Preparation and thermophysical property optimization of a new composite phase change material for cold storage

doi:10.11949/j.issn.0438-1157.20181505

Abstract

Abstract:

A new organic-inorganic composite phase change material (PCM) was prepared, which is composed of trimethylolpropane (TMP), ammonium chloride (NH₄Cl) and H₂O, for the application of cold chain logistic. The composite materials with different ratios were measured by using differential scanning calorimetry (DSC), and a composite PCM with excellent thermal performance was selected, which has a mass ratio of 1.0∶2.0∶7.0 (TMP∶NH₄Cl∶H₂O). To further optimize its performance, the supercooling degree and thermal conductivity of the PCM were studied by adding nucleating agent ( nano-Al₂O₃, nano-Fe₂O₃, nano-TiO₂), and phase separation of the PCM was studied by adding thickener, i.e., carboxymethyl cellulose (CMC) or polyacrylic acid sodium (PAAS), and the thermal cyclic experiment was also conducted. The results showed that adding 0.40%(mass) and 0.50%(mass) nano-TiO₂ had a better effect on reducing supercooling degree and enhancing thermal conductivity, respectively. CMC and PAAS could eliminate the phenomenon of phase separation with a little influence of thermophysical properties. The final ratio of the PCM was TMP-NH₄Cl-H₂O mixed at a mass ratio of 1.0∶2.0∶7.0 + 0.4%(mass) TiO₂ + 1.0% (mass) PAAS, and the phase-change temperature, latent heat enthalpy and thermal conductivity of the prepared PCM were －19.9℃, 246.8 kJ/kg and 0.81 W/(m·K), respectively.

Key words: cold-chain logistics, composites, cold storage, phase change, thermophysical properties, nanoparticles

摘要：

针对低温冷链物流应用场合，提出一种由三羟甲基丙烷（TMP）、氯化铵（NH₄Cl）和水组成的新型有机-无机复合相变蓄冷材料。首先对该复合材料的不同配比进行DSC热分析实验，筛选出热力性能较优异的材料混合比（TMP∶NH₄Cl∶H₂O质量比为1.0∶2.0∶7.0）。其次，以上述配比的复合材料为基液，研究了添加不同的纳米粒子（三氧化二铝、二氧化钛、三氧化二铁）对其过冷度、热导率的影响，以及增稠剂（羧甲基纤维素（CMC）、聚丙烯酸钠（PAAS））对其相分离现象的影响，并进行了热循环实验。实验结果表明：添加0.40%(质量分数)的TiO₂纳米粒子对降低该复合材料过冷度效果最佳；添加0.50%(质量分数)的TiO₂纳米粒子对增大其热导率效果最佳；增稠剂CMC和PAAS可以消除该复合材料相分离现象并对其相变温度、相变潜热、过冷度等热物性影响较小。经优化所得最终复合相变蓄冷材料的配比为以1.0∶2.0∶7.0质量比混合的TMP-NH₄Cl-H₂O + 0.40%(质量分数)TiO₂ + 1.0%(质量分数) PAAS，其相变温度为－19.9℃，相变潜热为246.8 kJ/kg，热导率为0.81 W/(m·K)，并具有较好的循环稳定性。

关键词: 冷链物流, 复合材料, 蓄冷, 相变, 热物性, 纳米粒子

CLC Number:

TK 02

Puyue JIA, Weidong WU, Yicong WANG, Bing ZHANG. Preparation and thermophysical property optimization of a new composite phase change material for cold storage[J]. CIESC Journal, 2019, 70(7): 2758-2765.

贾蒲悦, 武卫东, 王益聪, 张兵. 新型复合低温相变蓄冷材料的研制及热物性优化[J]. 化工学报, 2019, 70(7): 2758-2765.

Figures/Tables 12

Table 1 Experimental materials

材料名称	分子式	分子量	生产公司
三羟甲基丙烷	C₆H₁₄O₃	134	阿拉丁
氯化铵	NH₄Cl	53	国药集团
氧化铝（纳米颗粒）	Al₂O₃	102	国药集团
三氧化二铁（纳米颗粒）	Fe₂O₃	160	国药集团
二氧化钛（纳米颗粒）	TiO₂	80	国药集团
羧甲基纤维素钠	C₈H₁₆NaO₈	242	国药集团
聚丙烯酸钠	(C₃H₃NaO₂)_n	94	国药集团

Table 2 Experimental instruments

仪器名称	生产公司	型号	精度
热流型DSC热分析仪	德国NETZSCH	DSC 200 F3	温度精度±0.1℃，量热精度0.1 μW
Hotdisk热常数分析仪	瑞典Hotdisk	TPS 2500S	2%
优莱博低温恒温槽	德国JULABO	FP50-HL	温度稳定性±0.01℃
高精度天平	赛多利斯科学仪器	ALC-201.4	±0.01 mg
安捷伦数据采集仪	Agilent	34970A	温度系数0.03℃

Fig.1 Rough determination of DSC curves of ternary composite phase change materials

Fig.2 Precise determination of DSC curves of ternary composite phase change materials

Fig.3 Phase change temperature and latent heat enthalpy of different proportioning materials

Fig.4 Cooling curve of TAH70

Fig.5 Effect of nano-particle concentration in solution on supercooling degree of TAH70

Fig.6 Effect of nano-particle concentration in solution on thermal conductivity of TAH70

Fig.7 Morphology of TAH70 after adding thickener for 20 cycles

Fig.8 Morphology of TAH70 after adding thickener for 50 cycles

Fig.9 Comparison of DSC curve for initial TAH70A and after 100 and 500 cycles

Fig.10 Comparison of morphology for initial TAH70A and after 100 and 500 cycles

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