AlN composites experience a reduction of κ with the graphene addition for both orientations; actually the decrease of κ for the in-plane graphene orientation results rather unusual. This behavior is conveniently reproduced when an interface thermal resistance is introduced in effective media thermal conductivity models. Also remarkable is the change in the electrical properties of AlN becoming an electrical conductor (200 S m⁻¹) for graphene contents above 5 vol.%.     

Application of nitrogen-doped graphene nanosheets in electrically conductive adhesives

Nitrogen-doped graphene nanosheets (N-GNSs) were used as a conductive filler for a polymer resin adhesive and as a performance improver for a silver-filled electrically conductive adhesive (ECA). The N-GNS samples were prepared by the chemical-intercalation/thermal-exfoliation of graphite followed by a thermal treatment in NH₃. Only 1 wt.% of N-GNSs was required for the adhesive to reach a percolation threshold, and the performance using N-GNSs was much better than that obtained using carbon black or multi-walled carbon nanotubes (MWCNTs). The effect of N-GNS or MWCNT additives on reducing the electrical resistivity of Ag-particle filled ECAs at low Ag loading ratios was also investigated. With 30 wt.% of Ag filler, the polymer resin was still non-conducting, while a resistivity of 4.4 × 10⁻² Ω-cm was obtained using an Ag/N-GNS hybrid filler fortified with only 1 wt.% of N-GNSs due to large specific surface area, high aspect ratio, and good electrical conductivity of the doped graphene.     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electromagnetic interference shielding of graphite/acrylonitrile butadiene styrene composites

Dispersion of graphite within the acrylonitrile butadiene styrene matrix demonstrates enhanced electromagnetic interference shielding of composites through the use of tumble mixing technique. A shielding effectiveness of 60 dB with 15 wt % of graphite has been achieved. D shore hardness data revealed a little decrease in hardness of composites with rise in graphite content. DC conductivity measurements revealed a fairly low percolation threshold at 3 wt % of graphite. The conductivity exhibited by 15 wt % composite is 1.66 × 10⁻¹ S/cm. These composites are fit for use as an effective and convenient EMI shielding material because of easy processing, better hardness, light weight, and, reasonable shielding efficiency. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Wire electrical discharge machinable SiC with GNPs and GO as the electrically conducting filler

SiC based composites filled with graphene nano-platelets (GNPs) or graphene oxide (GO) prepared by rapid hot-pressing exhibit sufficient electrical conductivity for their machinability by wire electro-discharge machining (WEDM). Composites microstructure anisotropy caused by graphene alignment as a consequence of rapid hot pressing was confirmed by measuring of electrical conductivity and thermal diffusivity. Electrical conductivity increased significantly with increased weight fraction of graphene in both measured directions. Highest value of 2031 S/m was obtained for composites with 15 wt. % of GNPs in parallel direction and only 1246 S/m in perpendicular direction to aligned GNPs. Thermal diffusivity is 63.3 mm²/s in parallel and only 23.3 mm²/s in perpendicular direction. The increase of the electrical conductivity has resulted in successful WEDM. The MRR was almost doubled when the filler concentration increased from 5 wt. % GNPs/GO to 15 wt. % GNPs. At the same time, the surface roughness decreased.     

Improving tribological properties of phenolic resin/carbon fiber composites using m-Si3N4@PANI core–shell particles

Phenolic resin/carbon fiber (PF/CF) composites have good tribological properties; however, their extensive applications are limited because of the poor thermal conductivity of the phenolic resins. In this work, core‑shell particles of polyaniline-coated (3-aminopropyl) triethoxysilane-modified β-Si₃N₄ (m-SiN@PANI) were used to enhance the tribological, electrical, and thermal conductivity properties of a PF/CF composite. A core‑shell particle, consisting of m-SiN@PANI, was characterized by Fourier Transform Infrared Spectrometry, X-Ray Diffraction, Scanning Electron Microscope, and Transmission Electron Microscope. The friction, thermal, and electrical properties of the composites were characterized by multifunctional vertical friction testing, wear measurement testing, thermogravimetric analysis, thermal constant analysis, and electrical conductivity testing. Remarkably, the test results showed that compared with the wear surface of the PF/CF composite, that of the phenolic resin/(2.0 wt % m-SiN@PANI)/carbon fiber composite exhibited a smoother morphology. The results indicated that the addition of m-SiN@PANI effectively improved the thermal conductivity, electrical conductivity, friction coefficient, and wear rate of the composites, which were 3.164 Wm⁻¹ K⁻¹, 5.33 × 10⁻⁶ S/m, 0.1681 and 1.13 × 10⁻⁸ mm³/Nm, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47785.     

High electromagnetic interference shielding with high electrical conductivity through selective dispersion of multiwall carbon nanotube in poly (ε‐caprolactone)/MWCNT composites

This study presents the preparation of electrically conducting poly(ε‐caprolactone) (PCL)/multiwall carbon nanotube (MWCNT) composites with very low percolation threshold (p_c). The method involves solution blending of PCL and MWCNT in the presence of commercial PCL beads. The PCL beads were added into high viscous PCL/MWCNT mixture during evaporation of solvent. Here, the used commercial PCL polymer beads act as an ‘excluded volume’ in the solution blended PCL/MWCNT region. Thus, the effective concentration of the MWCNT dramatically increases in the solution blended region and a strong interconnected continuous conductive network path of CNT−CNT is assumed throughout the matrix phase with the addition of PCL bead which plays a crucial role to improve the electromagnetic interference shielding effectiveness (EMI SE) and electrical conductivity at very low MWCNT loading. Thus, high EMI SE value (∼23.8 dB) was achieved at low MWCNT loading (1.8 wt %) in the presence of 70 wt % PCL bead and the high electrical conductivity of ∼2.49×10⁻² S cm⁻¹ was achieved at very low MWCNT loading (∼0.15 wt %) with 70 wt % PCL bead content in the composites. The electrical conductivity gradually increased with increasing the PCL bead concentration, as well as, MWCNT loading in the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42161.     

Synergistic Effects of Carbon Fillers of Phenolic Resin Based Composite Bipolar Plates on the Performance of PEM Fuel Cell

The most essential and costly component of polymer electrolyte membrane fuel cells is the bipolar plate. The production of suitable composite bipolar plates for polymer electrolyte membrane fuel cell with good mechanical properties and high electrical conductivity is scientifically and technically very challenging. This paper reports the development of composite bipolar plates using exfoliated graphite, carbon black, and graphite powder in resole‐typed phenol formaldehyde. The exfoliated graphite with maximum exfoliated volume of 570 ± 10 mL g⁻¹ used in this study was prepared by microwave irradiation of chemically intercalated natural flake graphite in a few minutes. The composite plates were prepared by varying exfoliated graphite content from 10 to 35 wt.% in phenolic resin along with fixed weight percentage of carbon black (5 wt.%) and graphite powder (3 wt.%) by compression molding. The composite plates with filler weight percentage of 35/5/3/exfoliated graphite/carbon black/graphite powder offer in‐plane and trough‐plane electrical conductivities of 374.42 and 97.32 S cm⁻¹, bulk density 1.58 g cm⁻³, compressive strength 70.43 MPa, flexural strength 61.82 MPa, storage modulus 10.25 GPa, microhardness 73.23 HV and water absorption 0.22%. Further, I–V characteristics notify that exfoliated graphite/carbon black/graphite powder/resin composite bipolar plates in unit fuel cell shows better cell performance compared exfoliated graphite/resin composite bipolar plates. The composite plates own desired mechanical properties with low bulk density, high electrical conductivity, and good thermal stability as per the U.S. department of energy targets at low filler concentration and can be used as bipolar plates for proton exchange membrane fuel cells.     

Synthesis of conducting graphene/Si3N4 composites by spark plasma sintering

Graphene/silicon nitride (Si₃N₄) composites with high fraction of few layered graphene are synthesized by an in situ reduction of graphene oxide (GO) during spark plasma sintering (SPS) of the GO/Si₃N₄ composites. The adequate intermixing of the GO layers and the ceramic powders is achieved in alcohol under sonication followed by blade mixing. The reduction of GO occurs together with the composite densification in SPS, thus avoiding the implementation of additional reduction steps. The materials are studied by X-ray photoelectron and micro-Raman spectroscopy, revealing a high level of recovery of graphene-like domains. The SPS graphene/Si₃N₄ composites exhibit relatively large electrical conductivity values caused by the presence of reduced graphene oxide (∼1 S cm⁻¹ for ∼4 vol.%, and ∼7 S cm⁻¹ for 7 vol.% of reduced-GO). This single-step process also prevents the formation of highly curved graphene sheets during the thermal treatment as the sheets are homogeneously embedded in the ceramic matrix. The uniform distribution of the reduced GO sheets in the composites also produces a noticeable grain refinement of the silicon nitride matrix.     

Multifunctional polyimide/graphene oxide composites via in situ polymerization

In this article, we detail an effective way to improve electrical, thermal, and gas barrier properties using a simple processing method for polymer composites. Graphene oxide (GO) prepared with graphite using a modified Hummers method was used as a nanofiller for r‐GO/PI composites by in situ polymerization. PI composites with different loadings of GO were prepared by the thermal imidization of polyamic acid (PAA)/GO. This method greatly improved the electrical properties of the r‐GO/PI composites compared with pure PI due to the electrical percolation networks of reduced graphene oxide within the films. The conductivity of r‐GO/PI composites (30:70 w/w) equaled 1.1 × 10¹ S m^?1, roughly 10¹⁴ times that of pure PI and the oxygen transmission rate (OTR, 30:70 w/w) was reduced by about 93%. The Young's modulus of the r‐GO/PI composite film containing 30 wt % GO increased to 4.2 GPa, which was an approximate improvement of 282% compared with pure PI film. The corresponding strength and the elongation at break decreased to 70.0 MPa and 2.2%, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40177.     

In situ preparation of graphene‐ZnO composites for enhanced graphite exfoliation and graphene‐nylon‐6 composite films

An effective method for the fabrication of graphene‐ZnO nanoparticle (GZN) composites has been developed. GZN composites with high electrical conductivity (18,607 S/m) are prepared in situ from graphite‐ZnO composites. The GZN composites also exhibit visible‐light absorption and enable the effective exfoliation of graphite. The presence of the ZnO nanoparticles assists the exfoliation of graphite and enables the preparation of solutions of highly dispersed and concentrated graphene sheets (2.7 mg/mL) that exhibit high electrical conductivity without reduction (40,404 S/m). A solution of graphene sheets was used to produce a graphene‐nylon‐6 film with an excellent Young's modulus (3 GPa) and a high tensile strength (109 MPa). An exclusive mechanism was proposed for the improvement of mechanical properties of the nylon‐6 composite film. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45034.     

Segregated highly conductive linear low-density polyethylene/graphene nanoplatelet composite through aqueous dispersing and self-leveling method

Construction of segregated structure is an effective way of preparing highly conductive composite. Here, we report an environmentally friendly method to prepare highly conductive linear low-density polyethylene/graphene nanoplatelets composite with segregated structure (s-LLDPE/GN) and low GN content. Firstly, GN coated LLDPE granules are prepared through aqueous dispersing and gradually drying. Then, the s-LLDPE/GN composites are obtained by melting and self-leveling without extra pressure. This method not only favors the forming of GN segregated network, but also allows certain fusing of the polymer at the interfaces that contribute to good mechanical strength of the composite. The electrical conductivity of the composite increases to 4.5 S/m when the GN content is 1.0 wt%. The composite with 0.5 wt% GN shows 10⁻¹ S/m electrical conductivity, and retains 82% of the tensile strength of pure LLDPE. The facile and green process in this method can be applied in many other polymer composites and show high potential for industrial application.     

Electrical ac and dc behavior of epoxy nanocomposites containing graphene oxide

This article deals with the investigation of electrical properties of epoxy‐based nanocomposites containing graphene oxide nanofillers dispersed in the polymer matrix through two‐phase extraction. Broadband dielectric spectroscopy and dc electrical conductivity as a function of electric field have been evaluated in specimens containing up to 0.5 wt % of nanofiller. Nanocomposites containing pristine graphene oxide do not show significant changes of electrical properties. On the contrary, the same materials after a proper thermal treatment at 135°C, able to provoke the in situ reduction of graphene oxide, exhibit higher permittivity and electrical conductivity, without showing large decrease of breakdown voltage. Moreover, a nonlinear behavior of the electrical conductivity is observed in the range of electric fields investigated, i.e. 2–30 kV mm^?1. A new relaxation phenomenon with a very low temperature dependence is also evidenced at high frequency in reduced graphene oxide composites, likely associated to induced polarization of electrically conductive nanoparticles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41923.     

In situ fast polymerization of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites

A series of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites (GNS/PMMA) is successfully prepared by an in situ fast polymerization method with graphene weight fractions from 0.1 to 2.0 wt %. In situ polymerization is effective in well dispersing of GNS in matrixes and suitable for both low and high content of GNS. The synthesis processes of polymer composites could be simplified and fast by using industrial grade graphene. The GNS fillers are found to disperse homogeneously in the PMMA matrix. The maximum electrical conductivity of the composites achieves 0.57 S m^?1, with an extremely low percolation threshold of 0.3 wt %. The electrical conductivities are further predicted by percolation theory and found to agree well with the experimental results. The results indicate that the microstructures, thermal, electrical, and mechanical properties of PMMA polymer are significantly improved by adding a low amount of graphene nanosheets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43423.     

Self-healable and reprocessible liquid crystalline elastomer and its highly thermal conductive composites by incorporating graphene via in-situ polymerization

The booming of modern electronic devices featuring increasing power and multi-functionalization demands novel high thermal conductive materials with various functions, such as self-healing property and high deformability, while traditional polymer-based or metallic-based materials could hardly provide. Therefore, we report a high thermal conductive and disulfide-based self-healable and reprocessible liquid crystalline elastomer (SHLCE) composite by incorporating graphene nanoplates (GNPs) fillers. The obtained GNPs/SHLCE composites exhibited desired thermal conductivity (5.08 Wm⁻¹ K⁻¹) when the content of GNPs was 20 wt% to the composites. Moreover, the GNPs/SHLCE composites showed intriguing recycled performance (Tensile strength after recycle could maintain over 93% compared with that of original composites). Furthermore, we concluded that the improved thermal conductivity of GNPs/SHLCE composites was beneficial to the thermal induced reprocessible and shelf-healable systems.