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.     

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.     

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.     

LED用低热阻硅脂的制备

选用合适粒径的氮化铝和氧化铝为混杂导热填料、使用自制的硅烷低聚物为表面处理剂,以溶液插层法对混杂导热填料进行表面改性;然后与甲基苯基硅油混合制备了LED用低热阻导热硅脂。研究了导热填料的种类、粒径、表面处理剂种类及用量对导热硅脂的热导率和黏度的影响。采用LED灯作为实际测试平台表征了导热硅脂的导热性能。结果表明,当填料总质量分数为90.9%,粒径为5μm的氮化铝与粒径为1μm的氧化铝作混合填料且质量比为2.8∶1时,导热硅脂的热导率和黏度有较好的平衡;使用填料质量0.5%的硅烷低聚物对氮化铝和氧化铝混合填料进行表面处理有较好的处理效果;自制10号硅脂样品的黏度（25℃）为174 Pa·s,热阻为1.94℃/W,热导率为4.31 W/m·K。     

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     

Development of a ceramic-based composite for direct bonded copper substrate

In the present paper, a computational approach is presented to design alumina-based composite with tailored properties that could replace commercial alumina used in Direct Bonded Copper (DBC) substrates for applications in power electronic modules. A mean-field homogenization and effective medium approximation (EMA) using an in-house code is used for predicting potential optimum thermal and structural properties for DBC substrates by considering the effect of filler type, volume, and size in the alumina matrix. The primary goal for designing such alumina-based composites is to have enhanced thermal conductivity for effective heat dissipation and spreading capabilities together with a coefficient of thermal expansion (CTE) value that is close to the silicon chips in electronic circuits in order to avoid interface layers. At the same time, other functional properties like elastic modulus and electrical conductivity have to be maintained. Our strategy incorporates thermal and structural properties of composites as a constraint on the design process. Among various metallic and carbon-based fillers, chromium, silicon carbide and diamond fillers were found suitable candidates that could enhance the thermal and structural performance of the alumina-based substrates. As a validation, we developed alumina-silicon carbide (Al₂O₃-SiC) composites in line with the designed range of filler size and volume fraction using Spark Plasma Sintering (SPS) process. Thermal and structural properties including thermal conductivity, CTE, and elastic modulus are measured to complement the computational design. It is found that the developed computational design tool is accurate enough in predicting the desired properties of composite materials for DBC substrate applications.     

Hybridized reinforcement of natural rubber with silane‐modified short cellulose fibers and silica

Natural‐rubber‐based hybrid composites were prepared by the mixture of short cellulose fibers and silica of different relative contents with a 20‐phr filler loading with a laboratory two‐roll mill. The processability and tensile properties of the hybrid composites were analyzed. The tensile modulus improved, but the tensile strength and elongation at break decreased with increasing cellulose fiber content. The scorch safety improved with the addition of 5‐phr cellulose fiber in the composites. The Mooney viscosity significantly decreased with increasing cellulose fiber content. To modify the surface properties of the cellulose fiber and silica fillers, a silane coupling agent [bis(triethoxysilylpropyl)tetrasulfide, or Si69] was used. The effects of Si69 treatment on the processing and tensile properties of the hybrid composites were assessed. We found that the silane treatment of both fillers had significant benefits on the processability but little benefit on the rubber reinforcement. The strength of the treated hybrid composite was comparable to that of silica‐reinforced natural rubber. Furthermore, to investigate the filler surface modification and to determine the mixing effects, infrared spectroscopic and various microscopic techniques, respectively, were used. From these results, we concluded that the fillers were better dispersed in the composites, and the compatibility of the fillers and natural rubber increased with silane treatment. In conclusion, the hybridized use of short cellulose fibers from a renewable resource and silica with Si69 presented in this article offers practical benefits for the production of rubber‐based composites having greater processability and more environmental compatibility than conventional silica‐filler‐reinforced rubber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigation of the Influence of Fillers on the Properties of Poly(vinyl acetate) Adhesives

The properties of poly(vinyl acetate) compositions prepared as potential wood adhesives were investigated. The paper presents the results of the influence of various kinds of inorganic fillers based on calcium carbonate and alumino-silicate and an organic filler, starch, on the adhesive composition properties. The comparison among rheological behavior of the adhesive dispersions concerning the specific role of fillers were made. Mechanical and relaxation properties of the adhesive films could reveal the effect of filler characteristics on the polymer matrix. The significant influences of particle size distribution and specific surface area on the poly(vinyl acetate) adhesive composition were determined, along with other filler characteristics.     

Investigation of the Influence of Fillers on the Properties of Poly(vinyl acetate) Adhesives

The properties of poly(vinyl acetate) compositions prepared as potential wood adhesives were investigated. The paper presents the results of the influence of various kinds of inorganic fillers based on calcium carbonate and alumino-silicate and an organic filler, starch, on the adhesive composition properties. The comparison among rheological behavior of the adhesive dispersions concerning the specific role of fillers were made. Mechanical and relaxation properties of the adhesive films could reveal the effect of filler characteristics on the polymer matrix. The significant influences of particle size distribution and specific surface area on the poly(vinyl acetate) adhesive composition were determined, along with other filler characteristics.     

Effect of hybrid reinforcement based on precipitated silica and montmorillonite nanofillers on the mechanical properties of a silicone rubber

Silicone rubber (SR) nanocomposites containing precipitated silica (PS), montmorillonite (MMT), and PS/MMT hybrid fillers were prepared through melt‐mixing technique. In the SR/PS/MMT nanocomposite, the hybrid filler weight ratio was increased progressively from 0.4 to 1.7 while keeping the MMT weight constant. The viscosity, cure characteristics, and mechanical properties of the nanocomposites were subsequently measured. The optimum cure time increased, and the scorch time and rate of cure decreased. Furthermore, when the hybrid filler weight ratio was raised to its optimum, the tensile strength, Young's modulus, modulus at 100 and 300% elongation (M100 and M300), elongation at break, stored energy density at break, and hardness of the nanocomposite improved. The stress–strain properties of the nanocomposite with the hybrid filler improved at high deformation in comparison with those containing the PS and MMT fillers. The MMT filler exfoliated in the SR/MMT nanocomposite but did not in the nanocomposites containing the hybrid filler. Notably, the mechanical properties of the nanocomposite benefitted from the hybrid filler. This was due to the filler–filler and filler–rubber network formation in the rubber by the PS particles. Finally, effect of the PS, MMT, and hybrid fillers on the energy loss or hysteresis of the rubber was measured. POLYM. ENG. SCI., 54:1909–1921, 2014. © 2013 Society of Plastics Engineers     

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%.     

Mechanical and shape‐memory behavior of shape‐memory polymer composites with hybrid fillers

Shape‐memory polymer (SMP) materials have several drawbacks such as low strength, low stiffness and natural insulating tendencies, which seriously limit their development and applications. Much effort has been made to improve their mechanical properties by adding particle or fiber fillers to reinforce the polymer matrix. However, this often leads to the mechanical properties being enhanced slightly, but the shape‐memory effect of reinforced SMP composites being drastically reduced. The experimental results reported here suggested that the mechanical resistive loading and thermal conductivity of a composite (with hybrid filler content of 7.0 wt%) were improved by 160 and 200%, respectively, in comparison with those of pure bulk SMP. Also, the glass transition temperature of the composite was enhanced to 57.28 °C from the 46.38 °C of a composite filled with 5.5 wt% hybrid filler, as determined from differential scanning calorimetry measurements. Finally, the temperature distribution and recovery behavior of specimens were recorded with infrared video in a recovery test, where a 28 V direct current circuit was applied. The effectiveness of carbon black and short carbon fibers being incorporated into a SMP with shape recovery activated by electricity has been demonstrated. These hybrid fillers were explored to improve the mechanical and conductive properties of bulk SMP. Copyright © 2010 Society of Chemical Industry     

Filler-polymer combination: a route to modify gas transport properties of a polymeric membrane

Polydimethylsiloxane (PDMS) has been used as host matrix to prepare hybrid membranes, by a dry phase inversion process, where fillers with different surface and molecular sieving properties have been dispersed. The hybrid membranes have been characterised morphologically by scanning electron microscopy (SEM) and their gas transport properties have been measured at different temperatures.The influence of the temperature and different fillers on the gas separation performance of hybrid membranes has been analysed. These membranes showed higher selectivity values for some gas pairs combined to lower permeabilities with respect to pure PDMS films, as consequence of the contribution of the filler to the transport. A proper filler choice could be used to meet some specific requirements in industrial gas separations.     

A Novel Polymeric Coating with High Thermal Conductivity

A novel polymeric coating with high thermal conductivity was prepared using a hydroxyl-terminated polydimethylsiloxane-modified epoxy resin and hybrid aluminum nitride (AlN) particles with various sizes. It was found that the coating exhibited a maximum thermal conductivity of 1.78 W/m K at 50 wt% filler content and a preferable mass ratio. This was a result of the synergistic effect of hybrid fillers giving rise to a better heat conduction capability as opposed to a coating without fillers. Furthermore, thermogravimetric analysis revealed that the coating exhibited an excellent high temperature resistance owing to the modified matrix and interaction between filler and matrix; and a dielectric study demonstrated that the dielectric constant, volume resistivity and dielectric strength of the coating at 50 wt% filler concentration were 5.6, 8.2 × 10¹³ Ω·cm and 12 kV/mm, respectively. In addition, the mechanical properties declined obviously with filler content.     

Scratch behavior of nanoparticle Al2O3-filled gelatin films

Nanoscale alumina/protein gel composite films with 10–50 wt% filler were subjected to scratch testing and compared to micron-scale alumina/protein gel composites. Atomic force microscopy (AFM) was employed to examine the width, depth, and morphology of the as-produced scratches. The results show that the scratch depth in gelatin films and the tearing within the scratch decrease dramatically with the addition of the nanoscale (average particle size, 13 nm) alumina fillers. It was found that refining the particle size distribution of the Al₂O₃ powder (average particle size, 10 nm, with no particles larger than 70 nm) further reduced the scratch depth and width, while improving the dimensional integrity and surface roughness of the nanocomposites. Aging of the gelatin films improved the intrinsic scratch resistance of both filled and unfilled gelatin films. In comparison, micron-size Al₂O₃ filler not only increased the scratch width, but also resulted in poor particle dispersion and low transparency of the films. The optical clarity of the nanofilled composites was much higher than that of the composites with micron-size filler.     

Stabilized dispersions of titania nanoparticles via a sol–gel process and applications in UV‐curable hybrid systems

Organic–inorganic hybrid UV‐curable coatings were synthesized through blending UV‐curable components and stabilized titania sol prepared via a sol–gel process of tetrabutyl titanate (TBT) with three different stabilizers, acetylacetone (Acac), isopropyl tri(dioctyl)pyrophosphato titanate coupling agent (TTPO) and a polymerizable organic phosphoric acid (MAP). The size and the dispersion of titania particle in the UV‐cured organic matrix were dominated by the properties of these stabilizers. A cured hybrid film with titania particle size around 20 nm was obtained when TTPO was utilized as protection agent for the sol. It is interesting that the hardness and flexibility of the photocured hybrid films were improved simultaneously, in contrast to results with neat organic UV‐curable formulations. Copyright © 2006 Society of Chemical Industry     

The use of noncovalently modified carbon nanotubes for preparation of hybrid polymeric composite materials with electrically conductive and lightning resistant properties

In this work, approach to use of noncovalently modified carbon nanotubes is given for preparation of functional hybrid polymeric composite materials (HPCM) based on epoxy resin. Conductive glass‐fiber plastics with resistivity in transverse and lengthwise direction 9.0·× 10² and 30–50 Ohm cm, respectively, were obtained. The tetrafluoroethylene telomer and fluorocontaining organosilicon copolymer with amino groups were used as modifiers for carbon nanotubes. Thermal, electrical, and mechanical properties of the obtained materials were studied. The mechanism of the effect of noncovalent modification of carbon nanotubes on functional properties of HPCM was discussed. It was found, that type of modifier significantly affects the level of functional properties. The use of fluorocontaining organosilicon copolymer is more optimal in comparison with tetrafluoroethylene telomer. Thus, HPCM with carbon‐fiber filler and this modifier has higher electrical conductivity and lightning strike resistance in comparison with nonmodified HPCM. This approach is promising to impart antistatic properties for glass‐fiber plastics and increase lightning resistance of carbon‐fiber plastics. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46108.     

Improvement in physical and electrical properties of poly(vinyl alcohol) hydrogel conductive polymer composites

With an aim to develop anti‐electrostatic discharge materials based on biodegradable polymers, poly(vinyl alcohol) films composited with two different conductive fillers (carbon black and aluminium) at various fillers contents (20?60%wt), were manufactured using solvent‐casting technique. The mechanical properties of such the films were investigated through tensile stress‐strain tests. Wettability and morphology of the composite films were performed by water contact angle measurement and SEM, respectively. Young's modulus of the composite films can be increased with the addition of conductive fillers. The surface of the composite films showed non‐homogeneous appearance, in which the phase boundary within the composites was clearly observed and the conductive fillers formed aggregation structure at high filler concentration. In addition, the composite films exhibited better hydrophobicity when higher conductive filler content was added. TGA results suggested that both carbon black and aluminum have proven their efficiency to enhance thermal stability of poly(vinyl alcohol). Investigation of cross‐cut adhesion performance of the prepared composite films revealed that carbon black‐filled composites exhibited excellent adhesion strength. The effect of conductive filler content on surface resistivity of the composite films was also examined. The experimental results confirmed that both the fillers used in this study can improve the electrical conductivity of poly(vinyl alcohol) hydrogel. The surface resistivity of the composite films was reduced by several orders of magnitude when the filler of its critical concentration was applied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42234.     

Thermal conductivity of polypropylene composites with hybrid fillers of boron nitride and vapor‐grown carbon fiber

High thermal conductivity fillers of boron nitride (BN) and vapor‐grown carbon fiber (VGCF) were used alone or incorporate to prepare polypropylene (PP) composites. The effects of filler content, particle size and shape, and single vs. hybrid BN/VGCF fillers were investigated with respect to the thermal conductivity of the PP composites. The thermal conductivity of PP/BN composites depended upon the content and particle size of the BN. Increased content and length of VGCF had the effect of increasing the thermal conductivity of the PP composites. Hybrid fillers were created with a mixture of medium‐sized BN and long‐length VGCF; hybrid BN/VGCF fillers enhanced the thermal conductivity of PP composites with a lower total content compared with PP composites containing only medium‐sized BN particles. POLYM. COMPOS., 37:936–942, 2016. © 2014 Society of Plastics Engineers     

The effect of alkali treatment and filler size on the properties of sawdust/UPR composites based on recycled PET wastes

In this study, natural sawdust fillers from acacia were mixed with unsaturated polyester resin (UPR), which was prepared by recycling of polyethylene terephthalate (PET) waste bottles to prepare sawdust/UPR composite. PET wastes were recycled through glycolysis and depolymerized to produce a formulation for the resin. The effects of alkali treatment, filler content, and filler size on the tensile, flexural, hardness, and water absorption of the composites were investigated. The results show that the modulus of both tensile and flexural increased with increasing filler contents, but the tensile and flexural strength of composites decreased. The size of sawdust also played a significant role in the mechanical properties, with smaller size sawdust producing higher strength and modulus. This is due to the greater surface area for filler–matrix interaction. The results also show that alkali treatment causes a better adhesion between sawdust and UPR matrix and improves the mechanical properties of the composites. Furthermore, surface treatment reduced the water absorption of composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008