取向碳化硅晶须硅橡胶复合材料导热性及绝缘性

于天骄; 宋伟; 冯景涛; 彭修峰; 宋文宏

doi:10.13801/j.cnki.fhclxb.20230404.002

取向碳化硅晶须硅橡胶复合材料导热性及绝缘性

doi: 10.13801/j.cnki.fhclxb.20230404.002

1.
哈尔滨理工大学　电气与电子工程学院，工程电介质及其应用教育部重点实验室，哈尔滨 150086
2.
上海拜高高分子材料有限公司，上海 201400

基金项目: 国家自然科学基金(51541702；51607048)

详细信息

通讯作者:
宋伟，博士，教授，博士生导师，研究方向为导热复合材料研发及绝缘材料改性研究　E-mail: sw7912@hrbust.edu.cn

中图分类号: TM211；TB333
计量
- 文章访问数: 639
- HTML全文浏览量: 291
- PDF下载量: 51
- 被引次数: 0
出版历程
- 收稿日期: 2023-02-27
- 修回日期: 2023-03-20
- 录用日期: 2023-03-27
- 网络出版日期: 2023-04-06
- 刊出日期: 2024-01-01

Research on thermal conductivity and insulation of oriented silicon carbide whisker silicone rubber composites

1.
Key Laboratory of Engineering Dielectric and Its Application, Ministry of Education, School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150086, China
2.
Shanghai Baigao Polymer Material CO., LTD., Shanghai 201400, China

Funds: National Natural Science Foundation of China (51541702; 51607048)

摘要

摘要: 随着电子产品的集成密度和功率密度不断增加，优化热界面材料变的尤为重要。本文以一维碳化硅晶须(SiC_w)为填料，硅橡胶为基体制备出导热硅橡胶复合材料，综合分析了复合材料的微观形貌、物相结构、导热性及绝缘性。首先通过共沉淀法制备出Fe₃O₄对SiC_w包覆的改性材料，其次将包覆Fe₃O₄的SiC_w在液体硅橡胶基体中分散均匀，最后将其置于恒稳磁场中完成晶须取向及基体固化。结果表明：SiC_w晶须表面包覆一层Fe₃O₄纳米颗粒且在硅橡胶基体中呈现取向排列，制备出SiC_w取向结构的硅橡胶复合材料。当取向SiC_w含量达到10wt%时，相比于纯硅橡胶导热系数可提升72%，比未取向10wt%SiC_w填充的高40%。相比于纯硅橡胶体积电阻率下降两个数量级，但仍然具有良好的绝缘性。通过COMSOL对SiC_w随机分散与取向排列的硅橡胶复合材料进行模拟仿真，仿真结果表明，含量10wt%的SiC_w可使硅橡胶导热系数提升60%，体积电阻率在10¹⁵ Ω∙cm以上，而10wt%取向SiC_w可使硅橡胶导热系数提升170%，体积电阻率在10¹⁴ Ω∙cm以上，与实验结果的趋势相一致。
- 硅橡胶 /
- 碳化硅晶须 /
- 取向 /
- 导热性 /
- 绝缘性
Abstract: With the increasing integration density and power density of electronic products. It is particularly important to optimize the research of thermal interface materials. In this paper, one-dimensional silicon carbide whisker (SiC_w) was used as filler and silicone rubber was used as matrix to prepare thermal conductive silicone rubber composites. The microstructure, phase structure, thermal conductivity and insulation of the composites were comprehensively analyzed. Firstly, the modified material of SiC_w coated by Fe₃O₄ was prepared by coprecipitation method. Secondly, SiC_w coated with Fe₃O₄ was evenly dispersed in the liquid silicone rubber matrix. Finally, it is placed in a constant magnetic field to complete whisker orientation and matrix curing. The results show that the surface of SiC_w whiskers is coated with Fe₃O₄ nanoparticles, and they are oriented in the silicone rubber matrix. Silicone rubber composites with SiC_w oriented structure were prepared. When the oriented SiC_w reaches 10wt%, the thermal conductivity can be increased by 72% compared with pure silicone rubber, and it is 40% higher than that filled with non-oriented 10wt%SiC_w. Compared with pure silicone rubber, the volume resistivity decreases by two orders of magnitude. But it still has good insulation. The silicone rubber composites with randomly dispersed and oriented SiC_w were simulated by COMSOL. The simulation results show that the thermal conductivity of silicone rubber can be improved by 60% with 10wt%SiC_w. The volume resistivity is above 10¹⁵ Ω∙cm. However, 10wt% oriented SiC_w can improve the thermal conductivity of silicone rubber by 170% and the volume resistivity is above 10¹⁴ Ω∙cm. It is consistent with the trend of experimental results.
- silicone rubber /
- silicon carbide whisker /
- orientation /
- thermal conductivity /
- insulation

HTML全文

图 1 Fe₃O₄包覆碳化硅晶须(SiC_w)的制备流程

Figure 1. Preparation process of Fe₃O₄ coated SiC whisker (SiC_w)

下载: 全尺寸图片幻灯片

图 2 硅橡胶复合材料制备流程

Figure 2. Preparation process of silicone rubber composites

下载: 全尺寸图片幻灯片

图 3 XRD测试示意图

Figure 3. Schematic diagram of XRD test

下载: 全尺寸图片幻灯片

图 4 SiC_w及FE@SIC的SEM图像

Figure 4. SEM images of SiC_w and FE@SIC

下载: 全尺寸图片幻灯片

图 5 硅橡胶(SR)试样断面SEM图像

Figure 5. SEM images of silicone rubber (SR) section

下载: 全尺寸图片幻灯片

图 6 Fe₃O₄及FE@SIC的XRD图谱

Figure 6. XRD patterns of Fe₃O₄ and FE@SIC

下载: 全尺寸图片幻灯片

图 7 SR、SIC10、SICFE10*、FE@SIC10、FE@SIC10*的XRD图谱

Figure 7. XRD patterns of SR, SIC10, SICFE10*, FE@SIC10, FE@SIC10*

下载: 全尺寸图片幻灯片

图 8 SiC_w/SR导热系数对数值线性拟合图

Figure 8. Linear fitting diagram of SiC_w/SR thermal conductivity versus numerical value

下载: 全尺寸图片幻灯片

图 9 导热模型与SiC_w/SR的导热系数折线图

Figure 9. Thermal conductivity model and thermal conductivity line chart of SiC_w/SR

下载: 全尺寸图片幻灯片

图 10 SIC10、FE@SIC10*截面模拟图

Figure 10. Simulation diagram of SIC10, FE@SIC10* section

下载: 全尺寸图片幻灯片

图 11 FE@SIC10*与SIC10的几何仿真模型

Figure 11. Geometric simulation model diagram of FE@SIC10* and SIC10

下载: 全尺寸图片幻灯片

图 12 FE@SIC10*和SIC10几何模型在热场下的温度分布

Figure 12. Temperature distribution of geometric model of FE@SIC10* and SIC10 under thermal field

下载: 全尺寸图片幻灯片

表 1 仿真与实验数据对比表

Table 1. The comparison table of simulation results and experimental data

	Experimental data		Simulation results
Name of sample	SIC10	SIC10@FE10*	SIC10	SIC10@FE10*
Thermal conductivity/(W/(m·K))	0.167	0.235	0.221	0.374
Volume resistivity/Ω·cm	3.71×10¹⁵	8.11×10¹⁴	4×10¹⁵	1×10¹⁴

下载: 导出CSV

表 1 试样编号明细表

Table 1. Specimen details

Name of sample	Detailed description
FE@SIC	Fe₃O₄ coated SiC_w
SR	Pure silicone rubber sample
SiC_w/SR	SiC_w filled silicone rubber series samples
SIC10	10wt% SiC_w filled silicone rubber sample
FE@SIC10*	Magnetized sample of 10wt%FE@SIC silicone rubber
FE@SIC10	10wt%FE@SIC silicone rubber sample
SICFE10*	Magnetized sample of 10wt%SiC_w+Fe₃O₄ silicone rubber

下载: 导出CSV

表 2 SiC_w/SR的导热系数

Table 2. Thermal conductivity of SiC_w/SR

SiC_w/SR/wt%	Thermal conductivity/(W·(m·K)⁻¹)
0	0.137
5	0.148
10	0.167
15	0.181
20	0.236

下载: 导出CSV

表 3 FE@SIC10*导热系数对比表

Table 3. Comparison table of thermal conductivity of FE@SIC10*

Name of sample	Thermal conductivity/(W·(m·K)⁻¹)
SR	0.137
SIC10	0.167
SICFE10*	0.172
FE@SIC10	0.168
FE@SIC10*	0.235

下载: 导出CSV

表 4 SiC_w/SR体积电阻率

Table 4. Volume resistivity of SiC_w/SR

SiC_w/SR/wt%	Volume resistivity/(Ω·cm)
0	4.00×10¹⁶
5	7.84×10¹⁵
10	3.70×10¹⁵
15	5.60×10¹⁴
20	3.90×10¹⁴

下载: 导出CSV

表 5 FE@SIC10*体积电阻率对比

Table 5. Comparison of volume resistivity of FE@SIC10*

Name of sample	Volume resistivity/(Ω·cm)
SR	4.0×10¹⁶
SIC10	3.7×10¹⁵
FE@SIC10*	8.1×10¹⁴

下载: 导出CSV

表 6 试样性能的仿真与实验数据对比

Table 6. Comparison of simulation results and experimental data of sample properties

Sample	Thermal conductivity/(W·(m·K)⁻¹)		Volume resistivity/(Ω·cm)
Sample	Experimental data	Simulation results	Experimental data	Simulation results
SIC10	0.167	0.221	3.70×10¹⁵	4.00×10¹⁵
SIC10@ FE10*	0.235	0.374	8.11×10¹⁴	1.00×10¹⁴

下载: 导出CSV

参考文献(26)

[1]	FENG C P, YANG L Y, YANG J, et al. Recent advances in polymer-based thermal interface materials for thermal management: A mini-review[J]. Composites Communications,2020,22:100528. doi: 10.1016/j.coco.2020.100528
[2]	XUE Y, WANG H S, LI X F, et al. Exceptionally thermally conductive and electrical insulating multilaminar aligned silicone rubber flexible composites with highly oriented and dispersed filler network by mechanical shearing[J]. Composites Part A: Applied Science and Manufacturing,2021,144:106336. doi: 10.1016/j.compositesa.2021.106336
[3]	ZHANG L, DENG H, FU Q. Recent progress on thermal conductive and electrical insulating polymer composites[J]. Composites Communications,2018,8:74-82. doi: 10.1016/j.coco.2017.11.004
[4]	周文英, 王蕴, 曹国政, 等. 本征导热高分子材料研究进展[J]. 复合材料学报, 2021, 38(7):2038-2055. doi: 10.13801/j.cnki.fhclxb.20210312.001 ZHOU Wenying, WANG Yun, CAO Guozheng, et al. Research progress of polymer materials with intrinsic heat conduction[J]. Acta Materiae Compositae Sinica,2021,38(7):2038-2055(in Chinese). doi: 10.13801/j.cnki.fhclxb.20210312.001
[5]	NIU H Y, REN Y J, GUO H C, et al. Recent progress on thermally conductive and electrical insulating rubber composites: Design, processing and applications[J]. Composites Communications,2020,22:100430. doi: 10.1016/j.coco.2020.100430
[6]	ZHANG H, ZHANG X W, FANG Z, et al. Recent advances in preparation, mechanisms, and applications of thermally conductive polymer composites: A review[J]. Journal of Composites Science,2020,4(4):180-226. doi: 10.3390/jcs4040180
[7]	VYSOTSKY V V, ROLDUGHIN V I. Aggregate structure and percolation properties of metal-filled polymer films[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects,1999,160(2):171-180. doi: 10.1016/S0927-7757(99)00355-6
[8]	李宾, 刘妍, 孙斌, 等. 聚合物基导热复合材料的性能及导热机理[J]. 化工学报, 2009, 60(10):2650-2655. LI Bin, LIU Yan, SUN Bin, et al. Properties and thermal conductivity mechanism of polymer-based thermal conductivity composites[J]. Journal of Chemical Technology,2009,60(10):2650-2655(in Chinese).
[9]	YANG X, LI X F, WANG H S, et al. Improvement in thermal conductivity of through-plane aligned boron nitride/silicone rubber composites[J]. Materials & Design,2019,165:107580-107588.
[10]	XU S, LIU H, LI Q M, et al. Influence of magnetic alignment and layered structure of BN&Fe/EP on thermal conducting performance[J]. Journal of Materials Chemistry C,2016,4(4):872-878. doi: 10.1039/C5TC03791C
[11]	SONG S Q, WANG J Y, LIU C, et al. A facile route to fabricate thermally conductive and electrically insulating polymer composites with 3D interconnected graphene at an ultralow filler loading[J]. Nanoscale,2019,11(32):15234-15244. doi: 10.1039/C9NR05153H
[12]	伍垚屹, 陈松, 张雪娇, 等. 冰模板法制备取向氮化硼@聚多巴胺/纳米银导热网络及其硅橡胶复合导热垫片[J]. 复合材料学报, 2022, 39(7):3131-3143. doi: 10.13801/j.cnki.fhclxb.20210906.001 WU Yaoyi, CHEN Song, ZHANG Xuejiao, et al. Preparation of oriented boron nitride@polydopamine/nano silver thermal conductive network and its silicone rubber composite thermal conductive gasket by ice template method[J]. Acta Materiae Compositae Sinica,2022,39(7):3131-3143(in Chinese). doi: 10.13801/j.cnki.fhclxb.20210906.001
[13]	MA H Q, GAO B, WANG M, et al. Vertical alignment of carbon fibers under magnetic field driving to enhance the thermal conductivity of silicone composites[J]. Polymers for Advanced Technologies, 2021, 32(11): 4318-4325.
[14]	中国石油和化学工业联合会. 硫化橡胶或热塑性橡胶体积和/或表面电阻率的测定: GB/T 40719—2021[S]. 北京: 中国标准出版社, 2019. China Petroleum and Chemical Industry Federation. Rubber, vulcanized or thermoplastic—Determination of volume and/or surface resistivity: GB/T 40719—2021[S]. Beijing: Standards Press of China, 2019(in Chinese).
[15]	贾园, 马欢, 杨菊香, 等. 磁性四氧化三铁纳米粒子的制备及其应用研究进展[J]. 化学工业与工程, 2023, 40(5): 8-18. JIA Yuan, MA Huan, YANG Juxiang, et al. Progress in preparation and application of magnetic Fe₃O₄ nanoparticles[J]. Chemical Industry and Engineering, 2023, 40(5): 8-18(in Chinese).
[16]	侯涛, 徐仁扣. 胶体颗粒表面双电层之间的相互作用研究进展[J]. 土壤, 2008, 40(3):377-381. doi: 10.3321/j.issn:0253-9829.2008.03.008 HOU Tao, XU Renkou. Research progress on the interaction between electric double layers on the surface of colloidal particles[J]. Soil,2008,40(3):377-381(in Chinese). doi: 10.3321/j.issn:0253-9829.2008.03.008
[17]	MERLE MÉJEAN T, ABDELMOUNM E, QUINTARD P. Oxide layer on silicon carbide powder: A Ft-Ir investigation[J]. Journal of Molecular Structure, 1995, 349: 105-108.
[18]	WANG H Y, BERTAAND Y, FISCHMAN G S. Microstructure of silicon carbide whiskers synthesized by carbothermal reduction of silicon nitride[J]. Journal of the American Ceramic Society,1992,75(5):1080-1084. doi: 10.1111/j.1151-2916.1992.tb05541.x
[19]	SHEN M X, CUI Y X, HE J, et al. Thermal conductivity model of filled polymer composites[J]. International Journal of Minerals, Metallurgy, and Materials,2011,18(5):623-631. doi: 10.1007/s12613-011-0487-9
[20]	ACARI Y, UEDA A, NACAI S. Thermal conductivity of a polyethylene filled with disoriented short-cut carbon fibers[J]. Journal of Applied Polymer Science,1991,43(6):1117-1124. doi: 10.1002/app.1991.070430612
[21]	周文英, 丁小卫. 导热高分子材料[M]. 北京: 国防工业出版社, 2014: 29. ZHOU Wenying, DING Xiaowei. Thermal conductive polymer materials[M]. Beijing: National Defense Industry Press, 2014: 29(in Chinese).
[22]	ACARI Y, UEDA A, NACAI S. Thermal conductivities of composites in several types of dispersion systems[J]. Journal of Applied Polymer Science,1991,42(6):1665-1669. doi: 10.1002/app.1991.070420621
[23]	WONG C P, BOLLAMPALLY R S. Thermal conductivity, elastic modulus, and coefficient of thermal expansion of polymer composites filled with ceramic particles for electronic packaging[J]. Journal of Applied Polymer Science,1999,74(14):3396-3403.
[24]	GU J W, RUAN K. Breaking through bottlenecks for thermally conductive polymer composites: A perspective for intrinsic thermal conductivity, interfacial thermal resistance and theoretics[J]. Nano-Micro Letters,2021,13:110.
[25]	任佳, 蔡静. 导热系数测量方法及应用综述[J]. 计测技术, 2018, 38(S1):46-49. REN Jia, CAI Jing. Summary of thermal conductivity measurement methods and applications[J]. Measurement Technology,2018,38(S1):46-49(in Chinese).
[26]	张正荣. 传热学[M]. 北京: 高等教育出版社, 1982: 11-17. ZHANG Zhengrong. Heat transfer[M]. Beijing: Higher Education Press, 1982: 11-17(in Chinese).