Effect of titanium carbide coating on the microstructure and thermal conductivity of short graphite fiber/copper composites

Graphite fiber–Cu composites have drawn much attention in electronic packaging due to its excellent machinability and thermal properties. However, the weak interface bonding between graphite fiber and copper resulted in low thermo-mechanical properties of composites. In this work, a titanium carbide coating with thickness of 0.1 μm or 1 μm was synthesized on the surface of graphite fiber through molten salts method to strengthen interfacial bonding. The enhanced composites present 24–43 % increase in thermal conductivity and achieve the thermal conductivity of 330–365 W m^?1 K^?1 as well as the coefficient of thermal expansion of 6.5 × 10^?6–14 × 10^?6 K^?1. A Maxwell–Garnett effective medium approach on the anisotropic short fiber reinforcement with interfacial thermal resistance was established. The obtained enhancement was in good agreement with the estimates. The results suggest that the major factor that influences the thermal conductivities is not the interfacial thermal resistance but the low thermal conductivity of fiber in transversal direction when a well interfacial bonding is obtained.     

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.     

The thermal conductivity of Al(OH)3 covered MWCNT/epoxy terminated dimethyl polysiloxane composite based on analytical Al(OH)3 covered MWCNT

Aluminum-hydroxide-covered multi-walled carbon nanotubes (A–MWCNT) were fabricated as a thermally conductive material. The thermal conductivity of A–MWCNT was estimated based on Casimir theory. The effective thermal conductivity of A–MWCNT was estimated at about ∼26 W/mK. The thermal conductivity of A–MWCNT/epoxy-terminated polydimethylsiloxane (ETDS) composite was examined as a function of A–MWCNT loading, and the results showed the maximum value at 1.5 wt% of A–MWCNT loading, above which it decreased slightly. The effective medium approximation (EMA) developed by Maxwell–Garnett (M–G) was used to analyze the thermal conducting behavior of the composite. The experimental results showed negative deviation from the expected thermal conductivity, k_e, beyond 1.5 wt% of A–MWCNT loading, because the composites containing A–MWCNT were strongly affected by interfacial resistance. The interfacial resistance value calculated from M–G approximation increased when filler loading was higher than 1.5 wt% because of the folded and partially agglomerated A–MWCNT along with insufficient interfacial interactions.     

Effect of tungsten addition on thermal conductivity of graphite/copper composites

Graphite/copper composites with high thermal conductivity were fabricated by tungsten addition, which formed a thin tungsten carbide layer at the interface. The microstructure and thermal conductivity of the composite material were studied. The results indicated that the insertion of tungsten carbide layer obviously suppressed spheroidization of copper coating on the graphite particles during the sintering process, and decreased the interfacial thermal resistance of the composites. Compared with the graphite/copper composites without tungsten, the thermal conductivity of the obtained composites was increased by 43.6%.     

Enhanced thermal conductivity and dielectric properties of Al/β-SiCw/PVDF composites

Polymeric composites with high thermal conductivity, high dielectric permittivity but low dissipation factor have wide important applications in electronic and electrical industry. In this study, three phases composites consisting of poly(vinylidene fluoride) (PVDF), Al nanoparticles and β-silicon carbide whiskers (β-SiC_w) were prepared. The thermal conductivity, morphological and dielectric properties of the composites were investigated. The results indicate that the addition of 12 vol% β-SiC_w not only improves the thermal conductivity of Al/PVDF from 1.57 to 2.1 W/m K, but also remarkably increases the dielectric constant from 46 to 330 at 100 Hz, whereas the dielectric loss of the composites still remain at relatively low levels similar to that of Al/PVDF at a wider frequency range from 10⁻¹ Hz to 10⁷ Hz. With further increasing the β-SiC_w loading to 20 vol%, the thermal conductivity and dielectric constant of the composites continue to increase, whereas both the dielectric loss and conductivity also rise rapidly.     

Investigation of thermal conductivity and dielectric properties of LDPE-matrix composites filled with hybrid filler of hollow glass microspheres and nitride particles

The hybrid filler of hollow glass microspheres (HGM) and nitride particles was filled into low-density polyethylene (LDPE) matrix via powder mixing and then hot pressing technology to obtain the composites with higher thermal conductivity as well as lower dielectric constant (D_k) and loss (D_f). The effects of surface modification of nitride particles and HGMs as well as volume ratio between them on the thermal conductivity and dielectric properties at 1 MHz of the composites were first investigated. The results indicate that the surface modification of the filler has a beneficial effect on thermal conductivity and dielectric properties of the composites due to the good interfacial adhesion between the filler and matrix. An optimal volume ratio of nitride particles to HGMs of 1:1 is determined on the basis of overall performance of the composites. The thermal conductivity as well as dielectric properties at 1 MHz and microwave frequency of the composites made from surface-modified fillers with the optimal nitride to HGM volume ratio were investigated as a function of the total volume fraction of hybrid filler. It is found that the thermal conductivity increases with filler volume fraction, and it is mainly related to the type of nitride particle other than HGM. The D_k values at 1 MHz and microwave frequency show an increasing trend with filler volume fraction and depend largely on the types of both nitride particles and HGMs. The D_f values at 1 MHz or quality factor (Q × f) at microwave frequency show an increasing or decreasing trend with filler volume fraction and also depend on the types of both nitride particle and HGM. Finally, optimal type of HGM and nitride particles as well as corresponding thermal conductivity and dielectric properties is obtained. SEM observations show that the hybrid filler particles are agglomerated around the LDPE matrix particles, and within the agglomerates the smaller-sized nitride particles in the hybrid filler can easily form thermally conductive networks to make the composites with high thermal conductivity. At the same time, the increase of the value D_k of the composites is restricted due to the presence of HGMs.     

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.     

Highly mechanical strength and thermally conductive bismaleimide–triazine composites reinforced by Al2O3@polyimide hybrid fiber

Bismaleimide–triazine (BT) resins have received a great deal of attention in microelectronics due to its excellent thermal stability and good retention of mechanical properties. Thereafter, developing BT based composites with high mechanical strength, thermal conductivity and dielectric property simultaneously are highly desirable. In this study, one hybrid fiber of Al₂O₃ nanoparticle (200 nm) supported on polyimide fiber (Al₂O₃@PI) with core–shell structure was introduced into BT resin to prepare promising Al₂O₃@PI–BT composite. The results indicated that the resultant composites possessed high Young’s modulus of 4.06 GPa, low dielectric constant (3.38–3.50, 100 kHz) and dielectric loss (0.0102–0.0107, 100 kHz). The Al₂O₃@PI hybrid film was also conductive to improve thermal stability (T_d5% up to 371 °C), in-plane thermal conductivity (increased by 295% compared to that of the pure BT resin). Furthermore, the Al₂O₃@PI–BT composite were employed to fabricate a printed circuit substrate, on which a frequency “flasher” circuit and electrical components worked well.     

Grafting of nano-TiO2 onto flax fibers and the enhancement of the mechanical properties of the flax fiber and flax fiber/epoxy composite

In this article, a flax fiber yarn was grafted with nanometer sized TiO₂, and the effects on the tensile and bonding properties of the single fibers and unidirectional fiber reinforced epoxy plates were studied. The flax fiber yarn was grafted with nanometer sized TiO₂ through immersion in nano-TiO₂/KH560 suspensions under sonification. The measured grafting content of the nano-TiO₂ ranged from 0.89 wt.% to 7.14 wt.%, dependent on the suspension concentration. With the optimized nano-TiO₂ grafting content (∼2.34 wt.%), the tensile strength of the flax fibers and the interfacial shear strength to an epoxy resin were enhanced by 23.1% and 40.5%, respectively. The formation of Si–O–Ti and C–O–Si bonds and the presence of the nano-TiO₂ particles on the fiber surfaces contributed to the property enhancements. Unidirectional flax fiber reinforced epoxy composite (V_f = 35.4%) plates prepared manually showed significantly enhanced flexural properties with the grafting of nano-TiO₂.     

The effect of interfacial state on the thermal conductivity of functionalized Al2O3 filled glass fibers reinforced polymer composites

Rapidly increasing packaging density of electronic devices puts forward higher requirements for thermal conductivity of glass fibers reinforced polymer (GFRP) composites, which are commonly used as substrates in printed circuit board. Interface between fillers and polymer matrix has long been playing an important role in affecting thermal conductivity. In this paper, the effect of interfacial state on the thermal conductivity of functionalized Al₂O₃ filled GFRP composites was evaluated. The results indicated that amino groups-Al₂O₃ was demonstrated to be effective filler to fabricate thermally conductive GFPR composite (1.07 W/m K), compared with epoxy group and graphene oxide functionalized Al₂O₃. It was determined that the strong adhesion at the interface and homogeneous dispersion of filler particles were the key factors. Moreover, the effect of interfacial state on dielectric and thermomechanical properties of GFRP composites was also discussed. This research provides an efficient way to develop high-performance GFRP composites with high thermal conductivity for integrated circuit packaging applications.     

Preparation of high thermal conductivity copper–diamond composites using molybdenum carbide-coated diamond particles

Molybdenum carbide (Mo₂C) coatings on diamond particles were proposed to improve the interfacial bonding between diamond particles and copper. The Mo₂C-coated diamond particles were prepared by molten salts method and the copper–diamond composites were obtained by vacuum pressure infiltration of Mo₂C-coated diamond particles with pure copper. The structures of the coatings and composites were investigated using X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results indicated that the Mo₂C coatings effectively improved the wettability between diamond particles and copper matrix, and Mo₂C intermediate layers were proved to decrease the interfacial thermal resistance of composites. The thermal conductivity of the composite reached 608 Wm^?1 K^?1 with 65 vol.% Mo₂C-coated diamond, which was much higher than that with uncoated diamond. The greatly enhanced thermal conductivity is ascribed to the 1-μm-thick Mo₂C coatings. Mo₂C coatings on diamond particles are proved to be an effective way to enhance the thermal conductivities of copper–diamond composites.     

NR/CSM/biogenic silica rubber blend composites

Biogenic silica (BSi) was added at different ratios to some polymer blends of polyisoprene rubber (NR) and chlorosulphonated polyethylene rubber (CSM) cured by conventional sulfur system. The reinforcing performance of the filler was investigated using rheometric, mechanical and swelling measurements, differential scanning calorimetry (DSC), thermogravimetric (TGA) and scanning electron microscopy (SEM) analysis. There was a remarkable decrease in the optimum cure time (t_c90) and the scorch time (t_s2), which was associated with an increase in the cure rate index (CRI), with filler loading up to 30 phr in the different blend ratios. The tensile strength and hardness was 4–5 Sh-A higher in the case for the different blend compositions, while the resistance to swelling in toluene became higher. SEM photographs show that the filler is located at the interface between the different polymers which induces compatibilization in the immiscible blends. DSC scans of the filled blends showed shifts in the glass transition temperatures Tg which can be attributed to the improve interfacial bonding between filler and NR/CSM matrix. A higher thermal stability of NR/CSM/BSi composites was detected.     

Improvement of mechanical properties in aluminum/CNTs nanocomposites by addition of mechanically activated graphite

Carbon nanotubes reinforced aluminum nanocomposite was prepared by ball milling route. CNTs were initially mixed with mechanically amorphized graphite. Specimens were analyzed by X-ray diffractometry and Raman spectroscopy. Crystallite size and dislocation density were calculated by modified Warren–Averbach method. Carbide formation was semi-quantitatively investigated via Raman spectroscopy. A band located in 950 cm⁻¹ was considered to be corresponded to Al₄C₃. Hardness of the samples was also evaluated using a Vickers micro-hardness tester. The hardness strengthening contributions were modeled to evaluate interfacial bonding between CNTs and the aluminum matrix. In specimens, including amorphized graphite, hardening was due to both work hardening and second phase strengthening otherwise, only due to work hardening. It was deducted that the amorphized graphite has a major role for mechanical properties improvement. This seems to be due to the formation of aluminum carbide at the interface which consequently increases adhesion of CNTs to aluminum.     

Thermal conductivity of boron nitride reinforced polyethylene composites

The thermal conductivity of boron nitride (BN) particulates reinforced high density polyethylene (HDPE) composites was investigated under a special dispersion state of BN particles in HDPE, i.e., BN particles surrounding HDPE particles. The effects of BN content, particle size of HDPE and temperature on the thermal conductivity of the composites were discussed. The results indicate that the special dispersion of BN in matrix provides the composites with high thermal conductivity; moreover, the thermal conductivity of composites is higher for the larger size HDPE than for the smaller size one. The thermal conductivity increases with increasing filler content, and significantly deviates the predictions from the theoretic models. It is found also that the combined use of BN particles and alumina short fiber obtains higher thermal conductivity of composites compared to the BN particles used alone.     

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.     

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。     

Tensile and thermomechanical properties of short carbon fiber reinforced polyamide 6 composites

In this study, carbon fiber (CF) reinforced polyamide 6 (PA6) composites were prepared by using melt mixing method. Effects of fiber length and content, on the mechanical, thermal and morphological properties of CF reinforced PA6 composites were investigated. Fiber length distributions of composites were also determined by using an image analyzing program. It was seen that the maximum number of fibers were observed in the range of 0–50 μm. Mechanical test results showed that, increasing CF content increased the tensile strength, modulus and hardness values but decreased strain at break values of composites. DSC results showed that T_g and T_m values of composites were not changed significantly with increasing CF content and length. However, heat of fusion and the relative degree of crystallinity values of composites decreased with ascending CF content. DMA results revealed that storage modulus and loss modulus values of composites increased with increasing CF content.     

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.     

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.     

Effect of aspect ratio on thermal conductivity of high density polyethylene/multi-walled carbon nanotubes nanocomposites

This study aims to investigate experimentally the effects of aspect ratio (length/diameter ratio) and concentration of multiwalled carbon nanotubes (MWCNTs) on thermal properties of high density polyethylene (HDPE) based composites. The aspect ratios of two types of MWCNT fillers are in the range of 200–400 and 500–3000. Composite samples were prepared by melt mixing up to weight fraction of 19% filler content, followed by a compression molding. Measurements of density, specific heat and thermal diffusivity (by modulated photothermal radiometry, PTR) were performed and effective thermal conductivities k_e of nanocomposites were calculated using these values. The results show that the composites containing MWCNTs with higher aspect ratio have higher thermal conductivities than the ones with lower aspect ratio. In terms of conductivity enhancement k_e/k_m − 1, the results indicate that MWCNTs with higher aspect ratio provide three to fourfold larger enhancement than the ones with lower aspect ratio, at low filler concentrations.