Al2O3-Sn57Bi43/环氧树脂复合材料的导热及电性能

杨李懿; 葛凡; 汪蔚; 冉涛; 李艳飞

doi:10.13801/j.cnki.fhclxb.20230105.004

Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料的导热及电性能

doi: 10.13801/j.cnki.fhclxb.20230105.004

杨李懿^{1, 2},
葛凡²,
汪蔚^1, ,,
冉涛²,
李艳飞²

1.
嘉兴学院　材料与纺织工程学院，嘉兴 314001
2.
浙江荣泰科技企业有限公司，嘉兴 314007

基金项目: 浙江省基础公益研究计划项目(LGG19E030006)

详细信息

通讯作者:
汪蔚，博士，教授，研究方向为聚合物基复合材料　E-mail: zjxuwangwei@163.com

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2022-11-22
- 修回日期: 2022-12-14
- 录用日期: 2022-12-21
- 网络出版日期: 2023-01-06
- 刊出日期: 2023-11-15

Thermal conductivity and electrical properties of Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

YANG Liyi^{1, 2},
GE Fan²,
WANG Wei^{1
, ,},
RAN Tao²,
LI Yanfei²

1.
College of Materials and Textile Engineering, Jiaxing University, Jiaxing 314001, China
2.
Zhejiang Rongtai Technical Industry CO. LTD., Jiaxing 314007, China

Funds: Zhejiang Province Public Welfare Technology Application Research Project (LGG19E030006)

摘要

摘要: 在聚合物基体中构建由高导热填料相互连接而成的导热通路是提高复合材料导热性能的有效策略。本文采用共还原法，在Al₂O₃微球表面沉积低熔点纳米锡铋合金颗粒(Sn₅₇Bi₄₃)，制备杂化材料(Al₂O₃-Sn₅₇Bi₄₃)，用于环氧树脂的导热绝缘填料。当环氧树脂受热固化时，Al₂O₃-Sn₅₇Bi₄₃表面Sn₅₇Bi₄₃纳米颗粒熔融，将填料相互连接而形成有效的导热通路，提高复合体系导热性能。当填料体积含量为60vol%时，Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料的导热系数为2.95 W·(m·K)⁻¹，比Al₂O₃/环氧树脂复合材料的导热系数(1.82 W·(m·K)⁻¹)提高了62.1%。Fogyel及Agari模型分析表明，Al₂O₃表面沉积Sn₅₇Bi₄₃有利于降低填料间接触热阻，形成导热通路。与Al₂O₃/环氧树脂复合材料相比，Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料的介质损耗增加，介电强度及体积电阻率降低，但仍具有电绝缘性能。由于填料-基体间界面性能改善及Al₂O₃-Sn₅₇Bi₄₃形成的网链结构能起到传递应力，阻止裂纹扩张的作用，Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料的拉伸断裂强度提高。
- 环氧树脂 /
- Al₂O₃ /
- 低共熔合金 /
- 杂化材料 /
- 导热性能 /
- 绝缘
Abstract: Constructing thermal conductive pathways in polymer matrix with interconnected high conductive thermal fillers is an effective strategy to enhance the thermal conductivity of the composites. In this paper, eutectic Sn-Bi alloy (Sn₅₇Bi₄₃) nanoparticles are deposited on the surface of Al₂O₃ microspheres by coreduction method to prepare Al₂O₃-Sn₅₇Bi₄₃ hybrids as thermal conductive and electrical insulating fillers for epoxy resin. During the heat curing of epoxy resin, Sn₅₇Bi₄₃ nanoparticles on the Al₂O₃ surface melt and bridge the separate fillers together to form effective thermal conductive pathway, and thus enhance the thermal conductivity of the composites. When filler volume fraction is 60vol%, the thermal conductivity of Al₂O₃-Sn₅₇Bi₄₃/epoxy composites is 2.95 W·(m·K)⁻¹, 62.1% higher than that of Al₂O₃/epoxy composites (1.82 W·(m·K)⁻¹). The results of Fogyel and Agari simulation demonstrate that the deposition of Sn₅₇Bi₄₃ on Al₂O₃ surface reduces the thermal contact resistance between fillers and forms thermally conductive networks more easily. The Al₂O₃-Sn₅₇Bi₄₃/epoxy composites exhibit higher dielectric loss, lower dielectric strength and volume resistivity than Al₂O₃/epoxy composites, still with electrical insulating properties. What is more, the tensile strength of the Al₂O₃-Sn₅₇Bi₄₃/epoxy composites is improved, because the improved interfacial properties of filler-matrix and the formed networks could transfer stress and prevent crack expansion.
- epoxy resin /
- Al₂O₃ /
- eutectic Sn-Bi alloy /
- hybrid materials /
- thermal conductivity /
- electrical insulation

HTML全文

图 1 Al₂O₃-Sn₅₇Bi₄₃杂化材料及Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料的制备过程示意图

Figure 1. Schematic illustration of preparation for Al₂O₃-Sn₅₇Bi₄₃ hybrid fillers and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

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图 2 Al₂O₃和Al₂O₃-Sn₅₇Bi₄₃杂化材料的XPS全谱(a)和Sn3d (b)、Bi4f (c)高分辨率窄谱

Figure 2. Survey XPS (a) and high resolution spectra of Sn3d (b), Bi4f (c) region of Al₂O₃ and Al₂O₃-Sn₅₇Bi₄₃ hybrid fillers

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图 3 Al₂O₃和Al₂O₃-Sn₅₇Bi₄₃的DSC曲线

Figure 3. DSC curves of Al₂O₃ and Al₂O₃-Sn₅₇Bi₄₃

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图 4 Al₂O₃(a)、Al₂O₃-Sn₅₇Bi₄₃杂化材料(b)及经150℃/2 h处理后的Al₂O₃-Sn₅₇Bi₄₃杂化材料(c)的SEM图像

Figure 4. SEM images of Al₂O₃ (a), Al₂O₃-Sn₅₇Bi₄₃ hybrid fillers (b) and Al₂O₃-Sn₅₇Bi₄₃ after thermal treatment at 150℃ for 2 h (c)

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图 5 Al₂O₃/环氧树脂(a)及Al₂O₃-Sn₅₇Bi₄₃/环氧树脂(b)复合材料横截面的SEM图像

Figure 5. Cross section SEM images of Al₂O₃/epoxy (a) and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites (b)

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图 6 填料体积含量对Al₂O₃/环氧树脂和Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料导热系数的影响

Figure 6. Effects of filler volume fraction on thermal conductivity of Al₂O₃/epoxy and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

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图 7 Al₂O₃/环氧树脂和Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料的lg(λ-λ₁)-lg[(V_f-V_c)/(1-V_c)]曲线

λ₁ and λ₂—Thermal conductivity of polymer and fillers respectively; V_f—Volume fraction of fillers; V_c—Critical volume fraction of fillers

Figure 7. lg(λ-λ₁)-lg[(V_f-V_c)/(1-V_c)] curves of Al₂O₃/epoxy and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

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图 8 Al₂O₃/环氧树脂和Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料的lgλ-V_f曲线

Figure 8. lgλ-V_fcurves of Al₂O₃/epoxy and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

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表 1 Al₂O₃和Al₂O₃-Sn₅₇Bi₄₃的元素组成

Table 1. Element compositions of Al₂O₃ and Al₂O₃-Sn₅₇Bi₄₃ wt%

Sample	Al	O	Sn	Bi
Al₂O₃	50.72	47.36	0.00	0.00
Al₂O₃-Sn₅₇Bi₄₃	40.25	37.98	8.51	11.38

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表 2 Al₂O₃/环氧树脂和Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料的密度、比热容及热扩散系数

Table 2. Density, specific heat capacity and thermal diffusion coefficient of Al₂O₃/epoxy and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

V_f/%	Al₂O₃/epoxy			Al₂O₃-Sn₅₇Bi₄₃/epoxy
V_f/%	Density/ (kg·m⁻³)	Specific heat capacity/[J·(kg·K)⁻¹]	Thermal diffusion coefficients/(m²·s⁻¹)	Density/ (kg·m⁻³)	Specific heat capacity/[J·(kg·K)⁻¹]	Thermal diffusion coefficients/(m²·s⁻¹)
0	1.19×10³	1106.43	1.52×10⁻⁷	1.19×10³	1106.43	1.52×10⁻⁷
6	1.35×10³	1045.03	1.42×10⁻⁷	1.38×10³	1016.70	1.50×10⁻⁷
11	1.49×10³	1004.05	1.41×10⁻⁷	1.54×10³	958.87	1.49×10⁻⁷
14	1.57×10³	982.84	1.43×10⁻⁷	1.63×10³	929.55	1.51×10⁻⁷
17	1.65×10³	963.71	1.76×10⁻⁷	1.73×10³	903.46	2.05×10⁻⁷
22	1.78×10³	935.68	2.46×10⁻⁷	1.89×10³	865.83	3.12×10⁻⁷
29	1.97×10³	902.86	3.04×10⁻⁷	2.11×10³	822.64	4.09×10⁻⁷
38	2.21×10³	868.87	4.94×10⁻⁷	2.39×10³	778.87	7.77×10⁻⁷
48	2.48×10³	838.89	5.81×10⁻⁷	2.71×10³	741.04	10.05×10⁻⁷
55	2.67×10³	821.50	7.48×10⁻⁷	2.93×10³	719.42	12.90×10⁻⁷
60	2.80×10³	810.51	8.03×10⁻⁷	3.09×10³	705.88	13.51×10⁻⁷

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表 3 Al₂O₃/环氧树脂和Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料导热系数的非线性Foygel模拟结果

Table 3. Simulation results of nonlinear Foygel model for the thermal conductivity of Al₂O₃/epoxy and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

Sample	V_c/%	λ₀/(W·(m·K)⁻¹)	β	R_c/(K·W⁻¹)
Al₂O₃	19.23	3.42	1.088	1.17×10⁵
Al₂O₃-Sn₅₇Bi₄₃	18.25	6.73	1.253	8.35×10⁴
Notes: V_c—Critical volume fraction of filler; λ₀—Pre-exponential factor; β—Conductivity exponent that depends on the aspect of filler; R_c—Interface thermal resistance.

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表 4 Al₂O₃/环氧树脂和Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料导热系数的Agari模拟结果

Table 4. Agari simulation results for the thermal conductivity of Al₂O₃/epoxy and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

Sample	C₁	C₂
Al₂O₃	0.7661	0.8991
Al₂O₃-Sn₅₇Bi₄₃	0.7495	1.1465
Notes: C₁ is a factor affecting crystallinity and crystal size of polymer; C₂ is a factor of ease in forming conductive chains of fillers.

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表 5 填料体积含量对Al₂O₃/环氧树脂和Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料拉伸断裂强度的影响

Table 5. Effects of filler volume fraction on tensile properties of Al₂O₃/epoxy and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

V_f/%	Al₂O₃/epoxy		Al₂O₃-Sn₅₇Bi₄₃/epoxy
V_f/%	Tensile strength/MPa	Elongation at break/%	Tensile strength/MPa	Elongation at break/%
0	44.56±1.83	4.47±0.17	44.56±1.83	4.47±0.17
20	40.31±1.20	4.06±0.14	46.84±2.04	4.75±0.21
40	37.41±1.15	3.54±0.15	49.65±2.16	5.09±0.19
60	32.28±1.09	3.21±0.11	51.62±2.62	5.36±0.24

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表 6 填料体积含量对Al₂O₃/环氧树脂和Al₂O₃-Sn₅₇Bi₄₃/环氧树脂复合材料电性能的影响

Table 6. Effects of filler volume fraction on electric properties of Al₂O₃/epoxy and Al₂O₃-Sn₅₇Bi₄₃/epoxy composites

V_f/%	Al₂O₃/epoxy			Al₂O₃-Sn₅₇Bi₄₃/epoxy
V_f/%	Volume resistivity/ (10¹³ Ω·m)	Dielectric strength/ (MV·m⁻¹)	Dielectric loss tanδ/ 10⁻³	Volume resistivity/ (10¹³ Ω·m)	Dielectric strength/ (MV·m⁻¹)	Dielectric loss tanδ/ 10⁻³
0	2.67±0.68	25.8±1.6	4.75±0.08	2.670±0.680	25.8±1.6	4.75±0.08
20	2.79±0.51	25.2±2.1	3.98±0.06	0.921±0.106	22.1±1.4	11.02±0.22
40	2.81±0.62	24.5±1.9	5.22±0.07	0.264±0.096	19.6±1.2	15.46±0.97
60	2.87±0.75	24.3±1.3	4.75±0.07	0.086±0.034	18.5±1.3	19.43±1.46

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