Effects of emulsifier and reacting temperature on characteristics of phase change microcapsules

doi:10.11949/0438-1157.20241247

Abstract

Abstract:

In order to solve the problem of low energy storage and release efficiency, and to decrease both supercooling and superheat of heat exchangers due to large supercooling of ice, the preparation of phase change materials with low supercooling is a hotspot recently. It is an efficient solution to encapsulate n-tetradecane in a stable polystyrene shell. Based on our previous study on types and concentrations of crosslinking agents, the effects of hydrophilic-lipophilic balance of compound emulsifiers and reacting temperatures on the morphology and properties of phase change microcapsules were explored. The results show that when the reacting temperature was 60℃, the particle size increased from 2.735 μm to 24.690 μm with the increase of hydrophilic-lipophilic balance from 16.50 to 40.00. When the hydrophilic-lipophilic balance was 26.50, the particle size increased from 2.735 μm to 23.491 μm with the increase of reacting temperature from 60℃ to 80℃. And the surface morphologies of all m-PCMs was smooth. All the results showed that the microcapsules could provide the best thermal performance (148.12 J/g) and the smallest particle size (2.735 μm), when the concentration of the compound crosslinker was 1.0%, the emulsifier hydrophilic-lipophilic balance value was 26.50 and the reaction temperature was 60℃.

Key words: phase change microcapsules, emulsifier, HLB, latent heat of phase change, radical reaction, polymerization

摘要：

为解决由于冰过冷度大导致的系统蓄/释冷效率低、换热器的过冷度和过热度均增大的问题，制备过冷度较低的相变材料是当前研究的热点。将十四烷封装在具有较好稳定性的聚苯乙烯壳材中是一种高效的解决方式。基于前期研究中筛选的交联剂种类及浓度，研究了复合乳化剂的亲水亲油平衡（HLB）值和反应温度对相变微胶囊形貌及性能的影响。结果表明，反应温度为60℃时，随着亲水亲油平衡值由16.50增加到40.00，胶囊粒径由2.735 μm增大至24.690 μm；亲水亲油平衡值为26.50时，随着反应温度由60℃升高至80℃时，胶囊粒径由2.735 μm增加至23.491 μm。上述所有制备的相变微胶囊（m-PCMs）均具有光滑的形貌。所有的实验结果表明，复合交联剂浓度为1.0%，乳化剂亲水亲油平衡值为26.50，反应温度为60℃时，微胶囊具备最大潜热值（148.12 J/g）和最小粒径（2.735 μm）。

关键词: 相变微胶囊, 乳化剂, 亲水亲油平衡值, 相变潜热, 自由基反应, 聚合

CLC Number:

TK519

Shengmei ZHANG, Ming LI, Ying ZHANG, Xi YI, Yiting YANG, Yali LIU. Effects of emulsifier and reacting temperature on characteristics of phase change microcapsules[J]. CIESC Journal, 2025, 76(S1): 444-452.

张圣美, 李明, 张莹, 易茜, 杨依婷, 刘雅莉. 乳化剂和温度对相变微胶囊性能的影响分析[J]. 化工学报, 2025, 76(S1): 444-452.

Figures/Tables 13

Table 1 The technological parameters of m-PCMs

样品标记	HLB	反应温度/℃
M13006	13.00	60
M19756	19.75	60
M26504	26.50	40
M26505	26.50	50
M26506	26.50	60
M26507	26.50	70
M26508	26.50	80
M33256	33.25	60
M40006	40.00	60

Table 2 The compound emulsifier ratio and HLB value of m-PCMs

组别	乳化剂比例（SDS∶OP-10）	HLB
1	0∶1	13.00
2	0.25∶0.75	19.75
3	0.5∶0.5	26.50
4	0.75∶0.25	33.25
5	1∶0	40.00

Fig.1 SEM images of m-PCMs prepared with 60℃ and different HLB values

Fig.2 SEM images of m-PCMs prepared with HLB value of 26.50 and different reacting temperatures

Fig.3 FTIR images of m-PCMs prepared with different conditions

Fig.4 Particle size distributions of m-PCMs prepared with 60℃ and different HLB values

Fig.5 Particle size distributions of m-PCMs prepared with HLB value of 26.50 and different reacting temperatures

Table 3 Particle size distributions of m-PCMs prepared with different conditions

样品	d_0.1/μm	d_0.5/μm	d_0.9/μm
M26506	1.227	2.735	5.738
M33256	1.708	4.262	32.675
M40006	5.236	24.690	55.226
M26507	1.263	14.286	28.052
M26508	3.575	23.491	120.633

Fig.6 DSC curves of m-PCMs prepared at 60℃ with different HLB values

Fig.7 DSC curves of m-PCMs prepared with HLB value of 26.50 and different reacting temperatures

Table 4 The phase change characteristics of m-PCMs prepared with different conditions

样品	熔融过程		R_en/%
样品	熔融温度T_m/℃	熔融潜热H_m/(J/g)	R_en/%
M26506	9.04	148.12	69.85
M33256	4.36	50.39	23.76
M40006	4.51	105.24	49.63
M26507	4.17	111.83	52.74
M26508	3.80	110.88	52.29

Fig.8 TGA curves of m-PCMs prepared with different conditions

Table 5 The thermal stabilities of m-PCMs prepared with different conditions

样品	第一阶段质量损失			第二阶段质量损失
样品	开始温度/℃	结束温度/℃	损失质量占比/%	开始温度/℃	结束温度/℃	损失质量占比/%
M26506	112.20	248.00	69.67	310.00	455.80	26.88
M33256	78.98	203.32	20.14	290.20	468.13	79.80
M40006	105.57	221.14	47.43	332.23	444.68	48.24
M26507	88.09	233.09	55.33	338.04	454.86	37.90
M26508	72.22	225.59	60.01	327.50	439.40	36.21

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