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

伍垚屹; 陈松; 张雪娇; 王克文; 龙金; 刘岚

doi:10.13801/j.cnki.fhclxb.20210906.001

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

doi: 10.13801/j.cnki.fhclxb.20210906.001

伍垚屹^1,,
陈松¹,
张雪娇²,
王克文¹,
龙金²,
刘岚^1, ,

1.
华南理工大学　材料科学与工程学院，广东省高性能与功能高分子材料重点实验室，广州 510641
2.
华南理工大学　轻工科学与工程学院，广州 510641

基金项目: 国家自然科学基金 (52073099)；广东省自然科学基金(2021A1515010675；2021A1515010714)

详细信息

通讯作者:
刘岚，博士，教授，博士生导师，研究方向为导热及导电复合材料　 E-mail: psliulan@scut.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-06-25
- 修回日期: 2021-08-11
- 录用日期: 2021-08-16
- 网络出版日期: 2021-09-06
- 刊出日期: 2022-07-30

Preparation of oriented boron nitride@polydopamine/nanosilver network and silicone rubber thermally conductive composite by ice template method

1.
School of Materials Science and Engineering, Key Lab of Guangdong Province for High Property and Functional Macromolecular Materials, South China University of Technology, Guangzhou 510641, China
2.
School of Light Industry and Engineering, South China University of Technology, Guangzhou 510641, China

摘要

摘要: 制备具有垂直方向高导热、低压缩应力松弛的柔性导热复合材料，并将其应用于大功率电子元器件的导热垫片，对大幅度提升电子器件垂直散热能力具有重要的意义。本文基于冰模板法设计了自下而上垂直定向排列的导热网络来实现高热导率。首先，利用多巴胺改性的羟基化氮化硼纳米片并负载银纳米颗粒(BNNS@PDA/Ag)作为杂化导热填料，再与纤维素纳米纤维(Cellulose nanofiber，CNF)进行复合，采用半导体制冷台为冷源进行定向冷冻，对冷冻后的样品进行冷冻干燥形成气凝胶，再真空浇筑聚二甲基硅氧烷(Polydimethylsiloxane，PDMS)后制得具有高导热和低应力松弛的BNNS@PDA/Ag-PDMS导热垫片。结果表明，理论松弛时间损失随着银纳米颗粒(Ag NPs)含量的提升先减小后增大，气凝胶质量分数达到19.7wt%时，在20%的形变下，3wt%Ag NPs含量对应的导热垫片的理论松弛时间达到32204 s，导热垫片的垂直方向热导率达到3.23 W/(m·K)。利用冰模板法可以制备具有高度取向的垂直填料导热网络，在导热垫片领域具有很好的应用前景。
- 冰模板法 /
- 氮化硼纳米片 /
- 气凝胶 /
- 导热复合材料 /
- 柔性 /
- 硅橡胶复合导热垫片
Abstract: The preparation of thermally conductive pads with high vertical thermal conductivity and low compressive stress relaxation is of great significance for improving the vertical heat dissipation capability of current high-power electronic components. In this paper, based on the ice template method, a bottom-up vertically oriented thermal network is designed to achieve high thermal conductivity. First, we use dopamine-modified hydroxylated boron nitride nanosheets and silver nanoparticles (BNNS@PDA/Ag) as hybrid thermally conductive fillers, cellulose nanofibers (Cellulose nanofiber, CNF) are used to prepare composite, and a semiconductor is applied as refrigeration table for the composite’s directional freezing. The frozen samples are freeze-dried to form an aerogel, and then polydimethylsiloxane (PDMS) is vacuum poured into the aerogel to prepare BNNS@PDA/Ag-PDMS thermal pad with high thermal conductivity and low stress relaxation. The results show that the theoretical relaxation time loss decreases first and then increases with the increase of silver nanoparticles (Ag NPs) content. When the aerogel mass fraction reaches 19.7wt%, the theoretical relaxation time of the thermal pad corresponding to 3wt% Ag NPs content reaches 32204 at 20% deformation, the vertical thermal conductivity of thermal pad is up to 3.23 W/(m·K). The ice template method can be used to prepare the vertical packing thermal network with high orientation, which has a good application prospect in the field of thermally conductive pads.
- ice template method /
- boron nitride nanosheets /
- aerogel /
- thermal conductive composites /
- flexibility /
- silicone rubber thermally conductive composite

HTML全文

图 1 ((a)~(g)) 多巴胺改性羟基化氮化硼纳米片负载银纳米颗粒气凝胶(BNNS@PDA/Ag)及BNNS@PDA/Ag-聚二甲基硅氧烷(PDMS)复合导热垫片的制备示意图；(h) 气凝胶的内部取向网络和气凝胶实物图；((i), (j)) 导热垫片的实物及弯折过程照片；(k) BNNS@PDA/Ag导热网络示意图

Figure 1. ((a)-(g)) Fabrication of dopamine-modified hydroxylated boron nitride nanosheets and silver nanoparticles aerogel (BNNS@PDA/Ag) and BNNS@PDA/Ag-polydimethylsiloxane (PDMS))composite thermal conductivity pad; (h) Internal orientation network of the gel; ((i), (j)) Bending picture of thermal conductive pad; (k) Thermal conductive network of BNNS@PDA/Ag

CNF—Cellulose nanofiber

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图 2 (a) BNNS与BNNS@PDA的XPS全谱图；(b) BNNS的C1s轨道XPS图谱；(c) BNNS和BNNS@PDA的热失重曲线

Figure 2. (a) XPS full spectrum of BNNS and BNNS@PDA; (b) XPS spectrum of B1s of BNNS; (c) Thermal weight loss curve of BNNS and BNNS@PDA

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图 3 (a) h-BN、BNNS@PDA、BNNS@PDA/Ag的XRD图谱；(b)图3(a)的放大图

Figure 3. (a) XRD patterns of the h-BN powder, BNNS@PDA, and BNNS@PDA/Ag; (b) Enlarged view of Fig.3(a)

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图 4 BNNS (a)、BNNS@PDA (b) 和BNNS@PDA/Ag (c) 的TEM图像；BNNS@PDA/Ag (d) 的HR-TEM图像

Figure 4. TEM images of BNNS (a) , BNNS@PDA (b) and BNNS@PDA/Ag (c); HR-TEM image of BNNS@PDA/Ag (d)

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图 5 不同浓度的BNNS@PDA/Ag气凝胶截面图及在2 mg/mL固定浓度下不同Ag含量对应的气凝胶截面图

Figure 5. Cross-section images of aerogels prepared with different concentrations of BNNS@PDA and cross-section images of aerogels with different Ag contents at a fixed concentration of 2 mg/mL BNNS@PDA

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图 6 (a) BNNS@PDA/Ag-PDMS导热垫片截面的SEM图像；(b) 截面放大的SEM图像

Figure 6. (a) Cross-sectional SEM image of the BNNS@PDA/Ag-PDMS thermally conductive pad; (b) Enlarged cross-sectional SEM image of the BNNS@PDA/Ag-PDMS pad

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图 8 19.6wt%BNNS@PDA (a) 和3wt%Ag (b) 的BNNS@PDA/Ag-PDMS导热垫片的压缩应力松弛拟合图

Figure 8. Fitting curves of 19.6wt%BNNS@PDA (a) and 3wt%Ag (b) of BNNS@PDA/Ag-PDMS thermal conductive pads’ compression stress relaxation

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图 7 (a) 不同的AgNPs含量对应的BNNS@PDA/Ag-PDMS样品压缩应力松弛曲线； (b) 不同的Ag NPs含量对应的BNNS@PDA/Ag-PDMS样品压缩应力-应变曲线

Figure 7. (a) Compression stress loss curves of different Ag content of BNNS@PDA/Ag-PDMS; (b) Compression stress-strain curves of different Ag content of BNNS@PDA/Ag-PDMS

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图 9 不同质量份数的气凝胶及定份数下的不同含量Ag NPs的BNNS@PDA/Ag-PDMS导热垫片热导率图：(a) 不同份数的气凝胶热导率；(b)不同含量的Ag NPs热导率

Figure 9. Thermal conductivity of BNNS@PDA/Ag-PDMS thermally conductive pads with different mass fractions of aerogel and different content of Ag NPs under a fixed number of aerogel’s fraction: (a) Thermal conductivity of different fractions of aerogel; (b) Thermal conductivity of different content of Ag NPs

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图 10 相关报道的BNNS基复合材料垂直热导率对比^[23-30]

Figure 10. Vertical thermal conductivity of different BNNS-based composites in previous reports^[23-30]

PMMA—Polymethyl methacrylate; CNT—Carbon nanotube; PET—Polyethylene terephthalate; NFC—Nanocellulose; rGO—Reduced graphene oxide; GNP—Graphite nanosheet; PPS—Polyphenylene sulfite

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图 11 纯CNF、BNNS@PDA、BNNS@PDA/Ag三个不同填料类型的导热垫片热成像图

Figure 11. Infrared thermal image of thermally conductive pads with three different filler types: pure CNF, BNNS@PDA, and BNNS@PDA/Ag

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图 12 BNNS@PDA/Ag-PDMS导热垫片界面热阻应用模拟测试图

Figure 12. Simulation of interface thermal resistance of BNNS@PDA/Ag-PDMS thermally conductive pads

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图 13 纯纤维素纳米纤维(CNF)、BNNS@PDA和BNNS@PDA/Ag三个不同填料类型的导热垫片界面热阻热成像图

Figure 13. Infrared thermal image of interface thermal resistance of thermally conductive pad with three different filler types of pure cellulose nanofiber (CNF), BNNS@PDA and BNNS@PDA/Ag

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图 14 不同Ag NPs含量下BNNS@PDA/Ag-PDMS导热垫片的体积电阻率图

Figure 14. Electrical resistivity of of BNNS@PDA/Ag-PDMS thermally conductive pad with different Ag NPs contents

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表 1 BNNS@PDA/PDMS 导热垫片的填料质量分数表

Table 1. Mass fraction of filler in BNNS@PDA/PDMS thermally conductive pad

Concentration of the suspensions/(mg·mL⁻¹)	Mass of BNNS@PDA/mg	Mass of CNF/mg	Mass of aerogels/mg	Mass fraction of elastomer composites/wt%
1	10	25	35	16.4
2	20	25	45	19.6
3	30	25	55	24.3
4	40	25	65	26.9

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表 2 BNNS@PDA/PDMS导热垫片的理论松弛时间表

Table 2. Theoretical relaxation time of BNNS@PDA/PDMS thermal pad

Mass of BNNS@PDA/mg	Compressive stress at 20% strain/MPa	Theoretical relaxation time/s
0(Pure CNF)	0.27	28852
10	0.32	32107
20	0.40	34886
30	0.46	33471
40	0.54	32152

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表 3 不同填料分数的BNNS@PDA/PDMS 导热垫片的导热性能参数

Table 3. Thermal conductivity parameters of BNNS@PDA/PDMS thermal pads with different filler mass fractions

Filler concentration/ (mg·mL⁻¹)	Mass fraction of aerogel after infiltration/wt%	Density/ (g·cm⁻³)	Specific heat/ (J·(g·K)⁻¹)	Thermal diffusity/ (mm²·s⁻¹)	Thermal conductivity/ (W·(m·K)⁻¹)
0	Pure PDMS	0.78	1.82	0.14	0.21
1	16.4	1.15	1.70	0.29	0.57
2	19.6	1.26	1.63	0.83	1.70
3	24.3	1.31	1.55	1.14	2.32
4	26.9	1.40	1.38	1.56	3.02

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