用于墙体具有自调温功能相变储热微胶囊的制备及其性能研究
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摘要
相变材料应用于建筑材料的方式之一是将其微胶囊化(microPCM)，这可以解决相变材料的疲劳及相变材料与周围材料界面等问题，使材料具有较长的使用寿命。本文采用微胶囊技术，以不同包覆方法制备了不同壁材的相变储热微胶囊，并对其性能进行了研究。
采用复合凝聚法，以明胶-阿拉伯树胶为壁材，在水相体系中通过控制pH值和物料比，制得相变储热微胶囊。采用光学显微镜、TEM、SEM、激光粒度分析仪研究了微胶囊的表面形态、包覆效果和粒径分布；采用TG和DSC研究了微胶囊的热稳定性和储热调温效果。结果表明：以明胶-阿拉伯树胶为壁材制备的相变储热微胶囊平均粒径均匀；壁材完整，包覆效果较好；热分析显示，相变储热微胶囊具有自调温功能，但明胶-阿拉伯树胶为壁材的微胶囊热稳定性较差。
采用原位聚合法用三聚氰胺甲醛树脂包覆一种相变点为24℃的相变材料，制得相变储热微胶囊。利用激光粒度分布仪、SEM、DSC和TG分别研究了所得微胶囊的粒径分布、表面形态及热性能的影响因素。实验结果表明所得微胶囊粒径分布均匀，表面光洁，具有很好的致密性和一定的强度。其中当乳化速度为2500r／min、乳化时间大于5min、壁材滴加速度小于0.5 ml·min~(-1)且系统调节剂为芯材的30％～40％时微胶囊的粒径分布集中；DSC显示微胶囊包覆相变材料不影响其相变点，相变储热明显。此种微胶囊中的相变材料在发生相变时具有调温作用，将其应用于室内墙体材料中，可使墙体材料具有自调温作用。
采用乳液体系，以2，4-二异氰酸酯基甲苯(TDI)及二亚乙基三胺(DETA)为单体，应用界面聚合法制备直径约1μm的聚氨酯微胶囊。所用相变材料为十八烷，乳化剂是一种非离子型表面活性剂NP-10。制备聚脲树脂微胶囊的过程不仅包括TDI和DETA的反应，还包括TDI与自身水解产物的界面反应。TDI与DETA反应质量比为3：1。另外，NP-10还与TDI反应生成脲烷。包含十八烷的微胶囊在29℃～30℃范围内表现出了十八烷的相变温度特征。用十八烷熔融热法测得的芯材含量低于理论计算值。随芯材含量降低，十八烷的微胶囊化效率提高。
Phase change material (PCM) has been recently studied and applied for thermal energy storage. As PCM can absorb, store and release large amounts of latent heat over a defined temperature range during itself changes phase, it can be used in many fields. In this study, a kind of PCM is used in architecture field, it can make room comfortable and save energy. Microcapsulation of PCM (microPCMs) offers a measure to solve the super-cool problem and interfacial combine with circumstance materials. Also make the PCM have a long-life. MicroPCMs has been used in functional fiber, solar energy utilize, heat energy transfers, agriculture, and building materials. The objective of this study was to synthesize microcapsules containing a composite phase change materials for application in indoor wall controlling temperature, which would save energy and make comfort indoors. Three microcapsulation methods have been applied to preparation microPCMs.
First, the complex coacervation of gelatin-acacia system in microcapsulation process was investigated in this paper. The influence of different technological conditions including pH . mass ratio of gelation, the time of gelation, as well as the hardening time on yields of microcapsulation the efficiency of encapsulation were studied respectively. The microencapsulation condition were also optimized. The means of SEM, DSC and TGA were applied in this study. It was found that the gelation speed of the gelation had a great effect on its
microcapsulation process, there was a best fitting gelation time for high yield of the microcapsules and good encapsulation efficiency. The gelation with complete cooling time of 40min had a high yields and encapsulation efficiency, and the process may be contrplled. The microPCMs was stable and its diameter was uniformity. The thermal profile of microcapsule was not affected by the ratio of gelation, but the thermal was not good enough.
The microPCMs were prepared by using in-suit polymerization with prepolymer of melamine-formaldehyde (MF) and charactized the properties such as shape, diameter distribution, thermal prosperities, strength, shell thickness and penetration property. Double-shell heat energy storage microcapsule was prepared used the prosperities of microcapsules were investigated. A phase change material as core, which melt point was 24 C and phase transition heat was 225.5J/g .The microcapsules would been used in indoor wall to regulate the temperature and saving energy sources .The surface morphological structure was examined by means of scanning electron microscopy. The strength of shell was evaluated through observing the surface change after pressure by means of scanning electron microscopy. The melting point of the microcapsules was 24.7 C, nearly equaled to the pure phase change material. The DSC results make clearly that the polymer shell of microcapsules do not influence the proprieties of the phase change material. Also founded that the avoiding penetration property of double-shell microcapsules was better than that of single shell. It was necessary to investigate the shell for the thickness would affect the strength and penetration property of the microcapsules. In order to observe the double-shell shell we adapted the methods of in-bed the microcapsules in glutin, and got the SEM images of slices. The average thickness was 0.5-1 m. The thermal test showed the microPCMs had good resisted thermal properties and good absorb thermal property.
This article also calculated the microPCms quantities and energy saving effect in theory
designed the experimental apparatus to measure the energy saving effect, and analyzed the temperature equalization action of the microPCMs by comparing experimnt.
Last, polyurea microcapsule containing octadecane as phase change material was successfully synthesized by interfacial polycondensation using TDI and DETA as shell monomers in an emulsion only by reaction of TDI and DETA, but also reaction of TDI and amines which are formed by hydrolysis of TDI at the interface. In this study,
采用复合凝聚法，以明胶-阿拉伯树胶为壁材，在水相体系中通过控制pH值和物料比，制得相变储热微胶囊。采用光学显微镜、TEM、SEM、激光粒度分析仪研究了微胶囊的表面形态、包覆效果和粒径分布；采用TG和DSC研究了微胶囊的热稳定性和储热调温效果。结果表明：以明胶-阿拉伯树胶为壁材制备的相变储热微胶囊平均粒径均匀；壁材完整，包覆效果较好；热分析显示，相变储热微胶囊具有自调温功能，但明胶-阿拉伯树胶为壁材的微胶囊热稳定性较差。
采用原位聚合法用三聚氰胺甲醛树脂包覆一种相变点为24℃的相变材料，制得相变储热微胶囊。利用激光粒度分布仪、SEM、DSC和TG分别研究了所得微胶囊的粒径分布、表面形态及热性能的影响因素。实验结果表明所得微胶囊粒径分布均匀，表面光洁，具有很好的致密性和一定的强度。其中当乳化速度为2500r／min、乳化时间大于5min、壁材滴加速度小于0.5 ml·min~(-1)且系统调节剂为芯材的30％～40％时微胶囊的粒径分布集中；DSC显示微胶囊包覆相变材料不影响其相变点，相变储热明显。此种微胶囊中的相变材料在发生相变时具有调温作用，将其应用于室内墙体材料中，可使墙体材料具有自调温作用。
采用乳液体系，以2，4-二异氰酸酯基甲苯(TDI)及二亚乙基三胺(DETA)为单体，应用界面聚合法制备直径约1μm的聚氨酯微胶囊。所用相变材料为十八烷，乳化剂是一种非离子型表面活性剂NP-10。制备聚脲树脂微胶囊的过程不仅包括TDI和DETA的反应，还包括TDI与自身水解产物的界面反应。TDI与DETA反应质量比为3：1。另外，NP-10还与TDI反应生成脲烷。包含十八烷的微胶囊在29℃～30℃范围内表现出了十八烷的相变温度特征。用十八烷熔融热法测得的芯材含量低于理论计算值。随芯材含量降低，十八烷的微胶囊化效率提高。
Phase change material (PCM) has been recently studied and applied for thermal energy storage. As PCM can absorb, store and release large amounts of latent heat over a defined temperature range during itself changes phase, it can be used in many fields. In this study, a kind of PCM is used in architecture field, it can make room comfortable and save energy. Microcapsulation of PCM (microPCMs) offers a measure to solve the super-cool problem and interfacial combine with circumstance materials. Also make the PCM have a long-life. MicroPCMs has been used in functional fiber, solar energy utilize, heat energy transfers, agriculture, and building materials. The objective of this study was to synthesize microcapsules containing a composite phase change materials for application in indoor wall controlling temperature, which would save energy and make comfort indoors. Three microcapsulation methods have been applied to preparation microPCMs.
First, the complex coacervation of gelatin-acacia system in microcapsulation process was investigated in this paper. The influence of different technological conditions including pH . mass ratio of gelation, the time of gelation, as well as the hardening time on yields of microcapsulation the efficiency of encapsulation were studied respectively. The microencapsulation condition were also optimized. The means of SEM, DSC and TGA were applied in this study. It was found that the gelation speed of the gelation had a great effect on its
microcapsulation process, there was a best fitting gelation time for high yield of the microcapsules and good encapsulation efficiency. The gelation with complete cooling time of 40min had a high yields and encapsulation efficiency, and the process may be contrplled. The microPCMs was stable and its diameter was uniformity. The thermal profile of microcapsule was not affected by the ratio of gelation, but the thermal was not good enough.
The microPCMs were prepared by using in-suit polymerization with prepolymer of melamine-formaldehyde (MF) and charactized the properties such as shape, diameter distribution, thermal prosperities, strength, shell thickness and penetration property. Double-shell heat energy storage microcapsule was prepared used the prosperities of microcapsules were investigated. A phase change material as core, which melt point was 24 C and phase transition heat was 225.5J/g .The microcapsules would been used in indoor wall to regulate the temperature and saving energy sources .The surface morphological structure was examined by means of scanning electron microscopy. The strength of shell was evaluated through observing the surface change after pressure by means of scanning electron microscopy. The melting point of the microcapsules was 24.7 C, nearly equaled to the pure phase change material. The DSC results make clearly that the polymer shell of microcapsules do not influence the proprieties of the phase change material. Also founded that the avoiding penetration property of double-shell microcapsules was better than that of single shell. It was necessary to investigate the shell for the thickness would affect the strength and penetration property of the microcapsules. In order to observe the double-shell shell we adapted the methods of in-bed the microcapsules in glutin, and got the SEM images of slices. The average thickness was 0.5-1 m. The thermal test showed the microPCMs had good resisted thermal properties and good absorb thermal property.
This article also calculated the microPCms quantities and energy saving effect in theory
designed the experimental apparatus to measure the energy saving effect, and analyzed the temperature equalization action of the microPCMs by comparing experimnt.
Last, polyurea microcapsule containing octadecane as phase change material was successfully synthesized by interfacial polycondensation using TDI and DETA as shell monomers in an emulsion only by reaction of TDI and DETA, but also reaction of TDI and amines which are formed by hydrolysis of TDI at the interface. In this study,
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