可降解柔性相变薄膜的制备及其热性能

doi:10.11949/0438-1157.20221676

摘要/Abstract

摘要：

为解决相变材料易泄漏、热导率低和力学性能差的问题，以生物基可降解聚乳酸（PLA）为基底，聚乙二醇（PEG）为相变工质，改性氧化铝（Al₂O₃）为导热添加剂，通过溶液共混法制备PEG/PLA/Al₂O₃柔性相变薄膜，用于热储能。相变薄膜可任意卷曲和折叠而不发生断裂，表现出良好的柔性。对其热性能、导热性能和降解性能等进行测试，结果表明：PEG和PLA具有良好的相容性，PLA作为支撑基底有效防止了PEG液体的泄漏，所制备的柔性相变薄膜具有良好的形状稳定性。PEG/PLA的熔融和凝固过程中的潜热分别为120.2和128.5 J/g，潜热留存率分别为62.2%和67.6%，添加20%的氧化铝，潜热值仅降低12.5%，而热导率提高了75.0%，热传递效率得到明显提升。PEG/PLA的降解速率明显高于PLA，PEG/PLA薄膜在NaOH溶液（pH=13）中4 h左右可完全降解，具有良好的环境友好性。

关键词: 柔性相变薄膜, 氧化铝, 有机相变材料, 聚合物, 可降解, 传热

Abstract:

To solve the problems of easy leakage, low thermal conductivity and poor mechanical properties of phase change materials, flexible phase change films were prepared by solution blending method of PEG/PLA/Al₂O₃ with biodegradable poly(lactic acid) (PLA) as the substrate, poly(ethylene glycol) (PEG) as the phase change working fluid and alumina (Al₂O₃) as the thermal conductivity additive for thermal energy storage. The phase change films could be curled and folded arbitrarily without breaking, showing good flexibility. The results of the tests on thermal properties, thermal conductivity and degradation properties showed that PEG and PLA had good compatibility, PLA as a supporting substrate effectively prevented the leakage of PEG liquid, and the prepared flexible phase change films had good shape stability. The latent heats during melting and solidification of PEG/PLA were 120.2 J/g and 128.5 J/g, respectively, and the latent heat retention rates were 62.2% and 67.6%, respectively. Adding 20% alumina, the latent heat value was only reduced by 12.5%, while the thermal conductivity was increased by 75%, and the heat transfer efficiency was significantly improved. The degradation rate of PEG/PLA was significantly higher than that of PLA, and the PEG/PLA film could be completely degraded in NaOH solution for about 4 h, which has good environmental friendliness.

Key words: flexible phase change films, alumina, organic phase change materials, polymers, degradable, heat transfer

中图分类号:

TB 34

吴学红, 栾林林, 陈亚南, 赵敏, 吕财, 刘勇. 可降解柔性相变薄膜的制备及其热性能[J]. 化工学报, 2023, 74(4): 1818-1826.

Xuehong WU, Linlin LUAN, Yanan CHEN, Min ZHAO, Cai LYU, Yong LIU. Preparation and thermal properties of degradable flexible phase change films[J]. CIESC Journal, 2023, 74(4): 1818-1826.

图/表 12

图1 改性前后 Al2O3在DCM中的分散性能

Fig.1 Distributed function of Al2O3 in DCM before and after modification

图2 PEG/PLA/Al2O3柔性相变薄膜制备流程

Fig.2 Preparation process of PEG/PLA/Al2O3 flexible phase change film

图3 薄膜柔性测试及PEG、PEG/PLA、PEG/PLA/Al2O3的热定形效果图

Fig.3 Flexibility test of the film and heat setting photographs for PEG, PEG/PLA, PEG/PLA/Al2O3

图4 薄膜SEM图像

Fig.4 SEM images of samples

图5 PLA、PEG、PEG/PLA、Al2O3、PEG/PLA/Al2O3和DCM的FT-IR谱图

Fig.5 FT-IR spectra of PLA, PEG, PEG/PLA, Al2O3, PEG/PLA/Al2O3 and DCM

图6 PLA、PEG、PEG/PLA、Al2O3、PEG/PLA/Al2O3的XRD谱图

Fig.6 XRD patterns of PLA,PEG,PEG/PLA,Al2O3 and PEG/PLA/Al2O3

图7 PEG、PEG/PLA、PEG/PLA/Al2O3的DSC曲线[(a)~(b)]，PEG/PLA/Al2O3冷热循环DSC曲线(c)及循环测试对应的柱状图(d)

Fig.7 DSC curves of PEG,PEG/PLA,PEG/PLA/Al2O3 [(a)—(b)], DSC curves of PEG/PLA/Al2O3 (c) and corresponding column chart during cycle test (d)

表1 柔性相变薄膜的DSC数据

Table 1 DSC data of flexible phase change films

样品	ΔH/（J/g）		T_peak/℃		T_on/℃		T_end/℃
样品	M	S	M	S	M	S	M	S
PEG	193.3	190.1	54.15	24.26	49.04	16.67	60.85	28.82
PEG/PLA	120.2	128.5	55.85	24.4	47.30	18.1	65.74	32.32
PEG/PLA/Al₂O₃5%	115.0	121.0	54.52	29.84	46.18	20.76	65.94	35.30
PEG/PLA/Al₂O₃10%	107.6	109.7	53.87	23.66	45.46	15.57	62.22	30.69
PEG/PLA/Al₂O₃15%	106.5	108.6	53.34	14.25	34.11	6.25	54.39	22.62
PEG/PLA/Al₂O₃20%	105.2	99.6	52.97	26.34	43.25	18.83	59.68	30.77

表2 样品循环前后的DSC数据

Table 2 DSC data before and after the cycle

循环次数	ΔH/（J/g）		T_peak/℃
循环次数	M	S	M	S
0	107.6	109.7	53.34	24.65
100	107.5	109.7	53.51	24.30
200	106.6	109.1	53.41	23.90
300	105.8	108.7	53.51	24.65
400	105.2	108	53.36	23.09
500	104.7	107.7	53.51	25.24

图8 PLA薄膜和PEG/PLA/Al2O3复合薄膜在加热过程中的热成像图及柔性相变薄膜的降温曲线

Fig.8 Thermal image during heating process and cooling curves of flexible phase change films of PLA film and PEG/PLA/ Al2O3 composite film

图9 柔性相变薄膜的热导率

Fig.9 Thermal conductivity of flexible phase change films

图10 薄膜的降解性能

Fig.10 Degradation properties of films

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