Effect of the particle size of Al2O3 on the properties of filled heat‐conductive silicone rubber

An elastomeric thermal pad with a thermal conductivity of 1.45 W/m K, needed for the heat dissipation of microelectronics, was obtained with hybrid alumina of different particle sizes as a filler and silicone rubber (vinyl‐end‐blocked polymethylsiloxane) as the matrix. The effects of the amount, particle size, and mixing mass ratio of the filler particles on the thermal conductivity and mechanical properties of silicone rubber were investigated. The results indicated that the thermal conductivity of the rubber filled with larger particles was superior to that of the rubber filled with the smaller grain size, and the rubber incorporated with a mixture of hybrid particles at a preferable mass ratio exhibited higher thermal conductivity than the rubber for which a filler with only a single particle size was used. In addition, the surface treatment of the hybrid filler with 3‐methacryloyloxypropyltrimethoxysilane could increase the thermal conductivity of the composite rubber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1312–1318, 2007     

Thermal,electrical, and mechanical properties of addition-type liquid silicone rubber co-filled with Al2O3 particles and BN sheets

The addition-type liquid silicone rubber (ALSR) co-filled with spheroidal Al₂O₃ and flaky BN was prepared by the mechanical blending and hot press methods to enhance the thermal, electrical, and mechanical properties for industrial applications. Morphologies of ALSR composites were observed by scanning electron microscopy (SEM). It was found that the interaction and dispersion state of fillers in the ALSR matrix were improved by the introduction of BN sheets. Thermal, electrical, and mechanical performances of the ALSR composites were also investigated in this work. The result indicated that the thermal conductivity of ALSR can reach 0.64 W m⁻¹ K⁻¹ at the loading of 20 wt% Al₂O₃/20 wt% BN, which is 3.76 times higher than that of pure ALSR. The addition of Al₂O₃ particles and BN sheets also improve the thermal stability of ALSR composites. Moreover, pure ALSR and ALSR composites showed relatively lower dielectric permittivity (1.9–3.1) and dielectric loss factor (<0.001) at the frequency of 10³ Hz. The insulation properties including volume resistivity and breakdown strength were improved by the introduction of flaky BN in the ALSR matrix. The volume resistivity and characteristic breakdown strength E₀ are 6.68 × 10¹⁵ Ω m and 93 kV/mm, respectively, at the loading of 20 wt% Al₂O₃/20 wt% BN. In addition, the mechanical characteristics including elongation at break and tensile strength of ALSR composites were also enhanced by co-filled fillers. The combination of these improved performances makes the co-filled ALSR composites attractive in the field of electrical and electronic applications.     

高岭土填充橡胶共混物的性能及表征

以一种高岭土为增强相,分别填充天然橡胶、丁苯橡胶、顺丁橡胶、丁腈橡胶、三元乙丙橡胶、氯丁橡胶和硅橡胶,制备高岭土/橡胶复合材料,通过力学和热老化性能测试、红外光谱和偏光显微镜测试分析,确定了高岭土在各种橡胶中填充的最佳配比,研究高岭土的用量对橡胶力学性能、热老化性能和相容性上的影响,并与白炭黑填充橡胶进行比较。实验表明,除扯断伸长率外,高岭土/橡胶具有优异的力学和耐热性能,高岭土与橡胶有较好的相容性,且适合刚性橡胶的补强。     

氮化硼填充甲基乙烯基硅橡胶导热复合材料的性能

用0.3,6.0,20.0μm 3种粒径的氮化硼(BN)(质量比为1:1:3)混合填充甲基乙烯基硅橡胶(MVQ),研究了BN用量对MVQ导热系数、热失重、热膨胀系数、硫化特性的影响.结果表明,随着BN用量的增加,MVQ的导热系数和热分解温度升高,热失重量和热膨胀系数明显降低,但对MVQ的硫化反应影响不大;当BN填充量为150份时,MVQ的综合性能较佳.     

Ablation properties of zinc borate and aluminum hypophosphite filled silicone rubber composites

The ablative properties of epoxy modified silicone rubber composites filled with zinc borate (ZB) and aluminum hypophosphite (AHP) were studied. The decomposition of the added fillers and covering connection of residual on the substrate contribute to the improvement of heat insulation. The ablation test shows that the formation of a dense char layer with certain strength is key to improving the ablative properties. The optimal ablative performance is achieved when the concentration of ZB and AHP is 10 and 5 phr, respectively. Under such circumstances, the linear ablation rate is as low as 0.032 mm/s, which is about 61% lower than the pure silicone rubber. Furthermore, the structure and composition of the formed char layer were analyzed using X-ray diffraction analysis, scanning electron microscopy, and Fourier transform infrared spectroscopy.     

Thermal and mechanical properties of liquid silicone rubber composites filled with functionalized graphene oxide

To improve the thermal and mechanical properties of liquid silicone rubber (LSR) for application, the graphene oxide (GO) was proposed to reinforce the LSR. The GO was functionalized with triethoxyvinylsilane (TEVS) by dehydration reaction to improve the dispersion and compatibility in the matrix. The structure of the functionalized graphene oxide (TEVS‐GO) was evaluated by Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD), and energy dispersive X‐ray spectroscopy (EDX). It was found that the TEVS was successfully grafted on the surface of GO. The TEVS‐GO/LSR composites were prepared via in situ polymerization. The structure of the composites was verified by FTIR, XRD, and scanning electron microscopy (SEM). The thermal properties of the composites were characterized by TGA and thermal conductivity. The results showed that the 10% weight loss temperature (T₁₀) increased 16.0°C with only 0.3 wt % addition of TEVS‐GO and the thermal conductivity possessed a two‐fold increase, compared to the pure LSR. Furthermore, the mechanical properties were studied and results revealed that the TEVS‐GO/LSR composites with 0.3 wt % TEVS‐GO displayed a 2.3‐fold increase in tensile strength, a 2.79‐fold enhancement in tear strength, and a 1.97‐fold reinforcement in shear strength compared with the neat LSR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42582.     

Synchronization of thermal properties and constituents in Nanocomposite: Manufacturing,characterization, adjustable properties

This is critical to maintain better thermal properties, especially thermal conductivity as well as low particle content along with organized particle dispersion in polymer nanocomposites. Thus, this study is designed to develop a nanocomposite containing a constant reinforcing load of binary particles (carbon and alumina) in the binary matrix of polypropylene (PP)/poly ethylene-co-vinyl acetate (EVA). The samples were prepared through the melt blending and hot pressing technique. Compared to pure PP/EVA matrix, the nanocomposites showed a shift in Fourier-transform infrared spectroscopy peak and absorption intensity, which proves better interaction of nanoparticles with the matrix. The Scanning Electron Microscopy analysis showed the nanocomposite having carbon (C) and alumina (A) relative ratio 2:3 offered even structure with better distribution of nanoparticles compared to other nanocomposites. Also, Differential scanning calorimetry and Thermogravimetric analysis revealed that alumina-rich binary nanoparticles reinforced composites offer an efficient improvement in thermal behavior. Moreover, the nanocomposite containing high alumina relative ratio (C: A = 2:3) gives a sharp shift in thermal conductivity of 1.57 W/m-k from 1.2 W/m-k of carbon-rich nanocomposite (C: A = 3:2) and 0.16 W/m-k of pure PP/EVA. However, these relative properties emphasize the important role of this nanocomposite as a programmable thermal material.     

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.     

Property reinforcement of silicone dielectric elastomers filled with self‐prepared calcium copper titanate particles

In this article, submicron and micron calcium copper titanate (CCTO) crystallites with different morphologies were successfully designed and prepared by directly thermal treatment method and molten salt method, respectively. Then, the silicone elastomer filled with self‐prepared CCTO particles had high dieletric constant, low dielectric loss, and actuated strain which was greatly improved at low electric field. The dieletric constant at 50 Hz obviously increased from 2.15 for pure silicone elastomer to 4.37 and 4.18 for the submicron and micron CCTO/poly (dimethyl siloxane) (PDMS) composites. The dielectric loss of the composites retained at a low value (less than 0.06). Meanwhile, the elastic modulus of CCTO/PDMS composites was increased slightly only with a good flexibility. Compared to pure silicone elastomer (2.25%), the submicron and micron CCTO/PDMS composites with 2 wt % content exhibited a greater strain of 7.69% and 9.83% at a low electric field of 5 V/μm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42613.     

Ablation properties of aluminum silicate ceramic fibers and calcium carbonate filled silicone rubber composites

The ablative performance of aluminum silicate ceramic fiber (ASF) and calcium carbonate (CaCO₃) filled silicone rubber composites prepared through a two‐roll mill was examined. The properties of the composites were investigated by thermogravimetry, thermal conductivity measurements, and oxyacetylene torch testing. After the material was burnt, the structure and composition of the char were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy (SEM). The results of the ablation test showed that the ablation resistance improved greatly in an appropriate filler scope. Combined with SEM, it was proven that a firm, dense, and thermal insulation layer, which formed on the composites surface during the oxyacetylene torch test, was a critical factor in determining the ablation properties. Thermogravimetric analysis revealed that the thermal stability of the composites was enhanced by the incorporation of ASF and CaCO₃. The thermal conductivity measurements showed that the silicone rubber composites had a very low thermal conductivity ranging from 0.206 to 0.442 W m^?1 K^?1; this significantly prevented heat from transferring into the inner matrix at the beginning of the burning process. The proportion of 20/40 phr (ASF/CaCO₃) was optimum for improving the ablation resistance of the silicone rubber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41619.     

DC current voltage characteristics of silicone rubber filled with conductive carbon black

Direct current (DC) current‐voltage (I‐V) characteristics of silicone rubber filled with conductive carbon black (CB) were studied at room temperature in the voltage range of 1–46 V. The current‐voltage relationship can be expressed as I = AV^B, where A and B are constants that show capability and property of electrical conduction, respectively. The I‐V curve can be divided into ohmic and nonohmic regions. In nonohmic region, B < 1, and the resistance increases with the rise of voltage. Higher CB loading leads to lower transforming voltage from ohmic to nonohmic region and much deviation from Ohm's law. The reason for this deviation is the unbalance between the heat generated and the heat loss of conductive silicone rubber during the measurement. When the heat effect is eliminated completely, the electrical conduction is ohmic. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 587–592, 2004     

高结构导电炭黑填充硅橡胶复合材料的性能

研究了导电炭黑（ＨＧ－ＣＢ）的高结构对乙烯基甲基硅橡胶（ＶＭＱ－１１０）复合材料电性能和机构性能的影响。由ＴＥＭ观察看出,随ＨＧ－ＣＢ用量增加,其在硫化胶中形成的导电网络逐渐完善,用量达１９份（质量份,下同）时已形成完整的导电网络,导电机理可用电子隧道效应来解释,同时随ＨＧ－ＣＢ填充量增加,复合材料的拉伸强度、硬度增大,但对ＶＭＱ－１１０的硫化有影响。欠硫现象严重,ＨＧ－ＣＢ的用量一般控制在１０～１５份,所得硅橡胶复合材料具有较佳的电性能和机械性能。     

Composites based on CB/CF/Ag filled EPDM/NBR rubber blends with high conductivity

For many applications of conductive rubbers, it is desirable to endow the conductive rubber with high conductivity at low conductive filler loading. In this work, composites based on ethylene‐propylene‐diene monomer (EPDM) rubber and nitrile‐butadiene rubber (NBR) were prepared using carbon blacks, carbon fibers, and silver powders as fillers. As the weight fraction of silver powder increased, the hardness of composites increased gradually while the tensile strength and elongation at break decreased. SEM revealed that the EPDM/NBR blends exhibited a relatively co‐continuous morphology. The differential scanning calorimetry (DSC) curves reported the EPDM/NBR rubber blends were incompatibility. The thermogravimetry (TG) studies showed that adding a small amount of silver powder could improve the thermal stability of composites. These conductive composites exhibited good electrical property. At room temperature, when the total volume fraction of fillers was 15.20%, the volume resistivity of EPDM/NBR blend was only 0.0058 Ω cm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41357.     

Enhancement in ammonia sensitivity with fast response by doping Al2O3 in polyaniline

Al₂O₃ mixed polyaniline composite with different dopant concentrations have been synthesized successfully by chemical oxidation method. X‐ray diffraction, Fourier transform infrared spectroscopy, and UV–visible spectroscopy confirm the synthesis of the polyaniline and Al₂O₃ mixed polyaniline composite. Scanning electron microscopy shows the weak crystalline quality of the samples. The samples are found sensitive to ammonia gas. The sensing properties have been studied at different temperatures i.e. 25°C, 50°C, and 100°C by varying the ammonia concentration over a range of 100–1500 ppm. The sensitivity increases with increasing Al₂O₃ concentration, increasing ammonia concentration, and also with increasing the sensing temperature. Sensitivity of these samples to ammonia gas is good with fast response. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1941–1948, 2013     

填充氧化铝粉的高导热软质硅橡胶材料的制备

通过在软质硅橡胶中填充氧化铝粉制备了导热硅橡胶复合材料,分析了导热材料的热导率和硬度与氧化铝粉的粒径及填充量之间的关系,并对其变化趋势进行了探讨。结果表明,当不同粒径氧化铝的质量配比75μm/40μm/2μm为6/2/2时,氧化铝在硅橡胶中的填充质量分数可达到最高的80%,从而提高了硅橡胶的导热性能,此时硅橡胶复合材料的热导率为4.02 W/m·K,邵尔00硬度为78,可以满足电子元器件对于高导热、超柔软散热材料的需求。     

In situ sintered silver decorated 3D structure of cellulose scaffold for highly thermoconductive electromagnetic interference shielding epoxy nanocomposites

This study presents a 3-dimensional (3D) network structure of cellulose scaffold (CS), which was in situ decorated with silver nanoparticles (AgNPs). The scaffold was then infiltrated with epoxy matrix and cured at elevated temperature to sinter the AgNPs; finally, highly thermoconductive epoxy composites (Ag@CS/epoxy) was obtained. The resultant Ag@CS20/epoxy composite reached a thermal conductivity of 2.52 W·m⁻¹·K⁻¹ at 2.2 vol% of filler loading, which shows an enhancement of over 11-folds in the thermal conductivity compared to the neat epoxy. The superb electrical conductivity value of over 53,691 S·m⁻¹ of the Ag@CS20/epoxy was achieved, which led to exceptional EMI SE values of 69.1 dB. Furthermore, surface temperatures during heating and cooling were also investigated to demonstrate the superior heat dissipating capacity of the Ag@CS/epoxy composite, which can be potentially put an application as thermal dissipating material in the next generation of electronics.     

碳纳米管／Al2O3／硅橡胶导热复合材料结构和性能的研究

将碳纳米管混入Al2O3 /硅橡胶复合材料中,制得了导热硅橡胶复合材料并对其进行了研究。结果表明：随着碳纳米管用量的增加,材料导热性能逐渐增加;碳纳米管有助于填料网络结构的形成．达到了协同增加导热性能的效果;原预想碳纳米管在体系中伸展后能形成导热通路,可大幅提高导热效率．但由于开炼共混时未能保存住其高长径比的特点,增益效果不够显著。     

Thermal conductivity improvement in electrically insulating silicone rubber composites by the construction of hybrid three-dimensional filler networks with boron nitride and carbon nanotubes

In this study, we constructed hybrid three-dimensional (3D) filler networks by simply incorporating a relatively low content of one-dimensional carbon nanotubes (CNTs; 0.0005–0.25 vol %) and a certain content of two-dimensional boron nitride (BN; 30 phr) in a silicone rubber (SIR) matrix. As indicated by transmission electron microscopy observation, flexible CNTs can serve as bridges to connect BN platelets in different layers to form hybrid 3D thermally conductive networks; this results in an increase in thermally conductive pathways, and the isolation between CNTs can prevent the formation of electrically conductive networks. Compared to the SIR–BN composite with the same BN content, the SIR–BN–CNT composites exhibited improved thermal conductivity, slightly increased volume resistivity, and comparable breakdown strength without a largely decreased flexibility. When 0.25 vol % CNTs were incorporated, the SIR–BN–CNT composite exhibited 75 and 25% higher thermal conductivities relative to the neat SIR and SIR–BN composite with 30 phr BN, respectively, and a thermal conductivity that was even comparable to SIR–BN composite with 40 phr BN. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46929.     

Ultra-high compression and wear resistant hybrid filled polyimide composite: Synergistic effect of Fe2O3 decorated RGO

Herein, the tribological performance, thermal and compression resistance behavior of polyimide (PI) reinforced by Fe₂O₃ decorated reduced graphene is systematically investigated. The remarkable synergistic effect of Fe₂O₃ decorated reduced graphene oxide (RGO) is demonstrated in its PI wear resistance, and PI/RGO/Fe₂O₃ composites show good thermal stability and much higher compression resistant ability than PI, PI/RGO, and PI/Fe₂O₃ composites when the filling contents are same. Additionally, the PI/RGO/Fe₂O₃ composites also exhibited ultra-wear-resistant properties under high load condition, and the lowest wear rate is 3.18 × 10⁻⁸ mm³N⁻¹ m⁻¹, which is an order of magnitude lower than that of pure PI. The investigation of its tribological mechanism also showed strong synergistic effect and interface force of Fe₂O₃ decorated RGO, which contribute to its high-performance friction-reducing behaviors. These findings give an inside view to Fe₂O₃ decorated RGO and its polyimide composites, and open an avenue for the graphene oxide (GO) based composite to act as compression wear-resisting solid fillers and lubricants when polymer composite with excellent compressive, thermal and tribological properties is required.     

Thermal stability and ablation properties study of aluminum silicate ceramic fiber and acicular wollastonite filled silicone rubber composite

The thermal stability and ablation properties of silicone rubber filled with silica (SiO₂), aluminum silicate ceramic fiber (ASF), and acicular wollastonite (AW) were studied in this article. The morphology, composition, and ablation properties of the composite were analyzed after oxyacetylene torch tests. There were three different ceramic layers found in the ablated composite. In the porous ceramic layer, the rubber was decomposed, producing trimers, tetramers, and SiO₂. ASF and part of AW still remained and formed a dense layer. The SiO₂/SiC filaments in the ceramic layer reduced the permeability of oxygen, improving the ablation properties of the composites. The resultant ceramic layer was the densest, which acted as effective oxygen and heat barriers, and the achieved line ablation rate of the silicone composite were optimum at the proportion of 20 phr/40 phr (ASF/AW). Thermogravimetric analysis (TGA) confirmed that thermal stability of the composites was enhanced by the incorporation of ASF and AW. The formation of the ceramic layer was considered to be responsible for the enhancement of thermal stability and ablation properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39700.