Fabrication and characterization of shape-stabilized phase change materials of ZIF-8/P(tetradecyl acrylate-co-hexadecyl acrylate) and prussian blue/ (tetradecyl acrylate-co-hexadecyl acrylate)
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摘要: 形状稳定的相变材料(SPCMs)是绿色的可重复使用的储能材料。由于丙烯酸正烷基酯共聚物的熔融温度可通过控制侧链长度来调节，因此可以得到适宜的相变温度。用一种基于金属-有机骨架纳米粒子稳定悬浮聚合法制备出了功能MOFs/聚合物复合材料—ZIF-8/丙烯酸十四-十六酯共聚物(ZIF-8/P(TDA-co-HDA))与PB/丙烯酸十四-十六酯共聚物(PB/P(TDA-co-HDA))，通过使用此技术，可以将功能性纳米颗粒固定在聚合物表面上，ZIF-8和PB起到形状稳定的作用。ZIF-8/P(TDA-co-HDA)的吸放热温度分别为37.5℃和8.4℃，相变焓值为63 J/g，PB/P(TDA-co-HDA)在39.1℃吸热，10.1℃放热，相变焓值为68 J/g。该种材料在60℃时保持其形状没有任何泄漏，这远高于P(TDA-co-HDA)的熔融温度。在1000个热循环后，ZIF-8/P(TDA-co-HDA)和PB/P(TDA-co-HDA)仍表现出良好的结晶行为和热可靠性。制备的新型形状稳定相变材料在热能存储应用中具有潜在的用途。Abstract: A novel strategy based on Metal-organic frameworks nanoparticles (MOFs NPs)-stabilized suspension polymerization has been achieved for the fabrication of multifunctional ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA) composites. By using this technique, functional nanoparticles can be immobilized on the surface of polymer. In this paper, ZIF-8 and PB nanoparticles (NPs) were used as stabilizer for the suspension polymerization in water and ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA) composites are successfully synthesized. ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA) absorbed heat at 37.5℃, 39.1℃ and released it at 8.4℃, 10.1℃ with a heat storage capacity of 63 J/g, 68 J/g, respectively. The material retains its shape without any leakage at 60℃, which is much higher than that of the melting temperature of P(TDA-co-HDA). The ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA) composites exhibit good crystallization behaviors and excellent thermal reliabilities after 1000 thermal cycles. The thermal properties of the ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA) composites were also investigated. The novel shape-stabilized PCMs fabricated in this study have potential uses in thermal energy storage applications.
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图 1 沸石咪唑骨架材料(ZIF-8)/P(丙烯酸十四酯(TDA)-co-丙烯酸十六酯(HDA))和普鲁士蓝(PB)/P(TDA-co-HDA)合成示意图
Figure 1. Schematic illustration of zeolite imidazole skeleton material (ZIF-8)/P(tetradecyl acrylate (TDA)-co-hexadecyl acrylate (HDA)) and prussian blue (PB)/P(TDA-co-HDA)
PCM—Phase-change material
图 2 TDA、HDA、ZIF-8、PB、P(TDA-co-HDA)、ZIF-8/P(TDA-co-HDA)和PB/P(TDA-co-HDA)的FTIR图谱
Figure 2. FTIR spectra of TDA, HDA), ZIF-8, PB, P(TDA-co-HDA), ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA)
图 3 ZIF-8 ((a), (b)) 和PB ((c), (d)) 的TEM和SEM图像；ZIF-8/ P(TDA-co-HDA) (e) 和PB/ P(TDA-co-HDA) (f) 的SEM图像和EDS图谱
Figure 3. TEM and SEM images of ZIF-8 ((a), (b)) and PB ((c), (d)); SEM images and EDS spectra of ZIF-8/ P(TDA-co-HDA) (e) and PB/ P(TDA-co-HDA) (f)
图 4 P(TDA-co-HDA)、ZIF-8/P(TDA-co-HDA)和PB/P(TDA-co-HDA)加热和冷却过程中的DSC曲线
Figure 4. DSC curves of P(TDA-co-HDA), ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA) during heating and cooling processes
图 5 ZIF-8、PB、P(TDA-co-HDA)、ZIF-8/P(TDA-co-HDA)和PB/P(TDA-co-HDA)的TG曲线
Figure 5. TG curves of ZIF-8, PB, P(TDA-co-HDA), ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA)
图 6 ZIF-8、PB、P(TDA-co-HDA)、ZIF-8/P(TDA-co-HDA)、PB/P(TDA-co-HDA)的XRD图谱
Figure 6. XRD patterns of ZIF-8, PB, P(TDA-co-HDA), ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA)
图 7 烘箱热处理30 min前后ZIF-8/P(TDA-co-HDA)和PB/P(TDA-co-HDA)的照片
Figure 7. Photographs of ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA) before and after the thermal treatment in an oven, 30 min
图 8 热循环处理前后ZIF-8/P(TDA-co-HDA) ((a), (c)) 和PB/P(TDA-co-HDA) ((b), (d)) 的FTIR图谱和DSC曲线
Figure 8. FTIR spectra and DSC curves ofZIF-8/P(TDA-co-HDA) ((a), (c)) and PB/P(TDA-co-HDA) ((b), (d)) before and after the various thermal cycling treatments
表 1 P(TDA-co-HDA)、ZIF-8/P(TDA-co-HDA)和PB/P(TDA-co-HDA)的相变特性
Table 1. Thermal properties of P(TDA-co-HDA), ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA)
Sample ΔHm/(J·g−1) Tmo/℃ Tmp/℃ ΔHc/(J·g−1) Tco/℃ Tcp/℃ T5wt%/℃ P(TDA-co−HDA) 70 30.9 38.2 −70 19.9 9.1 290.8 ZIF-8/P(TDA-co-HDA) 62 27.9 37.5 −63 19.6 8.4 227.6 PB/P(TDA-co−HDA 68 31.9 39.1 −68 19.7 10.1 254.8 Notes: Tmo—Onset melting temperature on the DSC heating curve; Tmp—Peak melting temperature on the DSC heating curve; ΔHm—Melting enthalpy; Tco—Onset crystallizing temperature on the crystallization curve; Tcp—Peak crystallizing temperature on the crystallization curve; ΔHc—Crystallizing enthalpy; T5wt%—Temperature at mass loss of 5wt%. 
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表 2 热循环处理前后ZIF-8/P(TDA-co-HDA)和PB/P(TDA-co-HDA)的DSC数据
Table 2. DSC datas of ZIF-8/P(TDA-co-HDA) and PB/P(TDA-co-HDA) before and after thermal cycling treatments
Sample ΔHm/(J·g−1) Tmo/℃ Tmp/℃ ΔHc/(J·g−1) Tco/℃ Tcp/℃ ZIF-8/P(TDA-co-HDA) 1 cycle 62 27.9 37.5 −63 19.6 8.4 1000 cycles 60 27.6 37.4 −61 19.5 8.5 PB/P(TDA-co-HDA) 1 cycle 68 31.9 39.1 −68 19.7 10.1 1000 cycles 67 32.1 39.2 −66 19.9 9.9
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