Effect of processing technique on the transport and mechanical properties of graphite nanoplatelet/rubbery epoxy composites for thermal interface applications

Graphite nanoplatelet (GNP)/rubbery epoxy composites were fabricated by mechanical mixer (MM) and dual asymmetric centrifuge speed mixer (SM). The properties of the GNP/rubbery epoxy were compared with GNP/glassy epoxy composites. The thermal conductivity of GNP/rubbery epoxy composite (25 wt.% GNP, particle size 15 μm) reached 2.35 W m⁻¹ K⁻¹ compared to 0.1795 W m⁻¹ K⁻¹ for rubbery epoxy. Compared with GNP/rubbery epoxy composite, at 20 wt.%, GNP/glassy epoxy composite has a slightly lower thermal conductivity but an electrical conductivity that is 3 orders of magnitude higher. The viscosity of rubbery epoxy is 4 times lower than that of glassy epoxy and thus allows higher loading. The thermal and electrical conductivities of composites produced by MM are slightly higher than those produced by SM due to greater shearing of GNPs in MM, which results in better dispersed GNPs. Compression and hardness testing showed that GNPs increase the compressive strength of rubbery epoxy ∼2 times without significantly affecting the compressive strain and hardness. The GNP/glassy epoxy composites are 40 times stiffer than the GNP/rubbery epoxy composites. GNP/rubbery epoxy composites with their high thermal conductivity, low electrical conductivity, low viscosity before curing and high conformability are promising thermal interface materials.     

Comparison of carbon nanofiller-based polymer composite adhesives and pastes for thermal interface applications

Graphite nanoplatelets (GNP), carbon black (CB) and carbon nanotubes are extensively researched to produce thermal interface materials (TIMs). This work reports comparison of interfacial thermal conductance (ITC) of carbon nanofiller-based polymer composite adhesives and pastes. The results show that total thermal contact resistance (TTCR) of GNP/rubbery epoxy composite was the same as that of an equivalent glassy epoxy composite. Although CB-based rubbery epoxy and silicone composites can be applied as thin bondlines, their TTCRs were significantly higher than GNP/rubbery epoxy. GNP incorporation into CB/rubbery epoxy composite improves the ITC of the CB/rubbery epoxy composites but the performance of CB/GNP/rubbery epoxy was inferior to GNP/rubbery epoxy. The thermal paste of GNP/polyetheramine had TTCR of 4.8 × 10^− 6 m²·K/W which is comparable to commercial TIM-paste. The paste produced with silicone had relatively poor ITC versus that prepared with polyetheramine. The paste having smaller particle sized GNPs offers lower TTCR than that prepared with large sized GNPs. The GNP/rubbery epoxy adhesives produced from precursor pastes gave the lowest TTCRs in comparison with the other adhesives. This study suggests that GNPs offer potential for enhancing ITC of TIMs and that ITC of adhesives depends on fillers' thermal conductivity and their interfacial contact with substrates.     

Thermal and electrical conductivity of Al(OH)<Subscript>3</Subscript> covered graphene oxide nanosheet/epoxy composites

Al(OH)₃ functionalized graphene composites (Al–GO) were prepared using a simple sol–gel method. In this protocol, graphene oxide (GO) was prepared according to the Hummers method and functionalized to enhance its reactivity with aluminum isopropoxide by a LiAlH₄ treatment. The functionalized graphene sheets were characterized by X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy. These analyses confirmed that GO had been fabricated and the Al(OH)₃ layer could have a homogeneous distribution with large and dense coverage onto GO sheets. In addition, the thermal and electrical conductivity of the epoxy composites with GO and Al–GO fillers were measured. The thermal conductivities of the composites with graphene-based fillers were enhanced by the addition of fillers. In particular, the thermal conductivity of GO/epoxy composite containing 3 wt% was approximately two times higher than that of pure epoxy resin. In addition, the electrical conductivity of Al–GO embedded composites degenerated compared to GO composites.     

Fabrication and properties of CNTs/carbon fabric hybrid multiscale composites processed via resin transfer molding technique

Carbon nanotubes (CNTs) are effective fillers/reinforcements regarding improving the properties of polymer. In the present paper, carboxylic acid functionalized CNTs were used to modify epoxy with intent to develop a nanocomposite matrix for hybrid multiscale composites combining benefits of nanoscale reinforcement with well-established fibrous composites. CNTs were dispersed in epoxy by using high energy sonication. At low contents of CNTs, hybrid multiscale composites specimens were manufactured via resin transfer molding (RTM) process. The processibility of CNTs/epoxy systems was explored with respect to their viscosity. The dispersion quality and re-agglomeration behavior of CNTs in epoxy were characterized using optical microscope. A CNTs loading of 0.025 wt% significantly improved the glass transition temperatures (Tg) of the hybrid multiscale composites. Scanning electron microscopy (SEM) was used to examine the fracture surface of the failed specimens. It is demonstrated that the addition of small amount of CNTs (0.025 wt%) to epoxy for the fabrication of multiscale carbon fabric composites via RTM route effectively improves the matrix-dominated properties of polymer based composites. Hybridization efficiency in carbon fiber reinforced composites using CNTs is found to be highly dependent on the changes in the dispersion state of CNTs in epoxy.     

Synergetic effect of thermal conductive properties of epoxy composites containing functionalized multi-walled carbon nanotubes and aluminum nitride

This study investigates the thermal conductivity of epoxy composites containing two hybrid fillers which are multi-walled carbon nanotubes (MWCNTs) and aluminum nitride (AlN). To form a covalent bonds between the fillers and the epoxy resin, poly(glycidyl methacrylate) (PGMA) were grafted onto the surface of nano-sized MWCNTs via free radical polymerization and micro-sized AlN was modified by zirconate coupling agent. Results show that functionalized fillers improve thermal conductivity of epoxy composites, due to the good dispersion and interfacial adhesion, which is confirmed by scanning electron microscope. Furthermore, the hybrid fillers provide synergetic effect on heat conductive networks. The thermal conductivity of epoxy composites containing 25 vol.% modified AlN and 1 vol.% functionalized MWCNTs is 1.21 W/mK, comparable to that of epoxy composites containing 50 vol.% untreated AlN (1.25 W/mK), which can reduce the half quantity of AlN filler used.     

SiC颗粒-SiC晶须混杂填料/双马来酰亚胺树脂导热复合材料的制备与性能

以双马来酰亚胺树脂(BMI)为树脂基体,二烯丙基双酚A(DABA)为增韧剂,γ-缩水甘油醚氧丙基三甲氧基硅烷(KH-560)表面改性的SiC颗粒-SiC晶须(SiCP-SiCW)为复配导热填料,浇注成型制备SiC_P-SiC_W/BMI导热复合材料,分析研究SiC形状、用量、质量比及表面改性对SiC_P-SiC_W/BMI导热复合材料的导热性能、介电性能、力学性能和热性能的影响。结果表明,当改性SiC_P-SiC_W用量为40wt%且SiC_P∶SiC_W质量比为1∶3时,SiC_P-SiC_W/BMI导热复合材料具有最佳的综合性能,导热系数λ为1.125W(m·K)~(-1),介电常数ε为4.12,5%热失重温度为427℃。     

Morphology and thermal conductivity of polyacrylate composites containing aluminum/multi-walled carbon nanotubes

Polyacrylate composites with various fillers such as multi-walled carbon nanotube (CNT), aluminum flake (Al-flake), aluminum powders and Al–CNT were prepared by a ball milling. The thermal decomposition temperature increased by as much as 64 °C for polyacrylate/Al-flake 70 wt% composite compared to polyacrylate. The thermal conductivity of polyacrylate/Al–CNT composites increased from 0.50 to 1.67 W/m K as the Al–CNT content increases from 50 to 80 wt%. The thermal conductivity of the composite sheet increases with the sheet thickness. At the given filler concentration (90 wt%), the composite filled with aluminum powder of 13 μm has a higher thermal conductivity than the one filled 3 μm powder, and the composite filled with mixture of two powders showed a synergistic effect on the thermal conductivity. The morphology indicates that the dispersion of CNT in the polyacrylate/Al-flake + CNT composite is not perfect, and agglomeration of CNTs was observed.     

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.     

The thermal conductivity of embedded nano-aluminum nitride-doped multi-walled carbon nanotubes in epoxy composites containing micro-aluminum nitride particles

Amino-functionalized nano-aluminum nitride (nano-AlN) particles were doped onto the surfaces of chlorinated multi-walled carbon nanotubes (MWCNTs) to act as fillers in thermally conducting composites. These synthesized materials were embedded in epoxy resin. Then, the untreated micro-aluminum nitride (micro-AlN) particles were added to this resin, whereby the composites filled with nano-AlN-doped MWCNTs (0, 0.5, 1, 1.5, 2 wt%) and micro-AlN (25.2, 44.1, 57.4 vol%) were fabricated. As a result, the thermal diffusivity and conductivity of all composites continuously improved with increasing nano-AlN-doped MWCNT content and micro-AlN filler loading. The thermal conductivity reached its maximum, which was 31.27 times that of the epoxy alone, when 2 wt% nano-AlN-doped MWCNTs and 57.4 vol% micro-AlN were added to the epoxy resin. This result is due to the high aspect ratio of the MWCNTs and the surface polarity of the doped nano-AlN and micro-AlN particles, resulting in the improved thermal properties of the epoxy composite.     

Carbon black–clay hybrid nanocomposites based upon EPDM elastomer

The present study explored the effect of nanoclay on the properties of the ethylene–propylene–diene rubber (EPDM)/carbon black (CB) composites. The nanocomposites were prepared with 40 wt% loading of fillers, where the nanoclay percentage was kept constant at 3 wt%. As the modified nanoclay contains the polar groups and the EPDM matrix is nonpolar, a polar rubber oil extended carboxylated styrene butadiene rubber (XSBR), was used during the preparation of nanocomposites to improve the compatibility. Primarily the nanoclay was dispersed in XSBR by solution mixing followed by ultrasonication. After that EPDM-based, CB–clay hybrid nanocomposites, were prepared in a laboratory scale two roll mill. The dispersion of the different nanoclay in the EPDM matrix was observed by wide-angle X-ray diffraction (WAXD) and high resolution transmission electron microscopy. It was found that the mechanical properties of the hybrid nanocomposites were highly influenced by the dispersion and exfoliation of the nanoclays in the EPDM matrix. Thermo gravimetric analysis, scanning electron microscopy and dynamic mechanical thermal analysis was carried out for each nanocomposite. Among all the nanocomposites studied, the thermal and mechanical properties of Cloisite 30B filled EPDM/CB nanocomposite were found to be highest.     

Fabrication and characterization of carbon fiber reinforced clay/epoxy composite

In this study, dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and flexural tests were performed on unfilled, 1, 2, 3, and 4 wt% clay filled SC-15 epoxy to identify the effect of clay weight fraction on thermal and mechanical properties of the epoxy matrix. The flexural results indicate that 2.0 wt% clay filled epoxy showed the highest improvement in flexural strength. DMA studies also revealed that 2.0 wt% system exhibit the highest storage modulus and T _g as compared to neat and other weight fraction. However, TGA results show that thermal stability of composite is insensitive to the clay content. Based on these results, the nanophased epoxy with 2 wt% clay was then utilized in a vacuum assisted resin transfer molding set up with carbon fabric to fabricate laminated composites. The effectiveness of clay addition on thermal and mechanical properties of composites has been evaluated by TGA, DMA, tensile, flexural, and fatigue test. 5 °C increase in glass transition temperature was found in nanocomposite, and the tensile and flexural strengths improved by 5.7 and 13.5 %, respectively as compared to the neat composite. The fatigue strength was also improved significantly. Based on the experimental result, a linear damage model combined with the Weibull distribution function has been established to describe static failure processing of neat and nanophased carbon/epoxy. The simulated stress–strain curves from the model are in good agreement with the test data. Simulated results show that damage processing of neat and nanophased carbon/epoxy described by bimodal Weibull distribution function.     

Properties of calcium copper titanate and barium titanate filled epoxy composites for electronic applications: effect of filler loading and hybrid fillers

Inorganic ceramics such as calcium copper titanate, CaCu₃Ti₄O₁₂ (CCTO) and barium titanate (BaTiO₃) were used as fillers to produce epoxy thin film composites for capacitor application. The effects of filler types and loading range on the dielectric, tensile, morphology, and thermal properties of the epoxy thin film composites were determined. Results showed that epoxy thin film composites with 20 vol% filler loading of CCTO and BaTiO₃ showed good dielectric properties, thermal stability, and thermal conductivity. However, the tensile properties of the CCTO/epoxy thin film composite was reduced as the filler loading increased. On the other hand, the tensile properties of BaTiO₃/epoxy thin film composite improved as the filler loading increased. Hybrid fillers CCTO and BaTiO₃ filled epoxy composites were fabricated and the effect of hybrid fillers on the dielectric properties and morphology of the epoxy thin film composites were investigated. Results indicated that positive hybrid effect in dielectric constant and dielectric loss showed by the hybrid composites.     

石墨烯微片/聚丙烯导热复合材料的制备与性能

通过熔融共混法制备了两种不同型号石墨烯微片（GNPs）填加的GNPs/聚丙烯（PP）导热复合材料,研究了GNPs型号（KNG180,KNG150）和含量对其导热性能、密度、结晶性能和热稳定性能的影响。结果表明,KNG180 GNPs/PP复合材料密度高于KNG150 GNPs/PP,同时KNG180对提高聚丙烯结晶度的效果优于KNG150。随着石墨烯微片含量的增加,两种复合材料导热系数均明显增大,而且KNG180填充的复合材料导热性能明显优于KNG150;当KNG180的添加量为60%（质量分数）时,GNPs/PP复合材料的导热系数从纯聚丙烯的0.087 W/（m·K）提高到1.32 W/（m·K）,提高了14倍多。石墨烯微片的加入显著提高了聚丙烯的热稳定性,当KNG180或KNG150的质量分数为10%时,聚丙烯达到最大热失重速率时的温度从345.1 ℃分别提高到374.6 ℃和397.9 ℃,但是当石墨烯微片超过一定含量时,热稳定性会下降。     

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.     

The influence of compression molding techniques on thermal conductivity of UHMWPE/BN and UHMWPE/(BN + MWCNT) hybrid composites with segregated structure

Various ultra-high-molecular-weight polyethylene (UHMWPE)/boron nitride (BN) and UHMWPE/(BN + multi-wall carbon nanotube (MWCNT)) composites with segregated structure were prepared by using the compression molding process. The dispersion of fillers under different compression molding were observed by optical microscopy and scanning electron microscopy. The results showed that integrated thermal conductive networks were formed after cold-pressing sintering. However, these networks would be destroyed by middle-high pressure/high temperature treatment. Although the treatment of high pressure/high temperature can effectively improve the crystallinity and crystal size of UHMWPE, the thermal conductivity of composite dramatically decreased due to the replacement of filler-filler by filler-polymer-filler interface. The 1D-MWCNT is liable to entangle with 2D-BNs and formed MWCNT-BN networks even at high pressure/high temperature, leading to a nearly constant thermal conductivity (reached 1.794 W/m·K with the addition of 50% (BNs + MWCNT) hybrid fillers). Besides, the dispersion of the fillers have a great influence on thermal stability of the composites.     

Dielectric properties of epoxy/short carbon fiber composites

The dielectric properties of epoxy/short carbon fiber composites at different concentrations 0, 5, 10 and 15% by weight, different thicknesses 2 and 4 mm, and frequency in the range from 20 Hz to 1 MHz were characterized. Scanning electron microscopy and differential scanning calorimetry were utilized. The alternating current (ac) electrical properties (complex impedance, dielectric constant, dielectric loss, real part of electric modulus, imaginary part of electric modulus, electrical conductivity, and relaxation time) were determined. It was found that the applied frequency, filler concentrations, and composite thickness affected the ac electrical properties of the epoxy/carbon fiber composites. The dielectric behaviors of the interfacial polarization between epoxy matrix and carbon fibers could be described by the Maxwell–Wagner–Sillars relaxation. The analysis of the complex electric modulus in the frequency range from 20 Hz to 1 MHz revealed that the interfacial relaxation followed the Cole–Davidson distribution of relaxation times. The universal power-law of ac conductivity was observed in the epoxy/carbon fiber composites. The calculated power exponent (near unity) is physically acceptable within this applied model.     

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...     

Performance of graphite nanoplatelet/silicone composites as thermal interface adhesives

Graphite nanoplatelets (GNP)/silicone composites are potential thermal interface materials due to their high thermal conductivity and compliance. In this study, performance as thermal interface materials is studied by measuring thermal contact resistance. The effect of surface roughness, particle size of GNPs, wt% GNPs, temperature and applied pressure on the thermal contact resistance of the composite coatings was determined. The GNP/silicone coating performed much better on rough surfaces than on smooth surfaces. The composite coating consisting of large GNPs is more effective than small GNPs probably due to the two times higher thermal conductivity of the former. The thermal contact resistance of the GNP/silicone composite increased by ~3–10% with an increase of temperature but remained unaffected by an increase of pressure. The comparison of GNP/silicone composite coatings with GNP-based thermal pastes showed that the former perform much better in thick bond lines.     

Enhanced thermal conductivity and retained electrical insulation for polyimide composites with SiC nanowires grown on graphene hybrid fillers

Polyimide (PI) composites containing one-dimensional SiC nanowires grown on two-dimensional graphene sheets (1D–2D SiC_NWs-GSs) hybrid fillers were successfully prepared. The PI/SiC_NWs-GSs composites synchronously exhibited high thermal conductivity and retained electrical insulation. Moreover, the heat conducting properties of PI/SiC_NWs-GSs films present well reproducibility within the temperature range from 25 to 175 °C. The maximum value of thermal conductivity of PI composite is 0.577 W/mK with 7 wt% fillers loading, increased by 138% in comparison with that of the neat PI. The 1D SiC nanowires grown on the GSs surface prevent the GSs contacting with each other in the PI matrix to retain electrical insulation of PI composites. In addition, the storage modulus and Young’s modulus of PI composites are remarkably improved in comparison with that of the neat PI.     

Sandwiched epoxy–alumina composites with synergistically enhanced thermal conductivity and breakdown strength

Development of polymer-based composites with simultaneously high thermal conductivity and breakdown strength has attracted considerable attentions owing to their important applications in both electronic and electric industries. In this study, we successfully design novel epoxy-based composites with nano-Al₂O₃/epoxy composite layer sandwiched between micro-Al₂O₃/epoxy composite layers, which show synergistically and significantly enhanced thermal conductivity and breakdown strength. Compared with the traditional composites, the bottleneck that both thermal conductivity and breakdown strength cannot be simultaneously enhanced can be overcome successfully. An optimized sandwiched alumina–epoxy composite with 70 wt% micro-Al₂O₃ fillers in the outer layers and 3 wt% nano-Al₂O₃ in the middle layer simultaneously displays a high thermal conductivity of 0.447 W m^?1 K^?1 (2.4 times of that of epoxy) and a high breakdown strength of 68.50 kV mm^?1, which is 6.3 % higher than that of neat epoxy (64.45 kV mm^?1). The experimental results on the thermal conductivity of multi-layered alumina–epoxy composites were in well accordance with the theoretical values predicted from the series conduction model. This novel technique simultaneously improves thermal conductivity and breakdown strength, which is of critical importance for design of perspective composites for electronic and electric equipments.