界面聚合法制备正二十烷微胶囊化相变储热材料

采用界面聚合的方法, 以甲苯鄄2,4-二异氰酸酯(TDI)和乙二胺(EDA)为反应单体, 非离子表面活性剂聚乙二醇壬基苯基醚(OP)为乳化剂, 合成了正二十烷为相变材料的聚脲包覆微胶囊. 结果表明, 二异氰酸酯和乙二胺按质量比1.9:1 进行反应. 以透射电镜和激光粒度分析仪分析微胶囊, 测得空心微胶囊直径约为0.2 μm, 含正二十烷微胶囊约为2-6 μm. 红外光谱分析证明, 壁材料聚脲是由TDI 及EDA 两种单体形成的. 正二十烷的包裹效率约为75%. 微胶囊的熔点接近囊芯二十烷的熔点, 而其储热量在壁材固定时随囊芯的量而变. 热重分析表明, 囊芯正二十烷、含正二十烷的微胶囊以及壁材料聚脲, 能够耐受的温度分别约为130 ℃、170 ℃及270 ℃.     

一种致密的相变储能微胶囊的制备与表征

制备了以聚脲为第一壁材、苯乙烯-二乙烯苯为第二壁材,以相变点在16℃左右的石蜡为芯材的相变储能微胶囊。采用红外光谱、差示扫描量热分析、热重分析测试技术表征了制备的相变储能微胶囊的结构组成以及热性能;采用溶剂淋洗法研究了影响包覆率的因素。结果表明,相变储热微胶囊是复合相变材料,微胶囊的热稳定性好,致密性优良;通过对水油比、乳化剂及苯乙烯-二乙烯苯用量等各因素对微胶囊包覆率影响的讨论,得出在水与油质量比3.2,乳化剂相对于水的质量分数为2%时,加入苯乙烯与二乙烯苯质量比为10∶1混合液的质量分数为6.0%时,其包覆率达81.14%;制备的微胶囊能耐较高温度,在150℃以下无质量损失,且微胶囊储热能力高达80J/g。同时发现,储热能力与芯壁比有关,比值越大储热潜能越高。     

Preparation and Characterization of Microencapsulated Hexadecane Used for Thermal Energy Storage

Polyurea microcapsules about 2.5μm in diameter containing phase change material for thermal energy storage application were synthesized and characterized by interfacial polycondensation method with toluene-2,4-diisocyanate and ethylenediamine as monomers in an emulsion system. Hexadecane was used as a phase change material and OP, which is nonionic surfactant, and used as an emulsifier. The chemical structure and thermal behavior of the microcapsules were investigated by FTIR and thermal analysis respectively. The results show encapsulated hexadecane has a good potential as a solar energy storage material.     

界面聚合法制备正二十烷微胶囊化相变储热材料

用界面聚合的方法,以甲苯-2,4-二异氰酸酯(TDI)和己二胺(HDA)为反应单体,非离子表面活性剂聚乙二醇壬基苯基醚(OP)为乳化剂,合成了正二十烷为相变材料的聚脲包覆微胶囊. 结果表明,二异氰酸酯和己二胺按质量比为1.5∶ 0.8进行反应. 空心微胶囊的直径约为0.2 μm,含正二十烷微胶囊直径为2~6 μm. 红外光谱分析证明, 囊壁聚脲是由TDI及HDA 2种单体形成. 正二十烷包裹效率为65%~80%. 微胶囊的熔点接近囊芯正二十烷的熔点,而其储热量在壁材固定时随囊芯的量而变. 热重分析结果表明,囊芯正二十烷、含正二十烷的微胶囊以及壁材聚脲,能够耐受的温度分别约为130、165及250 ℃.     

复合相变储能材料的制备及应用研究进展

系统概述了复合相变储能材料的制备方法及其研究进展。特别介绍了固-液复合相变储能材料的制备方法,如熔融浸渍混合法、溶胶-凝胶法、静电纺丝法、真空渗入法和超声波法等。并结合实例探讨了复合相变储能材料在太阳能利用、建筑节能和纺织行业等领域的应用,在此基础上对其研究方向进行了展望。     

相变储能材料的研究进展

综述了相变材料的研究进展状况 ,介绍了相变材料的分类以及各类相变材料的性能、储能机理和优缺点 ,并介绍了一些新型的相变材料 ,指出了该领域中有待解决的问题 ,展望了未来相变材料的发展前景。     

Combination of Passive and Active Solar Heating with Thermal Energy Storage

This study investigated the impact of individual and combination of different sources of heating (passive solar heating, electric oil-heater, and solar air heater) in a pilot-scale building containing phase change material (PCM) for a potential reduction in energy consumption while maintaining thermal comfort. Unlike most of the recent simulations and modelling studies, this impact was tested experimentally using two identical control and test huts located at the University of Auckland. The control hut was equipped with standard gypsum boards while the test hut had gypsum boards containing PCM (PureTemp 20, PT20). The study found that combining both active and passive solar heating with a temperature-controlled electric oil heater demonstrated the ability to provide significant energy savings and maintain thermal comfort in the test hut, most notably overnight. The suggested combination was tested over different weather conditions and with different temperature constraints to maintain thermal comfort and achieve energy savings ranging from 33% to 87.5%.     

Effects of Total Thermal Balance on the Thermal Energy Absorbed or Released by a High-Temperature Phase Change Material

Front tracking and enthalpy methods used to study phase change processes are based on a local thermal energy balance at the liquid–solid interface where mass accommodation methods are also used to account for the density change during the phase transition. Recently, it has been shown that a local thermal balance at the interface does not reproduce the thermodynamic equilibrium in adiabatic systems. Total thermal balance through the entire liquid–solid system can predict the correct thermodynamic equilibrium values of melted (solidified) mass, system size, and interface position. In this work, total thermal balance is applied to systems with isothermal–adiabatic boundary conditions to estimate the sensible and latent heat stored (released) by KNO3 and KNO3/NaNO3 salts which are used as high-temperature phase change materials. Relative percent differences between the solutions obtained with a local thermal balance at the interface and a total thermal balance for the thermal energy absorbed or released by high-temperature phase change materials are obtained. According to the total thermal balance proposed, a correction to the liquid–solid interface dynamics is introduced, which accounts for an extra amount of energy absorbed or released during the phase transition. It is shown that melting or solidification rates are modified by using a total thermal balance through the entire system. Finally, the numerical and semi-analytical methods illustrate that volume changes and the fraction of melted (solidified) solid (liquid) estimated through a local thermal balance at the interface are not invariant in adiabatic systems. The invariance of numerical and semi-analytical solutions in adiabatic systems is significantly improved through the proposed model.     

正十六烷聚脲微胶囊化相变材料

用界面聚合法，合成了直径大约2.5 μm可用于热能储存含相变材料的聚脲包覆微胶囊.在含乳化剂的水溶液中，将溶有芯材正十六烷的有机相乳化成微米级油性液滴，随后加入的水溶性单体二胺与甲苯2,4-二异氰酸酯在胶束界面相互反应形成囊壁.分别用乙烯二胺，1,6-己二胺和它们的混合物作为水溶性单体进行了研究.并用红外光谱和热分析分别考察了不同胺类对微胶囊化学结构和热性质的影响.红外谱图显示合成了聚脲微胶囊，热重曲线表明含正十六烷的聚脲微胶囊能够耐受大约300 ℃高温，差示扫描量热测试表明所有样品均具有合适的相转变热，冷热循环实验揭示微胶囊能够维持储热容量不衰减.研究表明微胶囊化的正十六烷作为相变储热材料具有良好的应用前景.     

蓄热调温石蜡相变微胶囊的制备及性能

采用界面聚合法,以甲苯2,4-二异氰酸酯和哌嗪为反应单体、30号相变石蜡为芯材,制得了一种智能纺织品用蓄热调温相变微胶囊。通过红外光谱、扫描电镜、差示扫描量热仪对微胶囊的化学组成、形貌和蓄热性能进行了表征,测试了其耐热和耐溶剂性。结果表明:所得微胶囊主要为球形,表面光滑,平均粒径为10.6μm,对w=0.40的NaOH溶液、w=0.60的H2SO4溶液、无水乙醇、丙酮稳定,能被甲苯、二甲基甲酰胺、乙醚破坏。相变潜热为118 J/g,石蜡在微胶囊中的质量分数为84%。     

The Thermal Charging Performance of Finned Conical Thermal Storage System Filled with Nano-Enhanced Phase Change Material

A latent heat thermal energy storage (LHTES) unit can store a notable amount of heat in a compact volume. However, the charging time could be tediously long due to weak heat transfer. Thus, an improvement of heat transfer and a reduction in charging time is an essential task. The present research aims to improve the thermal charging of a conical shell-tube LHTES unit by optimizing the shell-shape and fin-inclination angle in the presence of nanoadditives. The governing equations for the natural convection heat transfer and phase change heat transfer are written as partial differential equations. The finite element method is applied to solve the equations numerically. The Taguchi optimization approach is then invoked to optimize the fin-inclination angle, shell aspect ratio, and the type and volume fraction of nanoparticles. The results showed that the shell-aspect ratio and fin inclination angle are the most important design parameters influencing the charging time. The charging time could be changed by 40% by variation of design parameters. Interestingly a conical shell with a small radius at the bottom and a large radius at the top (small aspect ratio) is the best shell design. However, a too-small aspect ratio could entrap the liquid-PCM between fins and increase the charging time. An optimum volume fraction of 4% is found for nanoparticle concentration.     

Characterization of Unripe and Mature Avocado Seed Oil in Different Proportions as Phase Change Materials and Simulation of Their Cooling Storage

Environmental problems have been associated with energy consumption and waste management. A solution is the development of renewable materials such as organic phase change materials. Characterization of new materials allows knowing their applications and simulations provide an idea of how they can developed. Consequently, this research is focused on the thermal and chemical characterization of five different avocado seed oils depending on the maturity stage of the seed: 100% unripe, 25% mature-75% unripe, 50% mature-50% unripe, 75% mature-25% unripe, and 100% mature. The characterization was performed by differential scanning calorimetry, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The best oil for natural environments corresponded to 100% matured seed with an enthalpy of fusion of 52.93 J·g−1, and a degradation temperature between 241–545 °C. In addition, the FTIR analysis shows that unripe seed oil seems to contain more lipids than a mature one. Furthermore, a simulation with an isothermal box was conducted with the characterized oil with an initial temperature of −14 °C for the isothermal box, −27 °C for the PCM box, and an ambient temperature of 25 °C. The results show that without the PCM the temperature can reach −8 °C and with it is −12 °C after 7 h, proving its application as a cold thermal energy system.     

环状氯化磷腈阻燃微胶囊制备研究

通过UV界面聚合法,制备了以环状氯化磷腈为囊芯,丙烯酸酯共聚物为囊壁的阻燃微胶囊。对产物微胶囊的性质进行了系统表征,具体包括粒径及其分布、化学结构、表面形态和热稳定。结果表明:包囊提高了环状氯化磷腈的热稳定性、阻燃性,且对环氧复合材料的力学性能影响甚微。     

Encapsulation of octadecane in poly(divinylbenzene-co-methyl methacrylate) using phase inversion emulsification for droplet generation

Octadecane (OD), a heat storage material, was encapsulated into poly(divinylbenzene-co-methyl methacrylate) or P(DVB-co-MMA) matrix via the microsuspension polymerization. The oil droplets were first generated by using the phase inversion emulsification, i.e., adding a sodium dodecyl sulphate (SDS) aqueous solution into an oil phase (monomers:OD = 1:1) containing various concentrations of poly(vinyl alcohol) (PVA). Results showed that 0.1 wt% of SDS in aqueous medium with the additional rate of 2 mL/min and 3 wt% of PVA in oil phase were the optimal conditions for the formation of nonspherical microcapsules. The smallest number- (d_n) and weight- (d_w) average diameters of P(DVB-co-MMA)/OD were, respectively, 3.1 and 3.2 µm with a narrow particle size distribution (d_w/d_n) of 1.02. The latent heats of the encapsulated OD increased with increasing MMA content of microcapsules. The heat of melting (ΔH_m; 223 J/g-OD) and crystallization (ΔH_c; 230 J/g-OD) of the OD encapsulated in microcapsules using DVB:MMA of 30:70 were higher than those using only PDVB (189 and 193 J g-OD for ΔH_m and ΔH_c, respectively) and comparable to those of bulk OD (233 and 234 J/g-OD for ΔH_m and ΔH_c, respectively). The obtained P(DVB-co-MMA)/OD microcapsules would be useful as high performance heat storage material.     

微胶囊化石蜡的制备和热性能

微胶囊化石蜡的制备和热性能;微胶囊;原位聚合法;相变材料;差示扫描量热法     

Thermal Charging Optimization of a Wavy-Shaped Nano-Enhanced Thermal Storage Unit

A wavy shape was used to enhance the thermal heat transfer in a shell-tube latent heat thermal energy storage (LHTES) unit. The thermal storage unit was filled with CuO–coconut oil nano-enhanced phase change material (NePCM). The enthalpy-porosity approach was employed to model the phase change heat transfer in the presence of natural convection effects in the molten NePCM. The finite element method was applied to integrate the governing equations for fluid motion and phase change heat transfer. The impact of wave amplitude and wave number of the heated tube, as well as the volume concertation of nanoparticles on the full-charging time of the LHTES unit, was addressed. The Taguchi optimization method was used to find an optimum design of the LHTES unit. The results showed that an increase in the volume fraction of nanoparticles reduces the charging time. Moreover, the waviness of the tube resists the natural convection flow circulation in the phase change domain and could increase the charging time.     

交联型聚氨酯固-固相变材料的相变性能及形态

聚氨酯;聚乙二醇;储能材料;固 固相变材料;相变行为     

Thermal Energy Storage and Heat Transfer of Nano-Enhanced Phase Change Material (NePCM) in a Shell and Tube Thermal Energy Storage (TES) Unit with a Partial Layer of Eccentric Copper Foam

Thermal energy storage units conventionally have the drawback of slow charging response. Thus, heat transfer enhancement techniques are required to reduce charging time. Using nanoadditives is a promising approach to enhance the heat transfer and energy storage response time of materials that store heat by undergoing a reversible phase change, so-called phase change materials. In the present study, a combination of such materials enhanced with the addition of nanometer-scale graphene oxide particles (called nano-enhanced phase change materials) and a layer of a copper foam is proposed to improve the thermal performance of a shell-and-tube latent heat thermal energy storage (LHTES) unit filled with capric acid. Both graphene oxide and copper nanoparticles were tested as the nanometer-scale additives. A geometrically nonuniform layer of copper foam was placed over the hot tube inside the unit. The metal foam layer can improve heat transfer with an increase of the composite thermal conductivity. However, it suppressed the natural convection flows and could reduce heat transfer in the molten regions. Thus, a metal foam layer with a nonuniform shape can maximize thermal conductivity in conduction-dominant regions and minimize its adverse impacts on natural convection flows. The heat transfer was modeled using partial differential equations for conservations of momentum and heat. The finite element method was used to solve the partial differential equations. A backward differential formula was used to control the accuracy and convergence of the solution automatically. Mesh adaptation was applied to increase the mesh resolution at the interface between phases and improve the quality and stability of the solution. The impact of the eccentricity and porosity of the metal foam layer and the volume fraction of nanoparticles on the energy storage and the thermal performance of the LHTES unit was addressed. The layer of the metal foam notably improves the response time of the LHTES unit, and a 10% eccentricity of the porous layer toward the bottom improved the response time of the LHTES unit by 50%. The presence of nanoadditives could reduce the response time (melting time) of the LHTES unit by 12%, and copper nanoparticles were slightly better than graphene oxide particles in terms of heat transfer enhancement. The design parameters of the eccentricity, porosity, and volume fraction of nanoparticles had minimal impact on the thermal energy storage capacity of the LHTES unit, while their impact on the melting time (response time) was significant. Thus, a combination of the enhancement method could practically reduce the thermal charging time of an LHTES unit without a significant increase in its size.     

Homogeneous-to-Heterogeneous-Strategy Enables Multifunctional Phase-Change Materials for Energy Storage

Functional phase-change materials (PCMs) are conspicuously absent in various organic or inorganic solids with diversified applications in which the attributes of these molecular materials have been highly realized. Leakage problem during the phase transition process is the main obstacle on the way of widely use of solid-liquid PCMs who has been recognized to be promisingly practical candidates for energy storage owing to the high energy storage density and small volume change in the phase transition process. Herein, a novel homogeneous-to-heterogeneous-strategy, in which all the starting materials involved display a homogeneous state and the encapsulation framework formed in situ in the encapsulation process, enabled by an aerogel reaction of silica was realized under the catalysis of an organic base. Besides the comprehensive study upon energy storage performance, light-to-thermal conversion and recyclability performance study of the obtained materials reveal the clear superiority over pristine paraffin wax (PW) thanks to the versatility and robustness of this fabrication method. More importantly, the homogeneous-to-heterogeneous-strategy endows a unique adsorption ability with respect to organic pollutant due to the PCMs inside and therefore bearing a great potential to be used in environment protection fields.     

Development of Novel Polypropylene Syntactic Foams Containing Paraffin Microcapsules for Thermal Energy Storage Applications

polypropylene (PP) syntactic foams (SFs) containing hollow glass microspheres (HGMs) possess low density and elevated mechanical properties, which can be tuned according to the specific application. A possible way to improve their multifunctionality could be the incorporation of organic Phase Change Materials (PCMs), widely used for thermal energy storage (TES) applications. In the present work, a PCM constituted by encapsulated paraffin, having a melting temperature of 57 °C, was embedded in a compatibilized polypropylene SF by melt compounding and hot pressing at different relative amounts. The rheological, morphological, thermal, and mechanical properties of the prepared materials were systematically investigated. Rheological properties in the molten state were strongly affected by the introduction of both PCMs and HGMs. As expected, the introduction of HGMs reduced both the foam density and thermal conductivity, while the enthalpy of fusion (representing the TES capability) was proportional to the PCM concentration. The mechanical properties of these foams were improved by the incorporation of HGMs, while they were reduced by addition of PCMs. Therefore, the combination of PCMs and HGMs in a PP matrix generated multifunctional materials with tunable thermo-mechanical properties, with a wide range of applications in the automotive, oil, textile, electronics, and aerospace fields.