Preparation of low-density polyethylene/low-temperature expandable graphite composites with high thermal conductivity by an in situ expansion melt blending process

A facile strategy with the advantages of low cost and ease of mass production was presented to prepare low-density polyethylene (LDPE)/low-temperature expandable graphite (LTEG) composites with relatively high thermal conductivity by an in situ expansion melt blending process. LTEGs were expanded and delaminated into graphite multi-layers and graphite nanoplatelets during processing which synergistically created more thermo-conducting paths in the composites and hence led to great improvements in thermal conductivity. Thermal conductivity of the composite with 60 wt% of LTEG loading was increased by 23 times as compared to the pure LDPE, increasing from 0.47 to 11.28 W/mK. The incorporation of LTEG decreased the melting temperature and the degree of crystallinity of LDPE. Percolation threshold of both the electrical conductivity and rheological measurements was observed at about 8 vol% of LTEG loading. Moreover, the LDPE/LTEG composites showed better thermal stability compared to the pure LDPE.     

Fabrication and thermal conductivity of copper matrix composites reinforced with Mo2C or TiC coated graphite fibers

Graphite fiber reinforced Cu-based composites have good thermal conductivity, low coefficient of thermal expansion for heat sink applications. In these composites, the quality of interfacial bonding between the copper matrix and the graphite fibers has significant influence on the thermal properties of composites. In this study, two different carbide coatings (Mo₂C or TiC) were synthesized on graphite fiber to promote the interfacial bonding in composites. Fibers/Cu composites had been produced by spark plasma sintering process. The results showed that the densification, interfacial bonding and thermal conductivity of coated composites were improved distinctly compared to that of uncoated ones. The enhanced composites present 16–44% increase of thermal conductivity in X–Y plane. An original theoretical model was proposed to estimate the interface thermal resistance. The result showed that the interfacial thermal resistance was largely reduced by one order of magnitude with the introduction of carbide interlayer.     

High‐Performance Thermally Conductive Phase Change Composites by Large‐Size Oriented Graphite Sheets for Scalable Thermal Energy Harvesting

Efficient thermal energy harvesting using phase‐change materials (PCMs) has great potential for cost‐effective thermal management and energy storage applications. However, the low thermal conductivity of PCMs (K_PCM) is a long‐standing bottleneck for high‐power‐density energy harvesting. Although PCM‐based nanocomposites with an enhanced thermal conductivity can address this issue, achieving a higher K (>10 W m^?1 K^?1) at filler loadings below 50 wt% remains challenging. A strategy for synthesizing highly thermally conductive phase‐change composites (PCCs) by compression‐induced construction of large aligned graphite sheets inside PCCs is demonstrated. The millimeter‐sized graphite sheet consists of lateral van‐der‐Waals‐bonded and oriented graphite nanoplatelets at the micro/nanoscale, which together with a thin PCM layer between the sheets synergistically enhance K_PCM in the range of 4.4–35.0 W m^?1 K^?1 at graphite loadings below 40.0 wt%. The resulting PCCs also demonstrate homogeneity, no leakage, and superior phase change behavior, which can be easily engineered into devices for efficient thermal energy harvesting by coordinating the sheet orientation with the thermal transport direction. This method offers a promising route to high‐power‐density and low‐cost applications of PCMs in large‐scale thermal energy storage, thermal management of electronics, etc.     

高密度石墨泡沫及其石蜡复合材料的热物理性能(英文)

以中间相沥青和添加中间相炭微球的沥青为原料,调整发泡压力和发泡温度制备沥青泡沫,经1273K炭化和2973K石墨化,制备了高密度石墨泡沫。为了进一步提高石墨泡沫的密度,采用573 K的沥青反复浸渍炭化未添加中间相炭微球的沥青在1273K下所制的泡沫炭,再经2973K石墨化获得增密度后的石墨泡沫。而后制备了相应石墨泡沫/石蜡复合材料。研究了石墨泡沫热物理性能的影响因素和石墨泡沫/石蜡复合材料的热行为。研究表明:沥青组分、发泡温度和发泡压力决定了石墨泡沫的结构和热物理性能,而石墨泡沫的热导率决定了复合材料的热行为。与石蜡相比,石墨泡沫/石蜡复合材料的热扩散系数提高了768至1588倍。石墨泡沫/石蜡复合材料的潜热与石蜡的质量分数成正比。该复合材料是快速响应电子散热材料的良好选择。     

Enhanced conductivity behavior of polydimethylsiloxane (PDMS) hybrid composites containing exfoliated graphite nanoplatelets and carbon nanotubes

Polydimethylsiloxane (PDMS) hybrid composites consisting of exfoliated graphite nanoplatelets (xGnPs) and multiwalled carbon nanotubes functionalized with hydroxyl groups (MWCNTs-OH) were fabricated, and the effects of the xGnP/MWCNT-OH ratio on the thermal, electrical, and mechanical properties of polydimethylsiloxane (PDMS) hybrid composites were investigated. With the total filler content fixed at 4 wt%, a hybrid composite consisting of 75% × GnP/25% MWCNT-OH showed the highest thermal conductivity (0.392 W/m K) and electrical conductivity (1.24 × 10⁻³ S/m), which significantly exceeded the values shown by either of the respective single filler composites. The increased thermal and electrical conductivity found when both fillers are used in combination is attributed to the synergistic effect between the fillers that forms an interconnected hybrid network. In contrast, the various different combinations of the fillers only showed a modest effect on the mechanical behavior, thermal stability, and thermal expansion of the PDMS composite.     

兼具阻燃和导热性能的环氧树脂复合材料：石墨烯纳米片杂化三聚氰胺磷酸盐的作用

研发制备低成本、少缺陷及高效率的石墨烯纳米片杂化阻燃剂对实现复合材料多功能性具有重要意义。以三聚氰胺为助剥离剂将微粉石墨(GRA)经机械球磨后与磷酸液相反应得到一种阻燃导热的石墨烯纳米片杂化三聚氰胺磷酸盐(GMP),在表征GMP形貌、结构、组成和热稳定性的基础上,研究了添加GMP环氧树脂(EP)复合材料的阻燃、热分解和导热性能。GMP的热失重分析结果表明：与三聚氰胺磷酸盐(MP)相比,初始分解温度提升了29.3℃,与环氧树脂的热分解温度更匹配,有助于提高阻燃效率。氧指数仪、锥形量热仪和导热性能研究表明,GMP添加30wt%时,EP复合材料的极限氧指数达到了30.4%,UL 94垂直燃烧达到V-0级,峰值热释放速率(PHRR)和峰值烟释放速率(PSPR)分别下降69%和74.0%;导热系数提升至2.10 W·m^-1·K^-1,相对于EP提升了708%。这是由于GMP中石墨烯纳米片(GNPs)与MP的相互作用促进了EP形成了致密的膨胀炭层,有效提高了EP复合材料的阻燃性;随着GMP添加量的增加,GNPs和石墨微片传热通道的形成改善了EP复合材料的导...     

Silica coating onto graphene for improving thermal conductivity and electrical insulation of graphene/polydimethylsiloxane nanocomposites

Graphene possess extremely high thermal conductivity, and they have been regarded as prominent candidates to be used in thermal management of electronic devices. However, addition of graphene inevitably causes dramatic decrease in electrical insulation, which is generally unacceptable for thermal interface materials(TIMs) in real electronic industry. Developing graphene-based nanocomposites with high thermal conductivity and satisfactory electrical insulation is still a challenging issue. In this study,we developed a novel hybrid nanocomposite by incorporating silica-coated graphene nanoplatelets(Silica@GNPs) with polydimethylsiloxane(PDMS) matrix. The obtained Silica@GNP/PDMS composites showed satisfactory electrical insulation(electrical resistivity of over 10~(13)Ωcm) and high thermal conductivity of 0.497 W m-1K-1, increasing by 155% compared with that of neat PDMS, even higher than that of GNP/PDMS composites. Such high thermal conductivity and satisfactory electrical insulation is mainly attributed to the insulating silica-coating, good compatibility between components, strong interfacial bonding, uniform dispersion, and high-efficiency heat transport pathways. There is great potential for the Silica@GNP/PDMS composites to be used as high-performance TIMs in electronic industry.     

A new heat transfer model of inorganic particulate-filled polymer composites

Thermal conductivity is an important parameter for characterization of thermal properties of materials. Various complicated factors affect the thermal conductivity of inorganic particulate-filled polymer composites. The heat transfer process and mechanisms in an inorganic particulate-filled polymer composite were analyzed in this article. A new theoretical model of heat transfer in these composites was established based on the law of minimal thermal resistance and the equal law of the specific equivalent thermal conductivity, and an relevant equation of effective thermal conductivity (K _eff) for describing a relationship between K _eff and filler volume fraction as well as other thermal parameters were derived based on this model. The values of K _eff of aluminum powder-filled phenol–aldehyde composites and graphite powder-filled phenol–aldehyde composites were estimated by using this equation, and the calculations were compared with the experimental measured data from these composites with filler volume fraction from 0 to 50% in temperature range of 50–60 °C and the predictions by Maxwell–Eucken equation and Russell equation. The results showed that the predictions of the K _eff by this equation were closer to the measured data of these composites than the other equations proposed in literature.     

Thermally conductive polyamide 6/carbon filler composites based on a hybrid filler system

Abstract

We explored the use of a hybrid filler consisting of graphite nanoplatelets (GNPs) and single walled carbon nanotubes (SWCNTs) in a polyamide 6 (PA 6) matrix. The composites containing PA 6, powdered GNP, and SWCNT were melt-processed and the effect of filler content in the single filler and hybrid filler systems on the thermal conductivity of the composites was examined. The thermal diffusivities of the composites were measured by the standard laser flash method. Composites containing the hybrid filler system showed enhanced thermal conductivity with values as high as 8.8 W (m · K)^?1, which is a 35-fold increase compared to the thermal conductivity of pure PA 6. Thermographic images of heat conduction and heat release behaviors were consistent with the thermal conductivity results, and showed rapid temperature jumps and drops, respectively, for the composites. A composite model based on the Lewis–Nielsen theory was developed to treat GNP and SWCNT as two separate types of fillers. Two approaches, the additive and multiplicative approaches, give rather good quantitative agreement between the predicted values of thermal conductivity and those measured experimentally.     

In-plane thermal enhancement behaviors of Al matrix composites with oriented graphite flake alignment

Oriented graphite flakes (G_f)/Si/Al composites were fabricated to study their thermal enhancement behaviors. The in-plane thermal conductivity (TC) of the composites increases with the increase of G_f volume fraction. At a given volume fraction, a larger G_f size can achieve a higher in-plane TC of the composites. Microstructural characterization revealed a clean and Al₄C₃-free interface between the side surface of G_f and the Al matrix. Based on the observed microstructures, an analytical model was presented to predict the in-plane TC of the composites with oriented G_f alignment by incorporating interfacial thermal resistance within the framework of effective medium approach (EMA). Comparisons of the present model predictions with the experimental data of the as-fabricated G_f/Si/Al and previously reported G_f/Al and G_f/polymer (polyvinyl butyral, PVB) composites show good agreement. The results indicate that our model can well predict the in-plane thermal enhancement behaviors of the composites at different effective phase contrasts (i.e. the ratio between effective TC of the G_f and TC of the matrix).     

Thermal conductivity of diamond/Ag composites with chromium carbide coated diamonds for the building materials of high power modules

Abstract

This paper reports on a study of the preparation and characterisation of diamond/Ag composites for the building materials of high power modules. The Cr₇C₃ coated diamond particles are utilised to improve the interfacial bonding between the Ag and diamond and composites are prepared by hot pressing technique. The characteristics of Cr₇C₃ coating layers were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that the Cr₇C₃ coatings on the diamonds result in a strong interfacial bonding and a greatly enhanced thermal conductivity of the composites. A largely enhanced thermal conductivity of 768 W m^?1 K^?1 is obtained in Cr₇C₃ coated composites, which increases 168% relative to that of uncoated composites at 65% diamond volume fraction. The measured thermal conductivity agrees reasonably well with the predictions by a differential effective-medium (DEM) model.     

Thermally conductive polyamide 6/carbon filler composites based on a hybrid filler system

We explored the use of a hybrid filler consisting of graphite nanoplatelets (GNPs) and single walled carbon nanotubes (SWCNTs) in a polyamide 6 (PA 6) matrix. The composites containing PA 6, powdered GNP, and SWCNT were melt-processed and the effect of filler content in the single filler and hybrid filler systems on the thermal conductivity of the composites was examined. The thermal diffusivities of the composites were measured by the standard laser flash method. Composites containing the hybrid filler system showed enhanced thermal conductivity with values as high as 8.8 W (m · K)⁻¹, which is a 35-fold increase compared to the thermal conductivity of pure PA 6. Thermographic images of heat conduction and heat release behaviors were consistent with the thermal conductivity results, and showed rapid temperature jumps and drops, respectively, for the composites. A composite model based on the Lewis–Nielsen theory was developed to treat GNP and SWCNT as two separate types of fillers. Two approaches, the additive and multiplicative approaches, give rather good quantitative agreement between the predicted values of thermal conductivity and those measured experimentally.     

纳米石墨片-羧基丁腈橡胶复合材料结构形态与电性能

利用电子束辐照法制备纳米石墨片(GnPs)-羧基丁腈橡胶(XNBR)复合材料,研究辐射剂量对胶乳共混体系稳定性的影响,并对GnPs-XNBR复合材料的交联度、热稳定性、电性能及其形貌予以表征。结果表明:辐照后GnPs-XNBR复合材料的交联度、热稳定性和体积电阻率提高,而共混乳液的稳定性显著降低。辐照强化了乳胶粒子与石墨片之间的界面结合,形成胶乳粒子包覆石墨片的核-壳结构,进而提高石墨片在基体中分散均匀性,并使GnPs-XNBR复合材料的热稳定性和介电常数提高,导电性和介电损耗降低。     

Thermal Conductivity of High-Temperature Multicomponent Materials with Phase Change

This work focuses on the investigation of the effective thermal conductivity (λ_eff) of heterogeneous materials consisting of a phase change material (PCM) and expanded graphite (EG). These composites may be employed in latent heat storage systems, where a PCM stores energy by being heated to a temperature higher than its melting point (T _m), and releases it during solidification. For the determination of λ_eff, the steady-state comparative method was used and modified to measure composite samples at temperatures above T _m. Results were compared with the thermal conductivity of the pure PCMs, and a significant increase could be observed. The dependence of λ_eff on temperature, as well as the influence of the material microstructure on the enhancement of λ_eff, were examined. Paper presented at the Seventeenth European Conference on Thermophysical Properties, September 5–8, 2005, Bratislava, Slovak Republic.     

Fabrication,interface characterization and modeling of oriented graphite flakes/Si/Al composites for thermal management applications

Highly thermally conductive graphite flakes (G_f)/Si/Al composites have been fabricated using G_f, Si powder and an AlSi₇Mg_0.3 alloy by an optimized pressure infiltration process for thermal management applications. In the composites, the layers of G_f were spaced apart by Si particles and oriented perpendicular to the pressing direction, which offered the opportunity to tailor the thermal conductivity (TC) and coefficient of thermal expansion (CTE) of the composites. Microstructural characterization revealed that the formation of a clean and tightly-adhered interface at the nanoscale between the side surface of the G_f and Al matrix, devoid of a detrimental Al₄C₃ phase and a reacted amorphous Al–Si–O–C layer, contributed to excellent thermal performance along the alignment direction. With increasing volume fraction of G_f from 13.7 to 71.1 vol.%, the longitudinal (i.e. parallel to the graphite layers) TC of the composites increased from 179 to 526 W/m K, while the longitudinal CTE decreased from 12.1 to 7.3 ppm/K (matching the values of electronic components). Furthermore, the modified layers-in-parallel model better fitted the longitudinal TC data than the layers-in-parallel model and confirmed that the clean and tightly-adhered interface is favorable for the enhanced longitudinal TC.     

Effect of chromium carbide coating on thermal properties of short graphite fiber/Al composites

A chromium carbide coating was synthesized onto graphite fibers by molten salts method to improve the interfacial bonding and thermal properties of short graphite fiber/Al composites which were fabricated by vacuum pressure infiltration technique. The graphite fiber/Al composites with different thicknesses of chromium carbide coatings were prepared through varying plating times to investigate the influence of chromium carbide layer on the microstructures and thermal properties of the composites. The combined Maxwell–Garnett effective medium approach and acoustic mismatch model schemes were used to theoretically predict thermal conductivities of the composites. The results indicated that the chromium carbide coating formed on graphite fiber surface in molten salts consists mainly of the Cr₇C₃ phase. The Cr₇C₃-coating layer with plating time of 60 min and thickness of 0.5 μm was found to be most effective in improving the interfacial bonding and decreasing the interfacial thermal resistance between graphite fiber and aluminum matrix. The 40 vol% Cr₇C₃-coated graphite fiber/Al composite with Cr₇C₃ thickness of 0.5 μm exhibited 45.4 % enhancement in in-plane thermal conductivity of 221 W m^?1 K^?1 compared to that of uncoated composite, as well as the coefficient of thermal expansion of 9.4 × 10^?6 K^?1, which made it as very interesting material for thermal management applications.     

Interfacial microstructure and its effect on thermal conductivity of SiCp/Cu composites

Thermal conductivity of SiCp/Cu composites was usually far below the expectation, which is usually attributed to the low real thermal conductivity of matrix. In the present work, highly pure Cu matrix composites reinforced with acid washed SiC particles were prepared by the pressure infiltration method. The interfacial microstructure of SiCp/Cu composites was characterized by layered interfacial products, including un-reacted SiC particles, a Cu–Si layer, a polycrystalline C layer and Cu–Si matrix. However, no Cu₃Si was found in the present work, which is evidence for the hypothesis that the formation of Cu₃Si phase in SiC/Cu system might be related to the alloying elements in Cu matrix and residual Si in SiC particles. The thermal conductivity of SiCp/Cu composites was slightly increased with the particle size from 69.9 to 78.6 W/(m K). Due to high density defects, the real thermal conductivity of Cu matrix calculated by H–J model was only about 70 W/(m K). The significant decrease in thermal conductivity of Cu matrix is an important factor for the low thermal conductivity of SiCp/Cu composites. However, even considered the significant decrease of thermal conductivity of Cu matrix, theoretical values of SiCp/Cu composites calculated by H–J model were still higher than the experimental results. Therefore, an ideal particle was introduced in the present work to evaluate the effect of interfacial thermal resistance. The reverse-deduced effective thermal conductivities of ideal particles according to H–J model was about 80 W/(m K). Therefore, severe interfacial reaction in SiCp/Cu composites also leads to the low thermal conductivity of SiCp/Cu composites.     

Preparation and thermal properties of zirconium tungstate/copper composites

ZrW₂O₈/Cu composites were prepared by the powder metallurgy method. Electroless plating was used to deposit copper on ZrW₂O₈ powder before sintering. The thermal expansion and thermal conductivity of composites were measured in the temperature range from 25 ^oC to 200 ^oC and compared with those predicted from various theoretical models. The results show that the coefficient of thermal expansion of ZrW₂O₈/ Cu composites with a different volume fraction of ZrW₂O₈ is greater than the theoretically calculated value. The thermal conductivities of ZrW₂O₈/ Cu composites increase with a higher copper content and decrease upon elevated temperature. The thermal conductivity of composites with a different volume fraction of ZrW₂O₈ is lower than the theoretically calculated value.     

粘结剂含量对石墨材料电、热传导性能的影响

以煅后石油焦和煤沥青为基本原料，采用热压工艺制备了一系列石墨材料。考察了粘结剂含量对石墨材料电、热传导性能的影响。在实验基础上，阐明了粘结剂与骨料颗粒在热混捏与热压过程中相互作用原理。结果表明，石墨材料的传导性能不仅依赖于原料种类、粒度，而且与其质量百分配比也有关系。经过分析认为，粘结剂含量小于25W／％时，随着粘结剂含量的增加，石墨材料传导性能增强的原因可归结为石墨材料的骨料颗粒气孔率得到降低和颗粒间微裂纹减少所致；而粘结剂含量超过25W／％时，材料的传导性能随着粘结剂含量的增加而降低的原因可归结为骨料颗粒间粘结剂的γ组分以气态形式挥发使得材料气孔率增加所致。     

一维高导热C/C复合材料的制备研究

以三种沥青作为基体前驱体, 实验室自制的AR中间相沥青基纤维为增强体, 通过500℃热压成型, 随后经炭化和石墨化处理制备出一维炭/炭(C/C)复合材料。研究了前驱体沥青种类和热处理温度对复合材料导热性能的影响, 并采用扫描电子显微镜和偏光显微镜对其石墨化样品的形貌和微观结构进行表征。结果表明; C/C复合材料在沿纤维轴向的室温热扩散系数和导热率均随热处理温度的升高而逐渐增大; 由AR沥青作为基体前驱体所制备的C/C复合材料具有更加明显的沿纤维轴向取向的石墨层状结构以及最好的导热性能, 其3000℃石墨化样品沿纤维轴向的室温热扩散系数和导热率分别达到594.5 mm²/s和734.4 W/(m·K)。