新型复合低温相变蓄冷材料的研制及热物性优化

doi:10.11949/j.issn.0438-1157.20181505

摘要/Abstract

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

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

中图分类号:

TK 02

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.

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.

图/表 12

表1 实验材料

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

表2 实验仪器

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℃

图1 三元复合相变蓄冷材料初选DSC曲线

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

图2 三元复合相变材料复选DSC曲线

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

图3 复选不同配比材料的相变温度和相变潜热

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

图4 基液TAH70步冷曲线

Fig.4 Cooling curve of TAH70

图5 纳米颗粒浓度对TAH70过冷度影响

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

图6 纳米颗粒浓度对TAH70热导率的影响

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

图7 添加增稠剂PAAS、CMC循环20次后TAH70状态

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

图8 添加增稠剂PAAS、CMC循环50次后TAH70状态

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

图9 TAH70A未循环与其循环100次、500次后的DSC曲线

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

图10 TAH70A与其循环100次、500次的状态图

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

参考文献 30

1	JiG, GuoR. Research on the security of cold-chain logistics[C]// International Conference on Service Systems & Service Management. 2009: 757-761.
2	ZhaoH, LiuS, TianC, et al. An overview of current status of cold chain in China[J]. International Journal of Refrigeration, 2018, 88: 483-495.
3	常丽娜, 韩星. 我国果蔬冷链物流建设现状及发展建议[J]. 中国果菜, 2015, (2): 5-10.
	ChangL N, HanX. Present situation and suggestions of cold chain logistics of fruits and vegetables in China[J]. China Fruit Vegetable, 2015, (2): 5-10.
4	黄艳, 章学来. 蓄冷技术在食品冷链物流中的研究进展[J]. 包装工程, 2015, (15): 23-29.
	HuangY, ZhangX L. Research progress of the application of cold storage technology in food cold chain logistics[J]. Packaging Engineering, 2015, (15): 23-29.
5	李志生, 张姝婷. 相变材料的研究进展与应用综述[J]. 建筑节能, 2016, 44(4): 57-60, 107.
	LiZ S, ZhangS T. Research progress and application of phase change materials[J]. Building Energy Efficiency, 2016, 44(4): 57-60, 107.
6	于永生, 井强山, 孙雅倩. 低温相变储能材料研究进展[J]. 化工进展, 2010, 29(5): 896-900, 913.
	YuY S, JingQ S, SunY Q. Progress in studies of low temperature phase-change energy storage materials[J]. Chemical Industry and Engineering Progress, 2010, 29(5): 896-900, 913.
7	陶文博, 谢如鹤. 有机相变蓄冷材料的研究进展[J]. 制冷学报, 2016, (1): 52-59.
	TaoW B, XieR H. Research and development of organic phase change materials for cool thermal energy storage[J]. Journal of Refrigeration, 2016, (1): 52-59.
8	谢鸿洲. 新型无机-有机复合壳层纳米胶囊相变蓄冷流体的热物性及传热性能[D]. 广州: 华南理工大学, 2015.
	XieH Z. Thermo-physical property and heat transfer performance of novel fluid for cool storage with inorganic-organic composite shell nanoencapsulated phase change material[D]. Guangzhou: South China University of Technology, 2015.
9	张庆, 王宏丽, 米欣. 月桂酸-肉豆蔻酸-癸酸/膨胀石墨定形相变材料的制备与性能研究[J]. 化工新型材料, 2015, 43(4): 46-48.
	ZhangQ, WangH L, MiX. Preparation and characterzation of lauric-myristic-capric acid/expanded graphite form-shaped composite phase change material[J]. New Chemical Materials, 2015, 43(4): 46-48.
10	李琳, 李东旭, 张树鹏, 等. 脂肪酸/SiO₂复合相变材料的制备和性能[J]. 材料研究学报, 2017, 31(8): 33-38.
	LiL, LiD X, ZhangS P, et al. Preparation and properties of fatty acid/SiO₂ composite phase change materials[J]. Chinese Journal of Materials Research, 2017, 31(8): 33-38.
11	吴淑英, 童旋, 龚曙光, 等. 纳米石墨烯片/石蜡复合相变蓄热材料的热性质研究[J]. 化工新型材料, 2014, 42(7): 105-107.
	WuS Y, TongX, GongS G, et al. Thermal property of nano-GnPs/paraffin heat storage phase change composite material[J]. New Chemical Materials, 2014, 42(7): 105-107.
12	FuX, LiuZ, XiaoY, et al. Preparation and properties of lauric acid/diatomite composites as novel form-stable phase change materials for thermal energy storage[J]. Energy & Buildings, 2015, 104: 244-249.
13	HanB, ChoiJ H, DantzigJ A, et al. A quantitative analysis on latent heat of an aqueous binary mixture [J]. Cryobiology, 2006, 52(1): 146-51.
14	戚晓丽. 复合相变蓄冷剂开发及在果蔬保鲜上的应用研究[D]. 杭州: 浙江大学, 2015.
	QiX L. Development of phase-changing coolant and its application on preservation of fruit and vegetables[D].Hangzhou: Zhejiang University, 2015.
15	黄雪, 崔英德, 尹国强, 等. 月桂酸-膨胀石墨复合相变材料的制备及性能[J]. 化工学报, 2015, 66(S1): 370-374.
	HuangX, CuiY D, YinG Q, et al. Preparation and performance of lauric acid-expanded graphite composite phase change materials[J]. CIESC Journal, 2015, 66(S1): 370-374.
16	SundarL S, SinghM K, SousaA C M. Investigation of thermal conductivity and viscosity of Fe₃O₄, nanofluid for heat transfer applications [J]. International Communications in Heat & Mass Transfer, 2013, 44(5): 7-14.
17	杜晓冬, 章学来, 丁锦宏, 等. 纳米成核剂对三水醋酸钠蓄热性能的影响[J]. 建筑节能, 2017, 45(9): 25-28, 59.
	DuX D, ZhangX L, DingJ H, et al. Effects of nanoparticles nucleating agents on the performance of sodiumacetate trihydrate[J]. Building Energy Efficiency, 2017, 45(9): 25-28, 59.
18	袁亚光, 袁艳平, 张楠, 等. 月桂酸-棕榈酸-硬脂酸/膨胀石墨复合相变材料的制备及性能[J]. 化工学报, 2014, 65(S2): 286-292.
	YuanY G, YuanY P, ZhangN, et al. Preparation and properties of lauric-palmitic-stearic acid eutectic mixture/expanded graphit composite phase change material for energy storage[J]. CIESC Journal, 2014, 65(S2): 286-292.
19	ZhouG, XiangY. Experimental investigations on stable supercooling performance of sodium acetate trihydrate PCM for thermal storage[J]. Solar Energy, 2017, 155: 1261-1272.
20	ZhangX Y, NiuJ L, WuJ Y, et al. Suppression of supercooling of PCM-water emulsions using nano-additives[J]. Energy Storage Science and Technology, 2014, 3(2): 133-136.
21	武卫东, 唐恒博, 苗朋柯, 等. 空调用纳米有机复合相变蓄冷材料分散稳定性[J]. 化工进展, 2015, 34(5): 1371-1376.
	WuW D, TangH B, MiaoP K, et al. Dispersion stability of nano-organic composite phase change materials for cool storage in air-conditioning [J]. Chemical Industry and Engineering Progress, 2015, 34(5): 1371-1376.
22	武卫东, 唐恒博, 苗朋柯, 等. 空调用纳米有机复合相变蓄冷材料制备与热物性[J]. 化工学报, 2015, 66(3): 1208-1214.
	WuW D, TangH B, MiaoP K, et al. Preparation and thermal properties of nano-organic composite phase change materials for cool storage in air-conditioning[J]. CIESC Journal, 2015, 66(3): 1208-1214.
23	刘欣, 高学农, 方玉堂. 相变储热材料Na₂SO₄·10H₂O的过冷和相分离研究[J]. 节能技术, 2012, 30(6): 499-503.
	LiuX, GaoX N, FangY T. Review on supercooling and phase separation occurring of Na₂SO₄·10H₂O[J]. Energy Conservation Technology, 2012, 30(6): 499-503.
24	纪珺, 陈跃, 章学来, 等. 甘露醇水溶液低温储能相变材料的制备及热物性[J]. 化工进展, 2018, 37(3): 1111-1117.
	JiJ, ChenY, ZhangX L, et al. Preparation and thermophysical properties of mannitol aqueous solution PCMs for thermal energy storage[J]. Chemical Industry and Engineering Progress, 2018, 37(3): 1111-1117.
25	李玉洋, 章学来, 徐笑锋, 等. 正辛酸-肉豆蔻酸低温相变材料的制备和循环性能[J]. 化工进展, 2018, 37(2): 689-693.
	LiY Y, ZhangX L, XuX F, et al. Preparation and cyclic properties of low temperature phase change materials of n-caprylic acid and myristic acid[J]. Chemical Industry and Engineering Progress, 2018, 37(2): 689-693.
26	黄艳, 章学来. 十二醇-癸酸-纳米粒子复合相变材料传热性能[J]. 化工学报, 2016, 67(6): 2271-2276.
	HuangY, ZhangX L. Heat transfer property of lauryl alcohol-capric acid-nanoparticle composite phase change materials[J]. CIESC Journal, 2016, 67(6): 2271-2276.
27	周孙希, 章学来, 刘升. 十四烷-正辛酸有机复合相变材料的制备和性能[J]. 储能科学与技术, 2018, 7(4): 692-697.
	ZhouS X, ZhangX L, LiuS. Preparation and thermal property of a tetradecane-octanoic acideutectic phase change material[J]. Energy Storage Science and Technology, 2018, 7(4): 692-697.
28	FangY , WeiH , LiangX , et al. Preparation and thermal performance of silica/n-tetradecane microencapsulated phase change material for cold energy storage[J]. Energy & Fuels, 2016, 30(11): 1-19.
29	吴东灵, 李廷贤, 何峰, 等. 三水醋酸钠相变储能复合材料改性制备及储/放热特性[J]. 化工学报, 2018, 69(7): 2860-2868.
	WuD L, LiT X, HeF, et al. Preparation and performance of modified sodium acetate trihydrate composite phase change material for thermal energy storage[J]. CIESC Journal, 2018, 69(7): 2860-2868.
30	何钦波, 童明伟, 刘玉东. 低温相变蓄冷纳米流体成核过冷度的实验研究[J]. 制冷学报, 2007, 28(4): 33-36.
	HeQ B, TongM W, LiuY D. Experimental study on super-cooling degree of nanofluids for cryogenic cool storage[J]. Journal of Refrigeration, 2007, 28(4): 33-36.

[1]	张双星, 刘舫辰, 张义飞, 杜文静. R-134a脉动热管相变蓄放热实验研究[J]. 化工学报, 2023, 74(S1): 165-171.
[2]	江河, 袁俊飞, 王林, 邢谷雨. 均流腔结构对微细通道内相变流动特性影响的实验研究[J]. 化工学报, 2023, 74(S1): 235-244.
[3]	吴延鹏, 刘乾隆, 田东民, 陈凤君. 相变材料与热管耦合的电子器件热管理研究进展[J]. 化工学报, 2023, 74(S1): 25-31.
[4]	胡兴枝, 张皓焱, 庄境坤, 范雨晴, 张开银, 向军. 嵌有超小CeO₂纳米粒子的碳纳米纤维的制备及其吸波性能[J]. 化工学报, 2023, 74(8): 3584-3596.
[5]	仪显亨, 周骛, 蔡小舒, 蔡天意. 光纤后向动态光散射测量纳米颗粒的浓度适用范围研究[J]. 化工学报, 2023, 74(8): 3320-3328.
[6]	史昊鹏, 钟达文, 廉学新, 张君峰. 朝下多尺度沟槽翅片结构表面沸腾换热实验研究[J]. 化工学报, 2023, 74(7): 2880-2888.
[7]	史方哲, 甘云华. 超薄热管启动特性和传热性能数值模拟[J]. 化工学报, 2023, 74(7): 2814-2823.
[8]	邢美波, 张中天, 景栋梁, 张洪发. 磁调控水基碳纳米管协同多孔材料强化相变储/释能特性[J]. 化工学报, 2023, 74(7): 3093-3102.
[9]	张贲, 王松柏, 魏子亚, 郝婷婷, 马学虎, 温荣福. 超亲水多孔金属结构驱动的毛细液膜冷凝及传热强化[J]. 化工学报, 2023, 74(7): 2824-2835.
[10]	张澳, 罗英武. 低模量、高弹性、高剥离强度丙烯酸酯压敏胶[J]. 化工学报, 2023, 74(7): 3079-3092.
[11]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[12]	蔡斌, 张效林, 罗倩, 党江涛, 左栗源, 刘欣梅. 导电薄膜材料的研究进展[J]. 化工学报, 2023, 74(6): 2308-2321.
[13]	李勇, 高佳琦, 杜超, 赵亚丽, 李伯琼, 申倩倩, 贾虎生, 薛晋波. Ni@C@TiO₂核壳双重异质结的构筑及光热催化分解水产氢[J]. 化工学报, 2023, 74(6): 2458-2467.
[14]	崔张宁, 胡紫璇, 吴雷, 周军, 叶干, 刘田田, 张秋利, 宋永辉. 可降解纤维素基材料的耐水性能研究进展[J]. 化工学报, 2023, 74(6): 2296-2307.
[15]	李振, 张博, 王丽伟. PEG-EG固-固相变材料的制备和性能研究[J]. 化工学报, 2023, 74(6): 2680-2688.