相变微胶囊改性及其在光热转换中的应用

doi:10.16085/j.issn.1000-6613.2022-0654

摘要/Abstract

摘要：

相变材料微胶囊化为相变材料提供良好密封保护，有效地解决了相变时的体积变化和泄漏问题。但相变微胶囊热导率低、机械强度和热稳定性差、功能单一等问题不容忽视。相变微胶囊改性是解决这些问题的有效途径。本文首先对相变微胶囊的组成、结构及制备方法进行介绍。重点综述了多芯材、多壳层和杂化壳等改性方式的原理及研究进展，概述了不同改性方式和改性材料对相变微胶囊的性能提升和功能拓展，主要包括增强其导热、蓄热能力、热稳定性、力学性能等，并使其多功能化。在此基础上，对改性相变微胶囊在光热转换中的发展做了详细阐述，对光热转换相变微胶囊的光热材料、工作原理和最新进展进行总结。最后讨论了相变微胶囊改性的现存问题和未来发展方向，指出应简化改性过程，加大多功能型相变微胶囊的开发力度，加快推进光热转换相变微胶囊的实际应用。

关键词: 相变材料, 相变微胶囊, 改性, 纳米材料, 聚合物, 光热转换

Abstract:

Microencapsulation of phase change materials (PCMs) provides good sealing protection for PCMs and solves the volume change and leakage problems during phase transition. However, the problems of low thermal conductivity, poor mechanical strength and thermal stability, and single function of microencapsulated phase change materials (MEPCMs) cannot be ignored. MEPCMs modification is an effective way to solve these problems. This review firstly introduced the compositions, structures and preparation methods of MEPCMs. The principles and research progress of modification methods such as multi-core materials, multi-shell layers and hybrid shells were emphatically reviewed. The performance enhancement and function expansion of MEPCMs by different modification methods and materials were outlined, mainly including enhancing their thermal conductivity, thermal storage capacity, thermal stability and mechanical strength to make them multifunctional. On this basis, the development of modified MEPCMs in photothermal conversion was elaborated. The photothermal materials, operating principles and latest progress of photothermal conversion MEPCMs were summarized. Finally, the existing problems and prospects of MEPCMs modification were discussed. It was pointed out that the modification process should be simplified, the development of multifunctional MEPCMs should be increased and the application of photothermal conversion MEPCMs in practical engineering should be promoted.

Key words: phase change materials, microencapsulated phase change materials, modification, nanomaterials, polymers, photothermal conversion

中图分类号:

TB34

郝旭波, 牛宝联, 郭昊天, 徐祥和, 张忠斌, 李应林. 相变微胶囊改性及其在光热转换中的应用[J]. 化工进展, 2023, 42(2): 854-871.

HAO Xubo, NIU Baolian, GUO Haotian, XU Xianghe, ZHANG Zhongbin, LI Yinglin. Modification of microencapsulated phase change material and its utilization in photothermal conversion[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 854-871.

图/表 14

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芯材	壳材	制备方法	性能提升	参考文献
正十八烷	甲基丙烯酸甲酯、丙烯酸和丙烯酸丁酯共聚	原位聚合法	储热放热性能提升：在加热/冷却过程中，相变微胶囊测量焓相对于理论焓分别上升了58.7%和63.9%	[82]
石蜡	丙烯酸丁酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯和甲基丙烯酸硬脂酯为单体与甲基丙烯酸甲酯共聚	悬浮聚合法	热稳定性提升：非交联聚合物壳的第1次降解开始于158℃，交联聚合物壳提升至238℃	[83]
石蜡	明胶-海藻酸钠	复合凝聚法	热稳定性提升：当工作温度为60.4℃，微胶囊的质量损失率仅为0.97%左右	[84]
石蜡和正十八烷	纤维素纳米晶-三聚氰胺甲醛树脂	Pickering乳液聚合法	热稳定性提升：加热/冷却循环200次后，相变焓保持率可达99.7%	[85]
石蜡	聚甲基丙烯酸甲酯-甲基丙烯酸甲酯	悬浮聚合法	热稳定性提升：在162.3~204.4℃，微胶囊的初始分解温度相比于石蜡提高了33.3℃	[89]

芯材	壳材	制备方法	性能提升	参考文献
正十八烷	甲基丙烯酸甲酯、丙烯酸和丙烯酸丁酯共聚	原位聚合法	储热放热性能提升：在加热/冷却过程中，相变微胶囊测量焓相对于理论焓分别上升了58.7%和63.9%	[82]
石蜡	丙烯酸丁酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯和甲基丙烯酸硬脂酯为单体与甲基丙烯酸甲酯共聚	悬浮聚合法	热稳定性提升：非交联聚合物壳的第1次降解开始于158℃，交联聚合物壳提升至238℃	[83]
石蜡	明胶-海藻酸钠	复合凝聚法	热稳定性提升：当工作温度为60.4℃，微胶囊的质量损失率仅为0.97%左右	[84]
石蜡和正十八烷	纤维素纳米晶-三聚氰胺甲醛树脂	Pickering乳液聚合法	热稳定性提升：加热/冷却循环200次后，相变焓保持率可达99.7%	[85]
石蜡	聚甲基丙烯酸甲酯-甲基丙烯酸甲酯	悬浮聚合法	热稳定性提升：在162.3~204.4℃，微胶囊的初始分解温度相比于石蜡提高了33.3℃	[89]

芯材	壳材	制备方法	性能提升	功能化	参考文献
石蜡	SiO₂-TiO₂	溶胶-凝胶法	导热能力提升：微胶囊的热导率比石蜡高11.63%	—	[90]
正二十烷	SiO₂-Cu	界面聚合法	导热能力提升：壳中掺杂铜纳米颗粒前后，微胶囊的热导率提升了83.3%	—	[38]
太阳盐	SiO₂-GO	溶胶-凝胶法	导热能力提升：微胶囊的热导率比纯硝酸盐提高约45%	光热转换	[91]
石蜡	TiO₂-GO	原位水解缩聚法	热稳定性提升：微胶囊的初始分解温度相比石蜡提高7℃	光热转换	[86]
正二十烷	TiO₂-ZnO	乳液模板界面缩聚法	热响应能力提升：能够对外界温度产生实时热响应	光催化和抗菌	[87]

芯材	壳材	制备方法	性能提升	功能化	参考文献
石蜡	SiO₂-TiO₂	溶胶-凝胶法	导热能力提升：微胶囊的热导率比石蜡高11.63%	—	[90]
正二十烷	SiO₂-Cu	界面聚合法	导热能力提升：壳中掺杂铜纳米颗粒前后，微胶囊的热导率提升了83.3%	—	[38]
太阳盐	SiO₂-GO	溶胶-凝胶法	导热能力提升：微胶囊的热导率比纯硝酸盐提高约45%	光热转换	[91]
石蜡	TiO₂-GO	原位水解缩聚法	热稳定性提升：微胶囊的初始分解温度相比石蜡提高7℃	光热转换	[86]
正二十烷	TiO₂-ZnO	乳液模板界面缩聚法	热响应能力提升：能够对外界温度产生实时热响应	光催化和抗菌	[87]

微胶囊样品编号	纳米Al₂O₃质量分数/%	熔化温度/℃	熔化焓/J·g^-1	结晶温度/℃	结晶焓/J·g^-1	包封率/%	包封效率/%	热导率/W·m^-1·K^-1
a	0	22.47	110.40	22.54	110.00	63.59	64.29	0.2442
b	5	23.43	105.50	23.19	104.30	60.77	61.20	0.2786
c	16	23.75	93.41	23.32	92.43	53.81	54.21	0.3104
d	27	23.14	84.54	22.76	83.99	48.70	49.16	0.3409
e	33	23.49	76.25	22.03	75.47	43.92	44.26	0.3591
f	38	22.96	75.40	22.58	75.13	43.43	43.91	0.3816
g	石蜡	27.72	173.60	24.73	169.20	—	—	—
h	PMMA	—	—	—	—	—	—	0.2111