无机填料的表面处理及其在导热天然橡胶复合材料中的应用

用季戊四醇、丙三醇和钛酸酯偶联剂分别对氧化铝、氧化镁和高岭土进行表面改性,并将改性填料填充天然橡胶(NR)制备了导热复合材料,考察了表面处理剂种类及其用量对无机填料的影响,并研究了季戊四醇改性氧化铝填充NR复合材料的硫化特性、物理机械性能和导热性能.结果表明,3种填料中季戊四醇的改性效果最好,且其用量为1.0～1.5份时对氧化铝的改性效果最佳;随着改性氧化铝填充量的增加,复合材料的最大转矩、300%定伸应力、拉伸强度和热导率均增大,当其用量为60份时,改性氧化铝填充NR复合材料的热导率比未填充NR复合材料提高了23.9%.     

Comparative study of thermally conductive fillers in underfill for the electronic components

General underfill for the flip-chip package had a low thermal conductivity of about 0.2 W/mK. Thermal properties of underfill were measured with various fillers, such as silica, alumina, boron nitride, (BN) and diamond. Coefficient of thermal expansion (CTE) was changed by filler content and CTE of silica 60 wt.% was 28 ppm; BN 30 wt.%, 25 ppm; alumina 60 wt.%, 39 ppm; and diamond 60 wt.%, 24 ppm. The viscosity of underfill was measured with the cone and plate rheometer. Thermal diffusivity was measured with the laser flash method. Diamond filler loaded underfill showed the highest thermal conductivity 60 wt.%; 1.17 W/mK at 55 °C. Thermal conductivity of underfill was changed with a transition of heat capacity by the temperature increment in same filler content. In case of different filler content, thermal conductivity was changed with a transition of the thermal diffusivity.     

Preparation and properties of polystyrene/SiCw/SiCp thermal conductivity composites

The silicon carbide whisker (SiCw) and silicon carbide particle (SiCp) were employed to prepare polystyrene/silicon carbide whisker/silicon carbide particle (PS/SiCw/SiCp) thermal conductivity composites, and the titanate coupling reagent of NDZ‐105 was introduced to functionalize the surface of fillers. The thermal conductive coefficient λ improved from 0.18 W/mK for native PS to 1.29 W/mK for the composites with 40% volume fraction of SiCw/SiCp (volume fraction, 3 : 1) hybrid fillers. Both the thermal decomposition temperature and dielectric constant of the composites increased with the addition of SiCw/SiCp hybrid fillers. At the same addition of SiCw/SiCp hybrid fillers, the surface modification of hybrid fillers by NDZ‐105 could improve the thermal conductivity and the mechanical properties of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Effect of single‐mineral filler and hybrid‐mineral filler additives on the properties of polypropylene composites

The present study was carried out to determine the filler characteristics and to investigate the effects of three types of mineral fillers (CaCO₃, silica, and mica) and filler loadings (10–40 wt%) on the properties of polypropylene (PP) composites. The characteristics of the particulate fillers, such as mean particle size, particle size distribution, aspect ratio, shape, and degree of crystallinity were identified. In terms of mechanical properties, for all of the filled PP composites, Young's modulus increased, whereas tensile strength and strain at break decreased as the filler loading increased. However, 10 wt% of mica in a PP composite showed a tensile strength comparable with that of unfilled PP. Greater tensile strength of mica/PP composites compared to that of the other composites was observed because of lower percentages of voids and a higher aspect ratio of the filler. Mica/PP also exhibited a lower coefficient of thermal expansion (CTE) compared to that of the other composites. This difference was due to a lower degree of crystallinity of the filler and the CTE value of the mica filler. Scanning electron microscopy was used to examine the structure of fracture surfaces, and there was a gradual change in tensile fracture behavior from ductile to brittle as the filler loading increased. The nucleating ability of the fillers was studied with differential scanning calorimetry, and a drop in crystallinity of the composites was observed with the addition of mineral filler. Studies on the hybridization effect of different (silica and mica) filler ratios on the properties of PP hybrid composites showed that the addition of mica to silica‐PP composites enhanced their tensile strength and modulus. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

SiC/Al2O3/MVQ导热复合材料的制备与性能研究

分别使用碳化硅(SiC)、氧化铝(Al2O3)和SiC/Al2O3复配物制备了导热甲基乙烯基硅橡胶材料(MVQ),研究了SiC,Al2O3和SiC/Al2O3用量及表面改性对MVQ导热系数和力学性能的影响,结果表明,随导热填料用量的增大,MVQ导热系数增大;同等用量下,SiC/Al2O3/MVQ复合材料的导热性能均优于SiC/MVQ和Al2O3/MVQ;当SiC/Al2O3总用量为50份且SiC/Al2O3质量比为3/1时,复合材料导热系数为0.76 W/mK;随SC/Al2O3用量的增加,拉伸强度与拉断伸长率均降低,邵尔A硬度增大.表面处理后,复合材料导热性能得到进一步改善.     

Preparation of polydimethylsiloxane‐coated α‐alumina fillers with cold plasma for elastomer thermal interface materials

A novel method for the organic modification of a ceramic thermal conductive filler (α‐alumina) with cold plasma was developed for the preparation of elastomer thermal interface materials with high thermal conductivities and low moduli. The α‐alumina fillers were first coated with low‐molecular‐weight polydimethylsiloxane (PDMS) by solution dispersion and then treated in argon plasma for different time. The modified α‐alumina fillers were characterized with high‐resolution transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The results revealed that a thin PDMS film with several nanometers thick was tightly coated on the surface of the alumina filler after plasma treatment, and this thin film could not be removed by 48 h of Soxhlet extraction with n‐hexane at 120°C. Plasma modification of the alumina could dramatically weaken the strength of the filler–filler networks and, thus, remarkably reduce the modulus of the alumina‐filled silicone rubber composites but did not affect the thermal conductivity of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Study on thermally conductive ESBR vulcanizates

The thermal conductivities of emulsion polymerized styrene-butadiene rubber (ESBR) vulcanizates filled with alumina (Al₂O₃), zinc oxide (ZnO), carbon nanotubes (CNTs), silicon carbide (SiC), are measured by steady-state method. The effects of types and loadings of the fillers and their mixture on thermal conductivities of the ESBR vulcanizates are investigated. The results show that the thermal conductivity of ESBR vulcanizates filled with alumina or zinc oxide, increases nearly linearly with increasing loading when the filler loading exceeded 20 phr; the ESBR vulcanizates filled with CNTs have the highest thermal conductivity at a given filler loading in comparison with other composite vulcanizates. At a given loading of 100 phr, the ESBR vulcanizate filled with two different particle sizes SiC of 1–3 and 5–11 μm at the mass ratio of 1:1 has the highest thermal conductivity and relatively good mechanical properties. The experimental results are analyzed using Geometric mean model and Agari’s equation to explain the effect of filler types and particle sizes on the formation of thermal conductive networks. The thermal conductivity of the ESBR vulcanizates filled with Al₂O₃ or ZnO or CNTs could be well predicted by optimized parameters using Agari’s equation for a polymer composite filled with mixtures of particles.     

Development of Silicon Carbide Reinforced Jute Epoxy Composites: Physical,Mechanical and Thermo-mechanical Characterizations

The aim of the present study was to investigate the physical and thermo-mechanical characterization of silicon carbide filled needle punch nonwoven jute fiber reinforced epoxy composites. The composite materials were prepared by mixing different weight percentages (0–15 wt.%) of silicon carbide in needle punch nonwoven jute fiber reinforced epoxy composites by hand-lay-up techniques. The physical and mechanical tests have been performed to find the void content, water absorption, hardness, tensile strength, impact strength, fracture toughness and thermo-mechanical properties of the silicon carbide filled jute epoxy composites. The results indicated that increase in silicon carbide filler from 0 to 15 wt.% in the jute epoxy composites increased the void content by 1.49 %, water absorption by 1.83 %, hardness by 39.47 %, tensile strength by 52.5 %, flexural strength by 48.5 %, and impact strength by 14.5 % but on the other hand, decreased the thermal conductivity by 11.62 %. The result also indicated that jute epoxy composites reinforced with 15 wt.% silicon carbide particulate filler presented the highest storage modulus and loss modulus as compared with the unfilled jute epoxy composite.     

Preparation of flexible transparent acryl/alumina nano-hybrid materials exhibiting low thermal expansion coefficient

In this study, flexible transparent hybrid films with low thermal expansion coefficient were prepared by combination of alumina fillers and polymerizable/non-polymerizable surface modifiers with carboxyl group. Four types of alumina fillers with different shape and size were used in this study, and could modify with surface modifiers containing carboxyl groups by electrostatic interaction and disperse homogeneously in resulting hybrid films regardless of the shape and size. So the hybrid films obtained showed high transmittance around 90%T, and it was considered, from transmission electron microscopic analysis, alumina fillers were dispersed at near original filler size, without aggregation. Moreover, thermal mechanical analysis cleared that the use of pillar or fiber type filler is more effective to reduce CTE compared with plate type fillers, especially CTE of hybrid film prepared with fiber type filler was drastically decreased to 17 ppm/K, while the influence by the difference of filler shape/size was not observed on tensile properties, surface hardness. By use of fiber type alumina filler and combination of polymerizable surface modifier and non-polymerizable surface modifier which seems to interact with matrix, for optimizing of the crosslink density, it was possible to reduce CTE, while the good mechanical properties was kept. Finally, hybrid film indicating low CTE value as 19 ppm/K, high flexibility (windable against 0.4 mm radius steel bar), and good tensile properties and surface hardness which were equal to or higher than those of matrix could prepared.     

New composites with high thermal conductivity and low dielectric constant for microelectronic packaging

Three composites based on cyanate (CE) resin, aluminum nitride (AlN), surface‐treated aluminum nitride [AlN(KH560)], and silicon dioxide (SiO₂) for microelectronic packaging, coded as AlN/CE, AlN(KH560)‐SiO₂(KH560)/CE, and AlN‐SiO₂/CE composite, respectively, were developed for the first time. The thermal conductivity and dielectric constant of all composites were investigated in detail. Results show that properties of fillers in composites have great influence on the thermal conductivity and dielectric constant of composites. Surface treatment of fillers is beneficial to increase the thermal conductivity or reduce dielectric constant of the composites. Comparing with binary composite, when the filler content is high, ternary composites possess lower thermal conductivity and dielectric constant. The reasons leading to these outcomes are discussed intensively. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Thermal conductivity,elastic modulus,and coefficient of thermal expansion of polymer composites filled with ceramic particles for electronic packaging

The effective thermal conductivity, elastic modulus, and coefficient of thermal expansion of epoxy resins filled with ceramic fillers like silica, alumina, and aluminum nitride were determined. The data obtained was compared with theoretical and semitheoretical equations in the literature that are used to predict the properties of two phase mixtures. It was found that Agari's model provided a good estimate of the composite thermal conductivity. The Hashin‐Shtrikman lower bound for composite modulus fits the modulus data fairly well at low concentrations of the filler. Also, it was found that the coefficients of thermal expansion of the filled composites lie in between Schapery's upper and lower bounds. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3396–3403, 1999     

A computational and experimental study on the effective properties of Al2O3‐Ni composites

It has been demonstrated that effective medium approximation and mean field homogenization technique is a useful computational tool to predict the effective thermal and structural properties of alumina‐nickel (Al₂O₃‐Ni) composites. Nickel particle size and volume fraction, thermal interface resistance and porosity are found significant factors that affect thermal conductivity, elastoplastic behavior, elastic modulus and thermal expansion coefficient of Al₂O₃‐Ni composite. To complement the computational design, Al₂O₃‐Ni composite samples with designed range of volume fractions and nickel particle size are developed using spark plasma sintering process and properties are measured for model verification.     

Sodium molybdate-hexagonal boron nitride composites enabled by cold sintering for microwave dielectric substrates

To fulfill the demands of more bandwidth in 5G and 6G communication technology, new dielectric substrates that can be co-fired into packages and devices that have low dielectric loss and improved thermal conductivity are desired. The motivation for this study is to design composites with low dielectric loss (tan δ) and high thermal conductivity (κ), while still limiting the electrical conductivity, for microwave applications involving high power and high frequency. This work describes the fabrication of high-density electroceramic composites with a model dielectric material for cold sintering, namely sodium molybdate (Na₂Mo₂O₇), and fillers with higher thermal conductivity such as hexagonal boron nitride. The physical properties of the composites were characterized as a function of filler vol.%, temperature, and frequency. Understanding the variation in measured properties is achieved through analyzing the respective transport mechanisms.     

Effect of particulate fillers on thermal expansions and other critical performances of polycarbonate‐based compositions

Influence of different inorganic particulate mineral fillers on polycarbonate composites was explored. Among all the fillers assessed here only boron nitride and mica could appreciably reduce the thermal expansion of polycarbonate, particularly along the direction of flow. While measured in the normal to flow (cross‐flow) direction, the coefficient of thermal expansion (CTE) values decreased marginally in presence of boron nitride and mica as compared to the unfilled specimen. The anisotropicity in CTE is presumable due to preferential orientation of boron nitride and mica along the direction of flow in the injection molded samples. The effectiveness of fillers in reducing CTE of the polycarbonate composites was correlated to the dispersion of fillers in the polymer matrix. Better dispersion of boron nitride and mica, as observed through SEM, ensured their improved interaction with the matrix and thereby reducing the CTE. It was observed that in presence of particulate fillers the impact performance of the composites decreased appreciably with an increase in tensile modulus, in general. The flow behavior of the composites was by large dependent on the types of fillers used. In presence of some of the fillers such as BaSO₄, ZnO, ZnS, TiO₂, and alumina, flow of the composites increases significantly, primarily associated to appreciable reduction in molecular weights of the polycarbonate. On the other hand, with boron nitride flow remained almost unchanged upon its addition of 5 vol %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Design and development of ceramic-based composites with tailored properties for cutting tool inserts

A successful approach to the development of tailored cutting tool materials requires the development of innovative concepts at each step of manufacturing, from the material design, synthesis of composite powders, to their processing and sintering. In this paper, a computational design approach is applied in the development of reinforced ceramic-based cutting tool inserts with tailored structural and thermal properties. Several potential filler materials are considered at the material design stage for the improvement of structural and thermal properties of a selected matrix material. Properties, such as an improved thermal conductivity and reduced coefficient of thermal expansion are essential for an effective cutting tool insert to absorb thermal shock at varying temperatures. In addition, structural properties such as elastic modulus have to be maintained within a moderate range. A mean-field homogenization theory and effective medium approximation using an in-house code are applied for predicting potential optimum structural and thermal properties for the required application. This is done by considering the effect of inclusions as a function of volume fraction and particle size in the ceramic base matrix. Single inclusion composites such as alumina-silicon (Al₂O₃-SiC) and alumina-cubic boron nitride (Al₂O₃-cBN) as well as hybrid composite such as alumina-silicon-cubic boron nitride (Al₂O₃-SiC-cBN) are developed using the Spark Plasma Sintering (SPS) process in line with the designed range of filler size and volume fraction to validate the computational results. It is found that the computational material design approach is precise enough in predicting the target properties of a designed hybrid composite material for cutting tool inserts.     

A Study of Encapsulation Resin Containing Hexagonal Boron Nitride (hBN) as Inorganic Filler

Preparation and property characterization of encapsulation resin contained hexagonal boron nitride (hBN) as inorganic filler were carried out in this work. The dielectric properties, coefficient of thermal expansion (CTE), thermal conductivity, curing kinetics, adhesion strength and viscosity of the resins with the load of hBN filler ranging from 9.2 to 25.7 vol.% (20–70 wt.%) were evaluated. It was found that the dielectric properties of resin containing SiO₂ filler are inferior to that containing hBN. Also, the resins possessed lower CTE and the higher T _g when the hBN contents were high (>15 vol.%) and the resin containing 25.7 vol.% hBN exhibited the largest thermal conductivity of 1.08 W/m K. Adhesion strength of the composite resins decreased with increase of hBN content and the adhesion strength on various substrates was found to be in the order of: alumina > Si wafer > eutectic PbSn solder. An erratum to this article can be found at     

Silver-filled epoxy composites: effect of hybrid and silane treatment on thermal properties

The combination effects of hybrid nano–micron fillers and filler treatment on the thermal properties of silver-filled epoxy composites are experimentally evaluated. These hybrid composites are fabricated using two different sizes and shapes of silver particles, namely 80 nm with spherical shape and 4–8 μm with flaky shape. In this study, the ratio of silver flakes to silver nanoparticles was varied from 100:0, 75:25, 50:50, 25:75, and 0:100 at a fixed silver loading of 6 vol.%. The silver fillers are treated with 3-aminopropyl triethoxysilane (3AMPTES) at different concentrations of 5, 10, and 30 wt%. The hybrid micro:nano at 50:50 shows the highest storage modulus and the lowest coefficient of thermal expansion (CTE) value compared with other ratios. The silver fillers with 10 wt% of 3AMPTES show improvement in storage modulus, CTE, and thermal stability compared with untreated and further increasing of 3AMPTES at 30 wt% did not show any significant improvement.     

Studies on the Preparation of Polystyrene Thermal Conductivity Composites

Various thermally conductive fillers including aluminum oxide(Al₂O₃), magnesium oxide(MgO), β-silicon carbide particle(β-SiCp) and β-silicon carbide whisker(β-SiCw) were used to prepare polystyrene thermal conductivity composites. Experimental results showed that, for given filler loading, the thermal conductivity of the composites was higher for PS flake than that of PS particle, and the thermal conductivity was optimal by powder blending method. The SiCw filler was more favorable to improve the thermal conductivity of the composites; a much higher thermal conductivity of 1.18 W/mK could be achieved for the composite with 40 vol% SiCw, about six times higher than that of native polystyrene. The experimental thermal conductivity values were in agreement with those predicted by lower bound of Maxwell-Eueken model. For given SiC loading, the thermal conductivity increased with the increasing shape parameter of n. The SiCw was much easier to form the thermal conductivity chains and network than that of SiCp.