Fabrication of surface-treated BN/ETDS composites for enhanced thermal and mechanical properties

The ceramic/polymer composites based on epoxy-terminated dimethylsiloxane (ETDS) and boron nitride (BN) were prepared for use as thermal interface materials (TIMs). 250 µm-sized BN was used as a filler to achieve high-thermal-conductivity composites. To improve the interfacial adhesion between the BN particles and the ETDS matrix, the surface of BN particles were modified with silica via the sol–gel method with tetraethyl orthosilicate (TEOS). The interfacial adhesion properties of the composites were determined by the surface free energy of the particles using a contact angle test. The surface-modified BN/ETDS composites exhibited thermal conductivities ranging from 0.2 W/m K to 3.1 W/m K, exceeding those of raw BN/ETDS composites at the same weight fractions. Agari׳s model was used to analyze the measured thermal conductivity as a function of the SiO₂-BN concentration. Moreover, the storage modulus of the BN/ETDS composites was found to increase with surface modification of the BN particles.     

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.     

Cactus-like double-oriented magnetic SiC and BN networks leading to simultaneously enhanced dielectric strength and thermal conductivity of epoxy composites

Epoxy-based composites with high insulation and thermal conductivity are desirable materials for electronic and electrical applications. However, resolving the tradeoff between insulation and thermal conductivity remains challenging. Based on the functional requirement, we designed and fabricated a cactus-like double-oriented epoxy composite by combining magnetic orientation and ice-templated methods. Semiconducting SiC endowed the composite with field-grading characteristics, thus relieving local electric field stress along the horizontal direction, while BN with high thermal conductivity promoted heat dissipation along the vertical direction. The composite exhibited its highest performance with 15 vol% filler, improving the breakdown voltage and thermal conductivity by 43.7% and 1312% compared with pure epoxy, respectively, outperforming recently developed packaging materials. It is believed that this work offers an efficient strategy for the fabrication of the filler structure and provides insights on the simultaneous enhancement in insulation and thermal conductivity of polymer composites.     

Enhanced thermal performance of hybrid interface materials supported by 3D thermally conductive SiC framework

The rapid development of microelectronic integration technology is placing increasing demands on the safety performance of electronic devices. Excellent thermal interface materials (TIM) facilitate the dissipation of heat from electronic components, which ensures the safety of electronic equipment. In this work, a three-dimensional (3D) thermally conductive framework is constructed from carbon fibers to form silicon carbide (SiC) in situ. This is followed by vacuum impregnation with paraffin wax (PW) to produce phase change composites (PCCs). The results show that the SiC-based 3D thermally conductive framework has a hierarchical porous network structure, and the PCC indicates enhanced thermal conductivity and good anti-leakage properties. The thermal conductivity of PW @ CF1–Si1-1550 is 0.81 W K⁻¹m⁻¹, which is 4 times that of PW. In addition, the PCC also shows good thermal cycling properties, high thermal storage capacity (179.06 Jg^-1), and good insulation properties. The PCC as described in this paper as TIM have considerable application potential in thermal management.     

Thermal conductivity and lap shear strength of GNP/epoxy nanocomposites adhesives

The addition of graphene nanoplatelets (GNPs) into the epoxy adhesives has been studied in order to increase their thermal conductivity. Thermally conductive adhesives are often used as thermal interface materials (TIMs). The incorporation of 8 and 10 wt% GNPs reinforcement caused a thermal conductivity enhancement of ~206 and ~306%, respectively. The wettability seems to decrease with low GNPs content (2–3 wt%) in comparison with the neat epoxy adhesive but the contact angle remains constant for higher GNPs contents. Lap shear strength remains constant for neat adhesives and resins doped with GNPs. The lack of enhancement of adhesive properties of doped resins is due to a weak interface reinforcement-matrix. In fact, the joint failure is in the adhesive except for high GNPs content (10 wt%) where a cohesive failure mode is observed.     

Carbon nanofiber based buckypaper used as a thermal interface material

Carbon nanofiber (CNF) based buckypaper was explored as a potential thermal interface material (TIM) for electronics. CNFs were subjected to heat treatment temperatures of 1100 °C, 1500 °C and 3000 °C. TIMs were prepared and characterized using thermal impedance test stand. Results show that the thermal impedance at the interface decreased in conjunction with the increasing heat-treatment temperature of CNFs. TIMs with graphitized CNF exhibit a significant decrease of 54% in thermal impedance in comparison with the dry contact. This improvement is likely due to the high degree of CNF graphitizibility and the resulting outstanding electrical and thermal conductivities.     

相变热界面材料导热增强及定形改善的研究进展

将相变时伴随潜热的相变材料（phase change material, PCM）特别是潜热值较大的固-液PCM引入热界面材料（TIM）领域,有望获得兼具储热和导热双功能的新型热界面材料——相变热界面材料（phase change thermal interface material, PCTIM）。然而,鉴于固-液相变材料的热导率普遍较低且存在液相流动泄漏问题,使得增强热传导并同时提升固-液相变材料的定形性成为研制高性能相变热界面材料（PCTIM）的关键。本文系统评述了国内外研究者在提升相变热界面材料热导率以及改善其定形性方面的策略及其研究进展。文中指出,目前强化PCTIM导热的手段主要有添加高导热填料、促使填料有序结构化以及使用低熔点金属等。在改善定形性方面,已运用的策略主要包括使用柔性载体负载固-液PCM以在保证一定柔性的基础上克服其液相泄漏问题,使用固-固PCM来取代固-液PCM来彻底避免液相泄漏问题的出现,以及将固-液PCM封装在微米级或纳米级胶囊内,旨在牺牲借助液相PCM增加柔性的功能,而且通过提高PCTIM的潜热值来提升其抗热流冲击性能。文章指出,当前已研制的PCTIM热...     

Superior hydrophobicity of nano-SiO2 porous thermal insulating material treated by oil-in-water microemulsion

Nano-SiO₂ porous thermal insulating material (TIM) has drawn tremendous research interests due to its advantages of low density, high porosity and low thermal conductivity. However, its long-term stability in humid environment can be severely deteriorated by the high hydrophilicity resulting from tetrahedral coordination of oxygen and capillary effect of porous structure. It is still a great challenge to cost-effectively fabricate bulk TIM with superior hydrophobicity and consequent remarkable self-cleaning capability. Herein, via an oil-in-water microemulsion treatment, we have proposed a new strategy to construct 3D superior hydrophobic nano-SiO₂ porous TIM. The polymethylhydrosiloxane-modified TIM exhibits a large water contact angle of 166°, and corresponding excellent self-cleaning characteristic while maintaining low thermal conductivity of 0.031 W/m·K. Moreover, our high hydrophobicity of TIM exhibits excellent durability under high temperature up to 400 °C, high humidity of 100%, and chemical erosions. Detailed knowledge of the physical chemistry basis of the superior hydrophobic nano-SiO₂ porous TIM can provide great opportunity to fabricate advanced self-cleaning and heat insulating devices especially targeted for harsh environments.     

Multi-contact hybrid thermal conductive filler Al2O3@AgNPs optimized three-dimensional thermal network for flexible thermal interface materials

In this work, a multi-contact Al₂O₃@AgNPs hybrid thermal conductive filler was synthesized by in-situ growth method to fill high thermal conductivity polydimethylsiloxane (PDMS)-based composites to prepare TIMs. And the thermal conductivity, electrical conductivity, and mechanical properties of the composite materials were studied. During the synthesis process of the multi-contact hybrid filler, different concentrations of silver ions were reduced to generate silver nanoparticles and attached to the surface of Al₂O₃. Al₂O₃@AgNPs/PDMS thermally conductive composites were prepared by changing the filler addition. Using SEM, XPS, and XRD is used to characterize the morphology and chemical composition of Al₂O₃@AgNPs hybrid filler. The thermal conductivity of PDMS-based composites with different AgNPs content under 70 wt% filler loading was studied. The results show that the thermal conductivity of PDMS-based composites filled with 7owt%Al₂O₃@3AgNPs/PDMS multi-contact hybrid filler is 0.67 W/m·K, which is 3.72 times that of pure PDMS, and is higher than that of unmodified Al₂O₃ with the same addition amount. /PDMS composite material has a high thermal conductivity of 24%. This work provides a new idea for the design and manufacture of high thermal conductivity hybrid fillers for TIMs.     

Simultaneous improvement of thermal conductivity and mechanical properties for mechanically mixed ABS/h-BN composites by using small amounts of hyperbranched polymer additives

Recently, thermal interface materials (TIMs) are in great demands for modern electronics. For mechanically mixed polymer composite TIMs, the thermal conductivity and the mechanical properties are generally lower than expected values due to the sharply increased viscosity and poor filler dispersion. This work shows that addition of a small amount of polyester-based hyperbranched polymer (HBP) avoided the trade-off in mechanically mixed ABS/hexagonal boron nitride (h-BN) composites. After adding 0.5 wt% HBP, the maximum h-BN content in the composites increased from 50 to 60 wt%. The out-of-plane, in-plane thermal conductivity, and tensile strength of ABS/h-BN with 50 wt% h-BN were 0.408, 0.517 W/mK, and 18 MPa, respectively, and were increased to 0.729, 0.847 W/mK, and 32 MPa by adding 0.5 wt% HBP, while 0.972, 1.12 W/mK, and 29.5 MPa were achieved for ABS/h-BN/HBP with 60 wt% h-BN. The morphological and rheological results proved that these enhancements are due to the improved h-BN dispersion by decreasing viscosity of composites during mixing. Theoretical modeling based on the modified effective medium theory confirmed such results and showed that the interfacial thermal resistance also decreased slightly. Thus, this work demonstrates a facile and scalable method for simultaneously improving the thermal conductivity and mechanical properties of thermoplastic-based TIMs.     

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.     

The effect of filler concentration on the electrical,thermal, and mechanical properties of carbon particle and carbon fiber‐reinforced poly(styrene‐co‐acrylonitrile) composites

Composite materials of poly (styrene‐co‐acrylonitrile) (luran) matrix with carbon fibers (CF)/carbon particles (CP) were prepared and their properties were evaluated. The mechanical and thermal properties of these composites were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Although, by increasing the filler concentration no significant difference was found in melting and crystallization temperatures of the luran. The storage and tensile modulus of the composites increased linearly with filler concentration up to 40 wt % that was approximately three times higher than that of the virgin luran. There is a shift in glass transition temperature of the composite with increasing the filler concentration and the damping peak became flatter that indicated the effectiveness of the filler–matrix interaction. The volume resistivity and thermal conductivity (TC) of the composites were also measured. At a given carbon filler content the CF–Luran composites have much less volume resistivity as compared to CP–Luran composites. The decreased percolation threshold and volume resistivity in case of CF–Luran composites indicated that conductive paths existed in the composites. The conductive pathways were probably formed through interconnection of the carbon fillers. The volume resistivity was also decreased as a function of temperature. The thermal conductivity was increased linearly as a function of temperature with increasing filler concentration up to 40% of CF and CP. This increase was more profound in case of CF–Luran as compared to CP–Luran composites. This was owing to greater thermal networks of fibers as compared to particles. POLYM. COMPOS., 28:186–197, 2007. © 2007 Society of Plastics Engineers     

Effects of cross-scale h-BN grains and orientation degree on the mechanical and thermal properties of BN-matrix textured ceramics

h-BN is a two-dimensional ceramic material with a lamellar structure, known for its typical orientation characteristics on mechanical and thermal properties. By optimizing the size and arrangement of h-BN grains in the matrix, the anisotropic characteristics of h-BN ceramics can be fully utilized to obtain ceramic materials with high thermal conductivity or high strength. In order to study the effect of grain orientation distribution on the mechanical and thermal properties of materials, the index of orientation distribution (IOP) was used to quantitatively characterize the orientation degree of h-BN grains and analyzed the effect of h-BN grain size on material properties. The results show when the initial h-BN size is 13.50 μm, the ceramic has the highest orientation degree/-507, and the mechanical and thermal properties show obvious anisotropy. While the related properties of BN-YAG ceramics varies significantly with the decrease of initial h-BN grain size.     

Thermal conductivity of a graphene oxide–carbon nanotube hybrid/epoxy composite

Thermally conductive graphene oxide (GO)–multi-wall carbon nanotube (MWCNT)/epoxy composite materials were fabricated by epoxy wetting. The polar functionality on the GO surface allowed the permeation of the epoxy resin due to a secondary interaction between them, which allowed the fabrication of a composite containing a high concentration of this hybrid filler. The thermal transport properties of the composites were maximized at 50 wt.% of filler due to fixed pore volume fraction in filtrated GO cake. When the total amount of filler was fixed 50 wt.% while changing the amount of MWCNTs, a maximum thermal conductivity was obtained with the addition of about 0.36 wt.% of MWCNTs in the filler. Measured thermal conductivity was higher than the predicted value based on the by Maxwell–Garnett (M–G) approximation and decreased for MWCNT concentrations above 0.4%. The increased thermal conductivity was due to the formation of 3-D heat conduction paths by the addition of MWCNTs. Too high a MWCNT concentration led to increased phonon scattering, which in turn led to decreased thermal conductivity. The measured storage modulus was higher than that of the solvent mixed composite because of the insufficient interface between the large amount of filler and the epoxy.     

Low thermal conductivity of atomic layer deposition yttria-stabilized zirconia (YSZ) thin films for thermal insulation applications

Thermal insulation applications have long required materials with low thermal conductivity, and one example is yttria (Y₂O₃)-stabilized zirconia (ZrO₂) (YSZ) as thermal barrier coatings used in gas turbine engines. Although porosity has been a route to the low thermal conductivity of YSZ coatings, nonporous and conformal coating of YSZ thin films with low thermal conductivity may find a great impact on various thermal insulation applications in nanostructured materials and nanoscale devices. Here, we report on measurements of the thermal conductivity of atomic layer deposition-grown, nonporous YSZ thin films of thickness down to 35 nm using time-domain thermoreflectance. We find that the measured thermal conductivities are 1.35–1.5 W m⁻¹ K⁻¹ and do not strongly vary with film thickness. Without any reduction in thermal conductivity associated with porosity, the conductivities we report approach the minimum, amorphous limit, 1.25 W m⁻¹ K⁻¹, predicted by the minimum thermal conductivity model.     

Thermal conductivity of several geopolymer composites and discussion of their formulation

We fabricated 50.8-mm cube-shaped samples of metakaolin geopolymer (GP) composites with various additives chosen to increase or decrease the thermal conductivity of the composite. Sodium-based GP (NaGP) and GP composites were more conductive than potassium-based GP (KGP) composites for a given phase fraction of filler, but the maximum amount of filler phase was higher with KGP due to the lower viscosity of the KGP mixture. The highest thermal conductivity achieved was about 8 W/m K by KGP + 44-vol% graphite flakes, whereas NaGP + 27 vol% graphite flakes reached 4.7 W/m K. The thermal conductivity was strongly affected by the moisture remaining in the composite, which appeared to have a greater effect at higher filler content. On the other hand, the size of alumina particles (6, 40, or 120 μm) did not have any apparent effect on thermal conductivity for the same filler content. Larger particles caused less change in mixture viscosity, though, thus permitting incorporation of higher filler phase fractions and therefore higher thermal conductivity.     

Thermal conductivity of boron nitride‐filled thermoplastics: Effect of filler characteristics and composite processing conditions

The thermal conductivity of boron nitride (BN)‐filled poly(butylene terephthalate) (PBT) was investigated as a function of particle size, aspect ratio, surface area, surface chemistry, and concentration of BN as well as composite processing methods and conditions. In the low filler concentration region, a larger BN surface area resulted in lower thermal conductivity of the composites as a result of phonon scattering at interfaces. In the high filler concentration region the ease in forming filler networks, as reflected by the aspect ratio of BN, played a more dominant role. A percolation‐like behavior was observed when BN networks were formed while the thermal conductivity at close vicinity of the percolation threshold was not completely governed by the scaling law of classic percolation theory. High shear force employed in extrusion was effective in dispersing BN agglomerates into fine platelets while also inducing PBT degradation. When a low screw speed was used in extrusion followed by injection molding, the samples exhibited significantly lower thermal conductivity, which may be attributed to flow‐induced orientation of BN platelets in the direction perpendicular to the heat flow, relatively low concentration of filler at sample surfaces (skin‐core effect), and agglomeration of the BN platelets. POLYM. COMPOS. 26:778–790, 2005. © 2005 Society of Plastics Engineers     

Preparation of a novel bi-layer modified alumina-based hybrid material and its effect on the thermal conductivity enhancement of polymer composites

In this work, a new kind of double layers modified alumina-based hybrid (silver@copper@alumina (Ag@Cu@Al₂O₃) hybrid) was successfully synthesized through the two-step layer-by-layer process. First, copper (Cu) nanoparticles were assembled onto alumina (Al₂O₃) particles by reduction of Cu²⁺. Second, Ag@Cu@Al₂O₃ hybrids were assembled via Ag deposition on the surface of Cu@Al₂O₃ particles. The obtained Ag@Cu@Al₂O₃ hybrids served as thermally conductive fillers to greatly boost the thermal conductivity of poly (dimethylsiloxane) (PDMS). The thermal conductivity reached 1.465 W m^?1 K^?1 at 85 wt% filler loading. The thermal conductivity of PDMS matrix was increased more than 7 times by the addition of Ag@Cu@Al₂O₃ hybrid, which was much higher than single layer modified alumina-based hybrids (Ag@Al₂O₃ and Cu@Al₂O₃ hybrids) and virgin Al₂O₃ particle. The effect of double layers modified filler, single layer modified filler and virgin filler on the thermal conductivity of PDMS matrix was discussed in detail and the mechanism of these fillers for improving thermal conductivity was studied through Foygel's thermal conduction model. Otherwise, electric, mechanical and thermal properties of Ag@Cu@Al₂O₃/PDMS composites were also further tested and analyzed.     

Novel nanometer alumina-silica insulation board with ultra-low thermal conductivity

Advanced nano-porous super thermal insulation materials are widely used in spacecraft, soler-thermal shielding, heat exchangers, photocatalytic carriers due to their low thermal conductivity. In this work, adopting dry preparation technology, nano-Al₂O₃, nano-SiO₂, SiC and glass fibers as raw materials, novel nanometer alumina-silica insulation board (NAIB) were prepared. The preparation process was simple, safe, and reliable. In addition, the NAIB exhibited a high porosity (91.3–92.3%), small pore size (39.83–44.15 nm), low bulk density (0.22–0.26 g/cm³), better volumetric stability, and low thermal conductivity (0.031–0.050 W/(m·K) (200–800 °C)), respectively. The as-prepared NAIB could render them suitable for application as high-temperature thermal insulation materials.     

Thermal properties of hydrating calcium aluminate cement pastes

As the hydration of calcium aluminate cements (CAC) is highly temperature dependent, yielding morphologically and structurally different hydration products that continuously alter material properties, a good knowledge of thermal properties at early stages of hydration is essential. Thermal diffusivity and thermal conductivity during CAC hydration was investigated by a transient method with a numerical approach and a transient hot wire method, respectively. For hydration at 15 °C (formation of mainly CAH₁₀), thermal diffusivity shows a linear decrease as a function of hydration degree, while for hydration at 30 °C there is a linear increase of thermal diffusivity. Converted materials exhibited the highest values of thermal diffusivities. The results on sealed converted material indicated that thermal conductivity increased with an increase in temperature (20-80 °C), while thermal diffusivities marginally decreased with temperature. The Hashin-Shtrikman boundary conditions and a simple law of mixtures were successfully applied for estimating thermal conductivity and heat capacity, respectively, of fresh cement pastes.