Thermomechanical properties of copper–carbon nanofibre composites prepared by spark plasma sintering and hot pressing

Several types of carbon nanofibres (CNF) were coated with a uniform and dense copper layer by electroless copper deposition. The coated fibres were then sintered by two different methods, spark plasma sintering (SPS) and hot pressing (HP). The Cu coating thickness was varied so that different volume fraction of fibres was achieved in the produced composites. In some cases, the CNF were pre-coated with Cr for the improvement the Cu adhesion on CNF. The results show that the dispersion of the CNF into the Cu matrix is independent of the sintering method used. On the contrary, the dispersion is directly related to the efficiency of the Cu coating, which is tightly connected to the CNF type. Overall, strong variations of the thermal conductivity (TC) of the composites were observed (20–200 W/mK) as a function of CNF type, CNF volume fraction and Cr content, while the coefficient of thermal expansion (CTE) in all cases was found to be considerably lower than Cu (9.9–11.3 ppm/K). The results show a good potential for SPS to be used to process this type of materials, since the SPS samples show better properties than HP samples even though they have a higher porosity, in applications where moderate TC and low CTE are required.     

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

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

Fabrication and effective thermal conductivity of multi-walled carbon nanotubes reinforced Cu matrix composites for heat sink applications

A novel particles-compositing method was used for the first time to disperse different contents of multi-walled carbon nanotubes (CNTs) in micron sized copper powders, which were subsequently consolidated into CNT/Cu composites by spark plasma sintering (SPS). Microstructural observations showed that the homogeneous distribution of CNTs and dense composites could be obtained for 0–10 vol.% CNT contents. The CNT clusters were appeared in the powder mixture with 15 vol.% CNTs, which resulted in an insufficient densification of the composites. The effective thermal conductivity of the composites was analyzed both theoretically and experimentally. The addition of CNTs showed no enhancement in overall thermal conductivity of the composites due to the interface thermal resistance associated with the low phase contrast of CNT to copper and the random tube orientation. Besides, the composite containing 15 vol.% CNTs led to a rather low thermal conductivity due possiblely to the combined effect of unfavorable factors induced by the presence of CNT clusters, i.e. large porosity, lower effective conductivity of CNT clusters themselves and reduction of SPS cleaning effect. The CNT/Cu composites may be a promising thermal management material for heat sink applications.     

Mechanical properties of epoxy composites with high contents of nanodiamond

Mechanical properties and thermal conductivity of composites made of nanodiamond with epoxy polymer binder have been studied in a wide range of nanodiamond concentrations (0-25 vol.%). In contrast to composites with a low content of nanodiamond, where only small to moderate improvements in mechanical properties were reported before, the composites with 25 vol.% nanodiamond showed an unprecedented increase in Young’s modulus (up to 470%) and hardness (up to 300%) as compared to neat epoxy. A significant increase in scratch resistance and thermal conductivity of the composites were observed as well. The improved thermal conductivity of the composites with high contents of nanodiamond is explained by direct contacts between single diamond nanoparticles forming an interconnected network held together by a polymer binder.     

Predicting the thermal conductivity of composite materials with imperfect interfaces

This paper compares the predicted values of the thermal conductivity of a composite made using the equivalent inclusion method (EIM) and the finite element method (FEM) using representative volume elements. The effects of inclusion anisotropy, inclusion orientation distribution, thermal interface conductance, h, and inclusion dimensions have been considered. Both methods predict similar overall behaviour, whereby at high h values, the effective thermal conductivity of the composite is limited by the inclusion anisotropy, while at lower h values, the effect of anisotropy is greatly diminished due to the more dominant effect of limited heat flow across the inclusion/matrix interface. The simulation results are then used to understand why in those cases where it has been possible to produce CNF reinforced Cu matrix composites with a large volume fraction of well dispersed CNFs, the measured thermal properties of the composite have failed to meet the expectations in terms of thermal conductivity, with measured conductivities in the range 200–300 W/m K. The simulation results show that, although degradation of the thermal properties of the CNFs and a poor interfacial thermal conductance are very likely the reasons behind the low conductivities reported, great care should be taken when measuring the thermal conductivity of this new class of materials, to avoid misleading results due to anisotropic effects.     

Effect of the incorporation of interfacial elements on the thermophysical properties of Cu/VGCNFs composites

Vapour grown carbon nanofibres exhibit high mechanical properties and thermal conductivities. Therefore they are potential reinforcements in composites materials for high strength and high thermal conductivity applications. A problem not yet solved is the promotion of an improved copper/carbon interface. Several strategies have been envisaged for the incorporation of alloying elements (Ni, Co, B and Ti) at the interface. These techniques are based on duplex electroless plating coatings (combination of Cu and Ni or Cu and Co), electroless plating of alloys (Cu-B) and addition of metal nanoparticles (Ti) to Cu matrix deposited by electroless plating. The effect of the incorporation of these metallic elements on the microstructure and thermophysical properties is discussed. B and Ti lead to higher interaction at the Cu/C interface over Ni and Co. This allows the reduction of the coefficient of thermal expansion but regarding the thermal conductivity it was not possible to obtain a value higher than that of copper.     

添加微量Ti 元素对Diamond/Cu复合材料组织及性能的影响

分别采用在Cu基体添加0. 1 wt%的Ti 元素形成Cu₂Ti合金和在Diamond 颗粒表面镀钛(DiamondTi) 的方法, 制备了含Diamond 体积分数为60 %的Diamond/Cu₂Ti 复合材料和DiamondTi/Cu 复合材料。对比分析了Ti 元素对复合材料微观组织、界面结合及性能的影响规律。结果表明: 添加0. 1 wt%Ti 元素能改善Diamond与Cu 的界面结合, 在界面处观察到明显的碳化物反应层; 且以Cu₂Ti合金的方式添加Ti 元素改善界面的效果优于在Diamond 颗粒表面镀Ti 的方式。所制备的Diamond/Cu₂Ti 复合材料的热导率为621 W(m·K) - 1, 而DiamondTi/Cu复合材料的热导率仅为403. 5 W(m·K) -1, 但均高于未添加Ti 制备的Diamond/Cu 复合材料。      

Thermal conductivity of Cu–Zr/diamond composites produced by high temperature–high pressure method

Copper matrix composites reinforced with about 90 vol.% of diamond particles, with the addition of zirconium to copper matrix, were prepared by a high temperature–high pressure method. The Zr content was varied from 0 to 2.0 wt.% to investigate the effect on interfacial microstructure and thermal conductivity of the Cu–Zr/diamond composites. The highest thermal conductivity of 677 W m⁻¹ K⁻¹ was achieved for the composite with 1.0 wt.% Zr addition, which is 64% higher than that of the composite without Zr addition. This improvement is attributed to the formation of ZrC at the interface between copper and diamond. The variation of thermal conductivity of the composites was correlated to the evolution of interfacial microstructure with increasing Zr content.     

Effect of titanium on copper–titanium/carbon nanofibre composite materials

Copper/carbon nanofibre composites containing titanium varying from 0.3 wt.% to 5 wt.% were made, and their thermal conductivities measured using the laser flash technique. The measured thermal conductivities were much lower than predicted. The difference between measured and predicted values has often been attributed to limited heat flow across the interface. A study has been made of the composite microstructure using X-ray diffraction, transmission electron microscopy and Raman spectroscopy. It is shown in these materials, that the low composite thermal conductivity arises primarily because the highly graphitic carbon nanofibre structure transforms into amorphous carbon during the fabrication process.     

Effect of copper content on the thermal conductivity and thermal expansion of Al–Cu/diamond composites

Al–Cu matrix composites reinforced with diamond particles (Al–Cu/diamond composites) have been produced by a squeeze casting method. Cu content added to Al matrix was varied from 0 to 3.0 wt.% to detect the effect on thermal conductivity and thermal expansion behavior of the resultant Al–Cu/diamond composites. The measured thermal conductivity for the Al–Cu/diamond composites increased from 210 to 330 W/m/K with increasing Cu content from 0 to 3.0 wt.%. Accordingly, the coefficient of thermal expansion (CTE) was tailored from 13 × 10⁻⁶ to 6 × 10⁻⁶/K, which is compatible with the CTE of semiconductors in electronic packaging applications. The enhanced thermal conductivity and reduced coefficient of thermal expansion were ascribed to strong interface bonding in the Al–Cu/diamond composites. Cu addition has lowered the melting point and resulted in the formation of Al₂Cu phase in Al matrix. This is the underlying mechanism responsible for the strengthening of Al–Cu/diamond interface. The results show that Cu alloying is an effective approach to promoting interface bonding between Al and diamond.     

Comparison of the thermal properties between composites reinforced by raw and amino-functionalized carbon materials

Carbon materials, such as graphite oxides, carbon nanotubes and graphenes, have exceptional thermal conductivity, which render them excellent candidates as fillers in advanced thermal interface materials for high density electronics. In this paper, these carbon materials were functionalized with 4,4′-diaminodiphenyl sulphone (DDS), to enhance the bonding between the carbon materials and the resin matrix. Their visibly different properties were investigated. It seems that DDS-functionalization can obviously improve the interfacial heat transfer between the carbon materials and the epoxy matrix. The thermal conductivity enhancement of D-Graphene composites (0.493 W/m K) was about 30% higher than that of D-MWNTs composites (0.387 W/m K) at 0.5 vol.% loading. The different effects among EGO, D-EGO, MWNTs, D-MWNTs and D-Graphene in polymer composites were also discussed. It was demonstrated that DDS-functionalized carbon materials had an obvious effect on the thermal performances of composite materials and were more effective in thermal conductivity enhancement.     

Thermal conductivity of Cu/diamond composites prepared by a new pretreatment of diamond powder

Cu/diamond composites were fabricated by spark plasma sintering (SPS) after the surface pretreatment of the diamond powders, in which the diamond particles were mixed with copper powder and tungsten powder (carbide forming element W). The effects of the pretreatment temperature and the diamond particle size on the thermal conductivity of diamond/copper composites were investigated. It was found that when 300 μm diamond particles and Cu–5 wt.% W were mixed and preheated at 1313 K, the composites has a relatively higher density and its thermal conductivity approaches 672 W (m K)⁻¹.     

Mechanical properties of 3D KD-I SiCf/SiC composites with engineered fibre-matrix interfaces

Three-dimensional (3D) silicon carbide (SiC) matrix composites reinforced with KD-I SiC fibres were fabricated by precursor impregnation and pyrolysis (PIP) process. The fibre-matrix interfaces were tailored by pre-coating the as-received KD-I SiC fibres with PyC layers of different thicknesses or a layer of SiC. Interfacial characteristics and their effects on the composite mechanical properties were evaluated. The results indicate that the composite reinforced with as-received fibre possessed an interfacial shear strength of 72.1 MPa while the composite reinforced with SiC layer coated fibres had a much higher interfacial shear strength of 135.2 MPa. However, both composites showed inferior flexural strength and fracture toughness. With optimised PyC coating thickness, the interface coating led to much improved mechanical properties, i.e. a flexural strength of 420.6 MPa was achieved when the interlayer thickness is 0.1 μm, and a fracture toughness of 23.1 MPa m^1/2 was obtained for the interlayer thickness of 0.53 μm. In addition, the composites prepared by the PIP process exhibited superior mechanical properties over the composites prepared by the chemical vapour infiltration and vapour silicon infiltration (CVI-VSI) process.     

基体中Ti元素含量对金刚石/Cu-Ti复合材料热导率的影响

采用真空热压法制备了金刚石体积分数为63%的金刚石/Cu-Ti复合材料,研究了基体中Ti含量对金刚石/Cu-Ti复合材料界面显微结构和热导率的影响。随着Ti含量的增加,金刚石/Cu-Ti复合材料热导率先增加后减小。当基体中Ti含量为1.1wt%时热导率最高,为511 W/（m·K）。Ti含量小于1.1wt%时,烧结过程中两相界面间生成的碳化物数量和面积随Ti含量的增加而增加,优化了界面结合,提高了界面结合强度,增加了界面传热通道数量,使金刚石/Cu-Ti复合材料导热性能提高。Ti含量的增加同时伴随着碳化物热阻增加和基体导热性能的恶化。过量的Ti元素使低导热性能的碳化物层厚度增加,碳化物层本身热阻增加,界面热导降低,金刚石/Cu-Ti复合材料导热性能下降。     

Fabrication and thermal conductivity of near-net-shaped diamond/copper composites by pressureless infiltration

Near-net-shaped diamond/copper composites with a relative density of over 99% and thermal conductivity of over 350 Wm⁻¹ K⁻¹ are successfully fabricated by powder press-pressureless infiltration processing. The effects of infiltration temperature, infiltration time, interfacial thickness, and type of protective atmosphere on the thermal conductivity of the diamond/copper composites were investigated. The results showed that the diamond-copper composites with complicated shape exhibited better thermal properties, which can be widely used in electronic packaging field. It was found that the properties of diamond-copper composites infiltrated in high vacuum atmosphere were better than that of composites infiltrated in other atmospheres. The thickness of interface showed great effects on the properties of composites. The carbide interfaces were attributed to the decrease of interfacial thermal resistance and enhancement of wetting properties between the diamonds and copper.     

Interfacial control of uni-directional SiCf/SiC composites based on electrophoretic deposition and their mechanical properties

Interfacial control of uni-directional SiC_f/SiC composites were performed by EPD, and their mechanical properties at room temperature were evaluated. The effect of the thickness of carbon interphase on SiC fibers by EPD on mechanical properties of uni-directional SiC_f/SiC composites was also investigated. The average thickness of carbon coating on SiC fibers increased from 42 nm to 164 nm with an increase in the concentration of colloidal graphite suspension for EPD. Dense SiC_f/SiC composites were achieved and their fiber volume fraction was 47–51%. The SiC_f/SiC composites had a bending strength of 210–240 MPa. As the thickness of carbon coating was below 100 nm, the SiC_f/SiC composites (SC01 and SC02) fractured in almost brittle manner. In contrast, the SiC_f/SiC composites (SC03) showed a pseudo-ductile fracture behavior with a large number of fiber pullout as the thickness of carbon coating was above 100 nm. The fracture energy of SC03 was 3–4 times as high as those of SC01 and SC02 and the value was about 1.7 kJ/m². In consideration of the results of mechanical properties, the thickness of carbon coating on SiC fibers should be at least 100 nm to obtain high-performance SiC_f/SiC composites. The fabrication process based on EPD method is expected to be an effective way to control the interfaces of SiC_f/SiC composites and to obtain high-performance SiC_f/SiC composites.     

Thermal conductivity of polymer composites based on the length of multi-walled carbon nanotubes

The anisotropic development of thermal conductivity in polymer composites was evaluated by measuring the isotropic, in-plane and through-plane thermal conductivities of composites containing length-adjusted short and long multi-walled CNTs (MWCNTs). The thermal conductivities of the composites were relatively low irrespective of the MWCNT length due to their high contact resistance and high interfacial resistance to polymer resins, considering the high thermal conductivity of MWCNTs. The isotropic and in-plane thermal conductivities of long-MWCNT-based composites were higher than those of short-MWCNT-based ones and the trend can accurately be calculated using the modified Mori-Tanaka theory. The in-plane thermal conductivity of composites with 2 wt% long MWCNTs was increased to 1.27 W/m·K. The length of MWCNTs in polymer composites is an important physical factor in determining the anisotropic thermal conductivity and must be considered for theoretical simulations. The thermal conductivity of MWCNT polymer composites can be effectively controlled in the processing direction by adjusting the length of the MWCNT filler.     

Texture,transport and mechanical properties of graphite nanoplatelet/silicone composites produced by three roll mill

Thermally conducting and highly compliant composites for thermal interface applications were developed by dispersing graphite nanoplatelets (GNPs) in silicone polymer using a three-roll mill process. X-ray diffraction and electron microscopy showed that the roll mill produces composites with better dispersion of GNPs than previously achieved by speed and mechanical mixing. The roll mill also allows production of a composite at 25 wt.% GNP loading. The thermal conductivities of the composites reached 1.03 and 3.15 W/m K at 8 and 25 wt.% of GNPs, respectively, compared to 0.17 W/m K for silicone. Compression testing showed that the composites’ moduli increase by 1.5 times up to 20 wt.% loading but the strength and strain to failure decrease. The Shore hardness was similar or slightly lower to that of silicone. The composites are thus promising alternatives to the commercial thermal interface materials currently available.     

Effect of interface debonding on the thermal conductivity of microencapsulated-paraffin filled epoxy matrix composites

Microcapsules containing phase change materials (microPCMs) can be filled in polymeric matrix forming smart temperature-controlling composites. The aim of this study was to investigate the effect of interface debonding on the thermal conductivity of microPCMs containing paraffin/epoxy composites. The shell thickness and average size of microPCMs were controlled by regulating the core/shell ratios and emulsion stirring rates. Test results indicated that the thermal conductivity (K_e) of all composites decreased after a thermal shock treatment. SEM and thermography measurements were applied to observe the interface behaviors of composites after a violent thermal treatment process. It was proved that the interface debonding was generated because of the mismatch of expansion coefficient between shell and epoxy. A modeling analysis of the relative thermal conductivity (K_r) indicated that the effective approach to decrease the debonding is to enhance the molecule tangling degree between shell and matrix.     

Influence of cobalt phase on thermal shock resistance of Al2O3-TiC composites evaluated by indentation technique

Cobalt-coated Al₂O₃ and TiC powders were prepared using an electroless method to improve resistance to thermal shock. The mixture of cobalt-coated Al₂O₃ and TiC powders (about 70 wt.% Al₂O₃-Co + 30 wt.% TiC-Co) was hot-pressed into an Al₂O₃-TiC-Co composite. The thermal shock properties of the composite were evaluated by indentation technique and compared with the traditional Al₂O₃-TiC composite. The composites containing 3.96 vol.% cobalt exhibited better resistance to crack propagation, cyclic thermal shock and higher critical temperature difference (ΔT_c). The calculation of thermal shock resistance parameters (R parameters) shows that the incorporation of cobalt improves the resistance to thermal shock fracture and thermal shock damage. The thermal physic parameters are changed very little but the flexure strength and fracture toughness of the composites are improved greatly by introducing cobalt into Al₂O₃-TiC (AT) composites. The better thermal shock resistance of the composites should be attributed to the higher flexure strength and fracture toughness.