Research progress on thermal conductivity enhancement and form stability improvement of phase change thermal interface materials

doi:10.16085/j.issn.1000-6613.2021-2411

Abstract

Abstract:

Thermal interface materials (TIMs) is a kind of material used to establish thermal conductive path between chip and heat sink for reducing heat transfer resistance and thus improving heat dissipation efficiency. Introducing phase change materials (PCMs) especially solid-liquid PCMs into TIMs is expected to develop a novel kind of TIM, that is, phase change TIM (PCTIM), which has the functions of both thermal storage and heat conductance. However, in view of the low thermal conductivity of solid-liquid PCMs as well as the problem of their liquid flow and leakage, the enhancement on heat conduction along with the improvement in form-stability has become the key to developing high-performance PCTIMs. In this paper, the strategies and research progress on improving thermal conductivity and formability of PCTIMs are reviewed. Specifically, the means of strengthening the thermal conductivity of PCTIMs mainly include adding the fillers with high thermal conductivity, forming the orderly structures of the fillers and employing low melting point metal, etc. As for improving the form-stability, the solid-liquid PCMs could be combined with flexible supporting materials for overcoming the problem of liquid leakage as well as maintaining the flexibility to some extent. The solid-solid PCMs are used to replace solid-liquid PCMs to avoid liquid leakage completely. The solid-liquid PCMs could be encapsulated into micron or nanoscale capsules followed by introducing TIMs, which would develop the PCTIMs with high latent heat and thus exhibiting good performance to resist thermal shock for chips. At present, the thermal conductivities of the PCTIMs are still low, and the synergistic influence mechanism of the two characteristics of heat storage and thermal conductivity on their heat dissipation performance is not well understood. In the future, new strategies should be explored for developing the form-stable PCTIMs with high thermal conductivity, low interface thermal resistance and large latent heat value with the purpose of meeting the heat dissipation requirements of high heat flux chips for the fields such as 5G communication.

Key words: electronic materials, interface, composites, heat conduction, phase change, enthalpy, nanomaterials

摘要：

将相变时伴随潜热的相变材料（phase change material, PCM）特别是潜热值较大的固-液PCM引入热界面材料（TIM）领域，有望获得兼具储热和导热双功能的新型热界面材料——相变热界面材料（phase change thermal interface material, PCTIM）。然而，鉴于固-液相变材料的热导率普遍较低且存在液相流动泄漏问题，使得增强热传导并同时提升固-液相变材料的定形性成为研制高性能相变热界面材料（PCTIM）的关键。本文系统评述了国内外研究者在提升相变热界面材料热导率以及改善其定形性方面的策略及其研究进展。文中指出，目前强化PCTIM导热的手段主要有添加高导热填料、促使填料有序结构化以及使用低熔点金属等。在改善定形性方面，已运用的策略主要包括使用柔性载体负载固-液PCM以在保证一定柔性的基础上克服其液相泄漏问题，使用固-固PCM来取代固-液PCM来彻底避免液相泄漏问题的出现，以及将固-液PCM封装在微米级或纳米级胶囊内，旨在牺牲借助液相PCM增加柔性的功能，而且通过提高PCTIM的潜热值来提升其抗热流冲击性能。文章指出，当前已研制的PCTIM热导率还较低，储热和导热这两个特性对其散热性能的协同影响机制缺乏深入了解。今后，需要探索研制高性能PCTIM的新策略，以期获得定形性好、热导率高、界面热阻小且潜热值大的PCTIM，从而满足5G通信等高热流密度芯片的散热需求。

关键词: 电子材料, 界面, 复合材料, 热传导, 相变, 焓, 纳米材料

CLC Number:

TK02

CAI Chuyue, FANG Xiaoming, LING Ziye, ZHANG Zhengguo. Research progress on thermal conductivity enhancement and form stability improvement of phase change thermal interface materials[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4907-4917.

蔡楚玥, 方晓明, 凌子夜, 张正国. 相变热界面材料导热增强及定形改善的研究进展[J]. 化工进展, 2022, 41(9): 4907-4917.

Figures/Tables 7

References 56

1	高丽娜, 赵领. 温度应力下基于步进加速退化试验的电子器件寿命预测[J]. 电子元件与材料, 2014, 33(6): 72-76.
	GAO Lina, ZHAO Ling. Life prediction of electronic equipments based on step-stress accelerated degradation test under temperature stress[J]. Electronic Components and Materials, 2014, 33(6): 72-76.
2	YOVANOVICH M M. Four decades of research on thermal contact, gap, and joint resistance in microelectronics[J]. IEEE Transactions on Components and Packaging Technologies, 2005, 28(2): 182-206.
3	SARVAR F, WHALLEY D C, CONWAY P P. Thermal interface materials: a review of the state of the art[C]//2006 1st Electronic Systemintegration Technology Conference. Dresden， IEEE, 2006: 1292-1302.
4	杨斌, 孙蓉. 热界面材料产业现状与研究进展[J]. 中国基础科学, 2020, 22(2): 56-62.
	YANG Bin, SUN Rong. The current industry status and research progress in thermal interface materials[J]. China Basic Science, 2020, 22(2): 56-62.
5	周四丽, 张正国, 方晓明. 固-固相变储热材料的研究进展[J]. 化工进展, 2021, 40(3): 1371-1383.
	ZHOU Sili, ZHANG Zhengguo, FANG Xiaoming. Research progress of solid-solid phase change materials for thermal energy storage[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1371-1383.
6	IRFAN LONE M, JILTE R. A review on phase change materials for different applications[J]. Materials Today: Proceedings, 2021, 46: 10980-10986.
7	AFTAB Waseem, HUANG Xinyu, WU Wenhao, et al. Nanoconfined phase change materials for thermal energy applications[J]. Energy & Environmental Science, 2018, 11(6): 1392-1424.
8	RAZEEB K M, DALTON E, CROSS G L W, et al. Present and future thermal interface materials for electronic devices[J]. International Materials Reviews, 2018, 63(1): 1-21.
9	史剑, 吴晓琳, 符显珠, 等. 相变热界面材料研究进展[J]. 材料导报, 2015, 29(S1): 151-156.
	SHI Jian, WU Xiaolin, FU Xianzhu, et al. Research progress of phase change thermal interface materials[J]. Materials Review, 2015, 29(S1): 151-156.
10	LIU C Q, CHEN C, YU W, et al. Thermal properties of a novel form-stable phase change thermal interface materials olefin block copolymer/paraffin filled with Al₂O₃ [J]. International Journal of Thermal Sciences, 2020, 152: 106293.
11	LIU Z, CHUNG D D L. Boron nitride particle filled paraffin wax as a phase-change thermal interface material[J]. Journal of Electronic Packaging, 2006, 128(4): 319-323.
12	AOYAGI Y, LEONG C K, CHUNG D D L. Polyol-based phase-change thermal interface materials[J]. Journal of Electronic Materials, 2006, 35(3): 416-424.
13	WANG J F, XIE H Q, XIN Z. Thermal properties of paraffin based composites containing multi-walled carbon nanotubes[J]. Thermochimica Acta, 2009, 488(1/2): 39-42.
14	LI M, CHEN M R, WU Z S, et al. Carbon nanotube grafted with polyalcohol and its influence on the thermal conductivity of phase change material[J]. Energy Conversion and Management, 2014, 83: 325-329.
15	LI M, GUO Q G, CHEN Q W. Thermal conductivity improvement of heat-storage composite filled with milling modified carbon nanotubes[J]. International Journal of Green Energy, 2019, 16(15): 1617-1623.
16	ZOU D Q, MA X F, LIU X S, et al. Thermal performance enhancement of composite phase change materials (PCM) using graphene and carbon nanotubes as additives for the potential application in lithium-ion power battery[J]. International Journal of Heat and Mass Transfer, 2018, 120: 33-41.
17	QU Y, WANG S, ZHOU D, et al. Experimental study on thermal conductivity of paraffin-based shape-stabilized phase change material with hybrid carbon nano-additives[J]. Renewable Energy, 2020, 146: 2637-2645.
18	MAO D S, XIE J Q, SHENG G Q, et al. Aluminum coated spherical particles filled paraffin wax as a phase-change thermal interface materials[C]//2017 18th International Conference on Electronic Packaging Technology (ICEPT). Harbin, IEEE, 2017: 828-830.
19	GUPTA N, KUMAR A, DHAWAN S K, et al. Metal nanoparticles enhanced thermophysical properties of phase change material for thermal energy storage[J]. Materials Today: Proceedings, 2020, 32: 463-467.
20	ZENG J L, CAO Z, YANG D W, et al. Thermal conductivity enhancement of Ag nanowires on an organic phase change material[J]. Journal of Thermal Analysis and Calorimetry, 2010, 101(1): 385-389.
21	ZENG J L, ZHU F R, YU S B, et al. Effects of copper nanowires on the properties of an organic phase change material[J]. Solar Energy Materials and Solar Cells, 2012, 105: 174-178.
22	KIM W. Strategies for engineering phonon transport in thermoelectrics[J]. Journal of Materials Chemistry C, 2015, 3(40): 10336-10348.
23	CHEN Z W, ZHANG X Y, PEI Y Z. Manipulation of phonon transport in thermoelectrics[J]. Advanced Materials, 2018, 30(17): 1705617.
24	ZHANG Q, LIU J. Anisotropic thermal conductivity and photodriven phase change composite based on RT100 infiltrated carbon nanotube array[J]. Solar Energy Materials and Solar Cells, 2019, 190: 1-5.
25	黄华, 吴扬, 刘长洪, 等. 热界面材料制备方法: CN100358132C[P]. 2007-12-26.
	HUANG Hua, WU Yang, LIU Changhong, et al. A preparation method of thermal interface materials: CN100358132C[P]. 2007-12-26.
26	ZHANG L, ZHOU K C, WEI Q, et al. Thermal conductivity enhancement of phase change materials with 3D porous diamond foam for thermal energy storage[J]. Applied Energy, 2019, 233/234: 208-219.
27	ARAMESH M, SHABANI B. Metal foam-phase change material composites for thermal energy storage: a review of performance parameters[J]. Renewable and Sustainable Energy Reviews, 2022, 155: 111919.
28	ZHANG P, MENG Z N, ZHU H, et al. Melting heat transfer characteristics of a composite phase change material fabricated by paraffin and metal foam[J]. Applied Energy, 2017, 185: 1971-1983.
29	WANG G, WEI G S, XU C, et al. Numerical simulation of effective thermal conductivity and pore-scale melting process of PCMs in foam metals[J]. Applied Thermal Engineering, 2019, 147: 464-472.
30	SABRINA FERFERA R, MADANI B, SERHANE R. Investigation of heat transfer improvement at idealized microcellular scale for metal foam incorporated with paraffin[J]. International Journal of Thermal Sciences, 2020, 156: 106444.
31	WANG X H, LU C N, RAO W. Liquid metal-based thermal interface materials with a high thermal conductivity for electronic cooling and bioheat-transfer applications[J]. Applied Thermal Engineering, 2021, 192: 116937.
32	HILL R F, STRADER J L. Practical utilization of low melting alloy thermal interface materials[C]//Twenty-Second Annual IEEE Semiconductor Thermal Measurement and Management Symposium. Dallas, IEEE, 2006: 23-27.
33	李元元, 程晓敏. 低熔点合金传热储热材料的研究与应用[J]. 储能科学与技术, 2013, 2(3): 189-198.
	LI Yuanyuan, CHENG Xiaomin. Review on the low melting point alloys for thermal energy storage and heat transfer applications[J]. Energy Storage Science and Technology, 2013, 2(3): 189-198.
34	DENG Y G, LIU J. Corrosion development between liquid gallium and four typical metal substrates used in chip cooling device[J]. Applied Physics A, 2009, 95(3): 907-915.
35	JI Y L, YAN H L, XIAO X, et al. Excellent thermal performance of gallium-based liquid metal alloy as thermal interface material between aluminum substrates[J]. Applied Thermal Engineering, 2020, 166: 114649.
36	HUANG K Y, QIU W K, OU M L, et al. An anti-leakage liquid metal thermal interface material[J]. RSC Advances, 2020, 10(32): 18824-18829.
37	ROY C K, BHAVNANI S, HAMILTON M C, et al. Investigation into the application of low melting temperature alloys as wet thermal interface materials[J]. International Journal of Heat and Mass Transfer, 2015, 85: 996-1002.
38	CHU W X, TSENG P H, WANG C C. Utilization of low-melting temperature alloy with confined seal for reducing thermal contact resistance[J]. Applied Thermal Engineering, 2019, 163: 114438.
39	Indigo[EB/OL]. .
40	ZHANG Y F, LI W, HUANG J H, et al. Expanded graphite/paraffin/silicone rubber as high temperature form-stabilized phase change materials for thermal energy storage and thermal interface materials[J]. Materials, 2020, 13(4): 894.
41	LIU C Q, YU W, CHEN C, et al. Remarkably reduced thermal contact resistance of graphene/olefin block copolymer/paraffin form stable phase change thermal interface material[J]. International Journal of Heat and Mass Transfer, 2020, 163: 120393.
42	邓志军, 万炜涛, 陈田安. 一种橡胶改性的相变导热界面材料及制备方法: CN105441034A [P]. 2016-03-30.
	DENG Zhijun, WAN Weitao, CHEN Tian’an. A rubber modified phase change thermal interface material and preparation method: CN105441034A [P]. 2016-03-30.
43	CAI Z D, LIU J, ZHOU Y X, et al. Flexible phase change materials with enhanced tensile strength, thermal conductivity and photo-thermal performance[J]. Solar Energy Materials and Solar Cells, 2021, 219: 110728.
44	RAJ C R, SURESH S, BHAVSAR R R, et al. Recent developments in thermo-physical property enhancement and applications of solid solid phase change materials[J]. Journal of Thermal Analysis and Calorimetry, 2020, 139(5): 3023-3049.
45	张杨飞, 李安然, 张聪. 一种固-固相变热界面材料及其制备方法: CN107163547A[P]. 2017-09-15.
	ZHANG Yangfei, LI Anran, ZHANG Cong, et al. Solid-solid phase change thermal interface material and preparation method thereof: CN107163547A[P]. 2017-09-15.
46	ZHANG C, SHI Z, LI A, et al. RGO-coated polyurethane foam/segmented polyurethane composites as solid–solid phase change thermal interface material[J]. Polymers, 2020, 12(12): 3004.
47	FENG J, LIU Z J, ZHANG D Q, et al. Phase change materials coated with modified graphene-oxide as fillers for silicone rubber used in thermal interface applications[J]. New Carbon Materials, 2019, 34(2): 188-195.
48	WENG Z S, WU K, LUO F B, et al. Fabrication of high thermal conductive shape-stabilized polyethylene glycol/silica phase change composite by two-step sol-gel method[J]. Composites Part A: Applied Science and Manufacturing, 2018, 110: 106-112.
49	ZHU X Y, LI X, SHEN J J, et al. Stable microencapsulated phase change materials with ultrahigh payload for efficient cooling of mobile electronic devices[J]. Energy Conversion and Management, 2020, 223: 113478.
50	ZHOU Y C, LI S S, ZHAO Y, et al. Compatible paraffin@SiO₂ microcapsules/polydimethylsiloxane composites with heat storage capacity and enhanced thermal conductivity for thermal management[J]. Composites Science and Technology, 2022, 218: 109192.
51	GU X K, WEI Y J, YIN X B, et al. Colloquium: phononic thermal properties of two-dimensional materials[J]. Reviews of Modern Physics, 2018, 90(4): 041002.
52	MAO D S, CHEN J H, REN L L, et al. Spherical core-shell Al@Al₂O₃ filled epoxy resin composites as high-performance thermal interface materials[J]. Composites Part A: Applied Science and Manufacturing, 2019, 123: 260-269.
53	DAI W, LYU L, LU J, et al. A paper-like inorganic thermal interface material composed of hierarchically structured graphene/silicon carbide nanorods[J]. ACS Nano, 2019, 13(2): 1547-1554.
54	DAI W, MA T, YAN Q, et al. Metal-level thermally conductive yet soft graphene thermal interface materials[J]. ACS Nano, 2019, 13(10): 11561-11571.
55	RAMASWAMY C, SHINDE S, POMPEO F, et al. Phase change materials as a viable thermal interface material for high-power electronic applications[C]//The Ninth Intersociety Conference on Thermal and Thermomechanical Phenomena In Electronic Systems (IEEE Cat. No.04CH37543). Las Vegas, IEEE, 2004: 687-691.
56	TOMIZAWA Y, SASAKI K, KURODA A, et al. Experimental and numerical study on phase change material (PCM) for thermal management of mobile devices[J]. Applied Thermal Engineering, 2016, 98: 320-329.

材料	热导率/W·m^-1·K^-1	材料	热导率/W·m^-1·K^-1
氧化铝	20~30	金刚石	2000
氮化硼	185~300	石墨	100~400
氮化铝	150~220	石墨烯	>2000
铜	398	碳化硅	80~120
铝	315	碳纤维	400~700
银	417	碳纳米管	3000
镍	158

材料	热导率/W·m^-1·K^-1	材料	热导率/W·m^-1·K^-1
氧化铝	20~30	金刚石	2000
氮化硼	185~300	石墨	100~400
氮化铝	150~220	石墨烯	>2000
铜	398	碳化硅	80~120
铝	315	碳纤维	400~700
银	417	碳纳米管	3000
镍	158

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