Improved thermal conductivity for chemically functionalized exfoliated graphite/epoxy composites

Chemically functionalized exfoliated graphite-filled epoxy composites were prepared with load levels from 2% to 20% by weight. The viscosities of the composites having load levels >4% by weight were over the processing window for the vacuum-assisted resin transfer molding process. Wide-angle X-ray diffraction revealed a rhombohedral carbon structure in the filler. Enhanced interaction between the epoxy and the graphite filler was evidenced by an improvement in the rubber modulus for the chemically functionalized graphite/epoxy composites. The thermal and electrical properties of the nanoparticle-filled epoxy composites were measured. The electrical property of the chemically functionalized graphite/epoxy composite deteriorated. Thermal conductivity of the chemically functionalized graphite/epoxy composite, however, increased by 28-fold over the pure epoxy resin at the 20% by-weight load level, increasing from 0.2 to 5.8 W/m K.     

0D surface modification and 3D silicon carbide network construction for improving the thermal conductivity of epoxy resins

With rapid advances in electronic device miniaturization and increasing power density, high thermal conductivity polymer composites with excellent properties are becoming increasingly significant for the progress of next-generation electronic apparatuses. In this work, a new type of three-dimensional (3D) network silicon carbide (SiC) frame and core-shell SiC@SiO₂ (SiC@SiO₂) were successfully prepared. The effects of different filler forms (dispersed particle filler and three-dimensional continuous filler network) on the thermal conductivity of the composites were compared. The composites based on the three-dimensional filler network exhibited evidently better thermal conductivity improvement rates, compared to their traditional counterparts. The thermal conductivity of the epoxy/SiC@SiO₂ composite having a total filler content of 17.0 vol% was 0.857 W/m/K, 328.5% higher than that of pure epoxy resin. Similarly, the thermal conductivity of the EP/3D-SiC composite having a total filler content of 13.8 vol% was 1.032 W/m/K, 416.0% higher than that of pure epoxy resin. The abovementioned stats were proven via molecular simulations. We estimated the interfacial thermal resistance (ITR) of the EP/3D-SiC composite to be 5.98 × 10^?8 m² K/W, which was an order of magnitude lower than that of the epoxy composites without a 3D network. Simultaneously, computerized molecular simulation technology was used to verify the feasibility of the experiment, which provided new ideas for the preparation of other highly thermally conductive materials.     

Thermally Conductive General-Purpose Polystyrene (GPPS)/Graphite Composite with a Segregated Structure: Effect of Size of Resin and Graphite Flakes

General-purpose polystyrene (GPPS)/graphite flake composites with a segregated structure were fabricated by newly developed binder mixing method, aiming at highly thermally conductive polymer composites. The coefficient of thermal conductivity of the GPPS/graphite composites can be easily improved to be 3.5?W?m^?1?k^?1 at a graphite flakes loading of 24.7?vol%, showing an improvement of more than 2,000% compared with pure GPPS. The thermal conductivity of the composites increased with the increasing particle size of graphite flakes, while the mechanical properties of composites are decreased with the increasing particle size of GPPS resin particles.     

Synthesis of silica-coated graphite by enolization of polyvinylpyrrolidone and its thermal and electrical conductivity in polymer composites

Silica-coated graphite flakes, which have electrical insulating property and high thermal conductivity, were synthesized by a polyvinylpyrrolidone (PVP)-assisted sol–gel reaction. The critical role of keto-enol tautomerism of PVP in base-catalyzed silica sol–gel reaction was elucidated. The degree of silica coating on graphite was controlled by the amount of PVP and silica precursor, tetraethyl orthosilicate. The silica-coated graphite was used as a filler in thermoplastic polyester elastomer (TPEE). The in-plane (Λ) and through-plane (Λ_⊥) thermal conductivity values of silica-coated graphite/TPEE composites are 67.5% and 86.6% of those of raw graphite/TPEE at 80 phr loading. Even after a severe mixing process under high shear at elevated temperature, silica-coated graphite/TPEE composites retain the perfectly insulating surface resistivity of >10¹³ Ω/sq up to high filler contents.     

Synergistic effects of multiple carbon fillers on the rheology of liquid crystal polymer based resins

Adding conductive carbon fillers to insulating thermoplastic resin increases composite electrical and thermal conductivity. Often, as much of a single type of carbon filler is added to achieve the desired conductivity, while still allowing the material to be molded into a bipolar plate for a fuel cell. In this study, varying amounts of three different carbons (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX liquid crystal polymer. The rheology of resulting single filler composites was tested. In addition, the rheological properties of composites containing combinations of two different carbon fillers were studied via a factorial design. In all cases, viscosity increased with increasing filler volume fraction for all shear rates. Over the range of shear rates studied, the viscosity followed a shear‐thinning power law model. The factorial design results indicated that each of the single fillers and all of the two filler combinations caused a statistically significant increase in composite viscosity at a shear rate of 1,000 s⁻¹. The composites containing carbon black and synthetic graphite caused the largest increase in viscosity. It is possible that the highly branched, high surface area structure of carbon black ‘links’ with the synthetic graphite particles, which results in increased composite viscosity. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

石墨填充PP-HDPE复合材料的电性能研究

采用聚丙烯(PP)和高密度聚乙烯（HDPE）共混物为基体材料,以石墨为导电填料, 通过熔融共混法制备了导电复合材料。重点研究了石墨在两相基体中的分散情况以及复合体系的电学性能。扫描电镜测试结果表明:石墨粒子选择性的分散在共混物基体中,构成双渗流导电网络结构。电性能测试结果显示:在相同石墨含量下双基体体系的室温电阻率与GP/HDPE相比下降了1～4个数量级。同时,双渗流导电网络结构的存在部分消除了负温度系数（NTC）效应, 提高了热循环稳定性。     

Preparation of Si–diamond–SiC composites by in-situ reactive sintering and their thermal properties

This article described a novel method of preparation of Si–diamond–SiC composites by in-situ reactive spark plasma sintering (SPS) process. The relative packing density of Si–diamond–SiC composite was 98.5% or higher in a volume fraction range of diamond between 20% and 60%. Si–diamond–SiC composites containing 60 vol% diamond particles yielded a thermal conductivity of 392 W/m K, higher than 95% the theoretical thermal conductivity calculated by Maxwell–Eucken's equation. Coefficients of thermal expansion (CTEs) of the composites are lower than the values of theoretical models, indicating strong bonding between the diamond particle and the Si matrix in the composite. The microstructures of these materials were studied by field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD). As a result of reaction between diamond and silicon, SiC phase formed.     

Effects of carbon fillers on the rheology of highly filled liquid‐crystal polymer based resins

Adding conductive carbon fillers to insulating resins increases the composite electrical and thermal conductivity. Often, enough of a single type of carbon filler is added to achieve the desired conductivity while still allowing the material to be molded into a bipolar plate for a fuel cell. In this study, various amounts of three different carbons (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX liquid‐crystal polymer. The rheological properties of the resulting single‐filler composites were measured. In addition, the rheological properties of composites containing combinations of different carbon fillers were studied via a factorial design. In all cases, the viscosity increased with increasing filler volume fraction and followed a shear‐thinning power‐law model. The factorial design results indicated that each of the single fillers and all the filler combinations caused a statistically significant increase in the composite viscosity when compared at a shear rate of 500 s^?1 or at a stress of 10⁵ Pa. For composites containing synthetic graphite particles and/or carbon fiber, the viscosity variation with the volume fraction of carbon followed a modified Maron–Pierce equation. When compared at a constant volume fraction of carbon, composites containing carbon black showed viscosity enhancement above and beyond that shown by the other composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

BN填充PA6基导热绝缘复合材料导热性能研究

以聚酰胺6（PA6）为基体, 氮化硼（BN）作为导热填料,经双螺杆挤出机熔融共混,模压成型制得导热绝缘复合材料。研究了BN含量、粒径、形状和不同BN粒径复配对复合材料导热性能的影响,并研究了BN含量和粒径对复合材料绝缘性能的影响。结果表明,在各种粒径下,复合材料热导率均随BN填充量的增加而增大;在BN粒径为5 μm、填充量为25 %（体积分数,下同）时,复合材料热导率达到1.2187 W/(m·K);在BN填充量相同时,填料粒径对复合材料热导率的影响不是简单的单调规律,呈现50、100 μm时较小,1、5、15 μm时较大,150 μm时最大的规律;片状BN填料比球状BN填料更有利于提高复合材料的热导率;2种不同粒径填料复配所填充的复合材料的热导率大于单一粒径填充的复合材料;5 μm与150 μm粒径BN复配,在填充量为20 %,配比为1:3时,复合材料的热导率最大,达到1.3753 W/(m·K),为纯PA6的4.9倍;在不同BN含量和粒径下,复合材料体积电阻率均能达到10000000000000 Ω·cm以上,满足绝缘性能。     

Effects of flake graphite on property optimisation in thermal conductive composites based on polyamide 66

In this study, in order to improve the thermal conductivity of polyamide 66(PA66), PA66 composites filled with flake graphite (FG) were prepared by twin-screw extruder. Effects of filler content, particle size and particle size mixing on thermal conductivity, mechanical and rheological properties of the composites were investigated. The results showed that as FG content increased from 0 to 50 wt-%, thermal conductivity of the composites filled with 100 μm FG gradually increased, whereas mechanical properties and rheological properties decreased. At 50 wt-% loading, thermal conductivity reached 3.07 W/(m K). With the increase of particle size, thermal conductivity and rheological properties of the composites improved, but mechanical properties increased first and then decreased. The composite filled with 100 μm FG had relatively optimal mechanical properties. Particle size mixing can improve thermal conductivity and the maximum value was achieved in the 1:2 mass ratio of 20 and 100 μm particles.     

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.     

Thermal and mechanical properties of graphite foam/Wood’s alloy composite for thermal energy storage

Thermal and mechanical properties of graphite foam/Wood’s alloy (50Bi/27Pb/13Sn/10Cd) composites for thermal energy storage were investigated. As compared with the alloy and graphite foam, thermal conductivity of the composites (193.74 W/mK) increased 2 times. Significant reduction in coefficient of thermal expansion of the composite compared with that of the alloy (7.82 vs. 24.81 ppm/K) was obtained. The latent heat of the composite remained very close to the value of the alloy alone. Moreover, alloy filled into graphite foam enhanced the mechanical properties of the graphite foam both in the solid phase and melting phase.     

Polymer composites with enhanced thermal conductivity via oriented boron nitride and alumina hybrid fillers assisted by 3-D printing

Herein, oriented boron nitride (BN)/alumina (Al₂O₃)/polydimethylsiloxane (PDMS) composites were obtained by filler orientation due to the shear-inducing effect via 3-D printing. The oriented BN platelets acted as a rapid highway for heat transfer in the matrix and resulted in a significant increase in the thermal conductivity along the orientation direction. Extra addition of spherical Al₂O₃ enhanced the fillers networks and resulted in the dramatic growth of slurry viscosity. This, together with filler orientation induced the synergism and provided large increases in the thermal conductivity. A high orientation degree of 90.65% and in-plane thermal conductivity of 3.64 W/(m∙K) were realized in the composites with oriented 35 wt% BN and 30 wt% Al₂O₃ hybrid fillers. We attributed the influence of filler orientation and hybrid fillers on the thermal conductivity to the decrease of thermal interface resistance of composites and proposed possible theoretical models for the thermal conductivity enhancement mechanisms.     

Nano- and microstructural effects on thermal properties of poly (l-lactide)/multi-wall carbon nanotube composites

In this work the thermal properties of poly (l-lactide)/multi-wall carbon nanotube (PLLA/MWCNT) composites have been investigated. Thermal conductivity was determined after measuring specific heat capacity (C_p), thermal diffusivity (D) and bulk density (ρ) of composites. Thermal conductivity rises up to 0.345 W/m K at 5 wt.% after reaching a minimum value of about 0.12 W/m K at 0.75 wt.%. In order to understand the heat-conduction process, experimentally obtained thermal conductivities were fitted to an existing theoretical model. The much lower thermal conductivity of composites compared with the value estimated from the intrinsic thermal conductivity of the nanotubes and their volume fraction could be explained in terms of the obtained large thermal resistance (R_k) of 1.8 ± 0.3 × 10^?8 m² K/W at nanotube–matrix interface. The CNT dispersion in the composites was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Although the thermal resistance dramatically reduces the estimated bulk thermal conductivity of composites, the existence of an interconnected conductive nanotube network for thermal diffusion in PLLA/MWCNT composites demonstrates that the addition of carbon nanotubes represents an efficient strategy in order to successfully enhance the thermal conductivity of insulator polymers.     

Formation of SiC whiskers/leucite-based ceramic composites from low temperature hardening geopolymer

In this study, SiC whiskers (SCWS) reinforced geopolymer composites (SCWS/KGP) and their ceramic products (SCWS/leucite) were prepared, and effects of SiC whiskers contents on the microstructure and flexural strength of the SCWS/KGP and SCWS/leucite composites were investigated. The results show that the whisker addition has little influence on both phase composition and thermal shrinkage of the KGP composites, but a suitable content of whisker will result in the improved flexural strength, and when the SCWS content is 2 wt%, flexural strength of the SCWS/KGP composite is enhanced by 95% compared with the neat geopolymer. The flexural strength of the composites can be further enhanced significantly after the composites being treated at 1100 °C and 1200 °C and flexural strength of the composite with SCWS content of 2 wt% was 107% and 125% higher than the untreated counterpart, respectively. The increase in flexural strength of the composites should be attributed to the strong leucite formation, whisker debonding and pulling out from matrix during the fracturing process based on the good interfacial bonding state between whisker and leucite matrix.     

Bimodal distribution of filler on viscosity and thermal expansion of glass composites

This paper investigates the bimodal oxide filler system to study the viscous behavior and thermal expansion properties of glass composites. Zinc oxide and cordierite, which are two types of filler, with different average diameters (10 μm and 1 μm, respectively), were considered in a Bi2O3 containing glass with various volume fractions (up to 40 vol%). The experimental results for the composites with the bimodal filler distribution show a reduced viscosity. The viscosity increased from fine particles to coarse particles with an increase in the volume fraction of the composite. Both viscosity and coefficient of thermal expansion (CTE) decreased significantly in the composite with the cordierite filler. The CTE is determined from the volume fraction with respect to particle size and distribution. On the other hand, viscosity is dependent on the particle distribution, particle size, and volume fraction of the composite.     

Improvement in thermal conductivity and mechanical properties of ethylene‐propylene–diene monomer rubber by expanded graphite

Thermally conductive fillers are usually employed in the preparation of rubber composites to enhance thermal conductivity. In this work, ethylene‐propylene‐diene monomer rubber (EPDM)/expanded graphite (EG) and EPDM/graphite composites with up to 100 phr filler loading were prepared. Compared to EPDM/graphite compounds with the same filler loading, stronger filler network was demonstrated for EPDM/EG compounds. Thermal conductivity and mechanical properties of EPDM/graphite and EPDM/EG composites were compared and systematically investigated as a function of the filler loading. The thermal conductivity of both EPDM/graphite and EPDM/EG composites increased with increasing volume fraction of fillers, and could be well fitted by Geometric Mean Model. The thermal conductivity as high as 0.910 W · m⁻¹ · K⁻¹ was achieved for the EPDM/EG composite with 25.8 vol% EG, which was ∼4.5 times that of unfilled EPDM. Compared to EPDM/graphite composites, EPDM/EG composites exhibited much more significant improvement in thermal conductivity and mechanical properties, which could be well correlated with the better filler‐matrix interfacial compatibility and denser structure in EPDM/EG composites, as revealed in the SEM images of tensile fracture surfaces. POLYM. COMPOS., 38:870–876, 2017. © 2015 Society of Plastics Engineers     

Dielectric properties of epoxy/graphite flakes composites: Influence of loading and surface treatment

Epoxy-rich carbon-based composites are well recognized materials in industries owing to their good mechanical properties and thermal stability. Here, dielectric properties of composites based on bisphenol-A-epoxy resin loaded with 5, 6, 10, and 15 wt% of graphite flakes (GF) have been studied. The frequency and temperature dependence of the dielectric permittivity, dielectric loss, and ac conductivity have been examined in temperature (−103 to 97°C) and frequency (20 Hz–200 kHz) range. Influence of the filler surface chemistry have been studied for composites loaded with 5 wt% GF obtained: (i) under wet milling, without or with adding Triton-100x as a surfactant, or (ii) under dry milling in the presence of KOH. The composite made of epoxy loaded with 5 wt% exfoliated expanded graphite flakes (EEG), was also prepared. The surface treatment with KOH notably increased dielectric constant of the composite, keeping low dielectric loss, while treatment with Triton-100x significantly increased tanδ. The composite loaded with exfoliated expanded graphite shows higher ac conductivity than those obtained with flaky graphite, GF. Possibility to change dielectric properties of the composites without changing the loading content can be used as an approach in tailoring one with desired dielectric properties.     

Densification and toughening mechanisms in spark plasma sintered ZrB2-based composites with zirconium and graphite additives

The densification behavior and toughening mechanisms of ZrB₂-based composites with in-situ formed ZrC were investigated. The composites were spark plasma sintered at 1700 °C for 7 min under the applied pressure of 40 MPa. Metallic zirconium and graphite flakes were used as precursors to achieve ZrC reinforcement. Microstructural and phase analyses as well as mechanical characterizations were carried out on the near fully-dense composite samples. Results indicated ZrC as the only secondary phase in composite with 5 vol% of metallic Zr and graphite flakes. However, higher volume fractions of precursor materials led to the formation of ZrO₂ as the dominant secondary phase. Whereas decreasing trend of the hardness number versus volume fraction of the precursors was observed, the highest indentation fracture toughness was achieved in sample with 15 vol% metallic Zr/graphite flakes. Finally, the formation of secondary phases and their effects on densification, and mechanical behavior of the composites were discussed.