Microencapsulation of phase change material with poly(ethylacrylate) shell for thermal energy storage

Microcapsules containing caprylic acid and polyethylacrylate shells were prepared using an emulsion polymerization technique for thermal energy storage applications. Ethylene glycol dimethacrylate was used as a crosslinking agent. The influence of the crosslinking agent concentration on the phase change properties of microcapsules was examined. The caprylic acid microcapsules (MicroPCMs) were analyzed by Fourier transform infrared spectroscopy, thermal gravimetric analysis, scanning electron microscopy, and differential scanning calorimetry. The results showed that microcapsules were synthesized successfully and that the best shell material:crosslinking agent concentration ratio was 1:0.2. The melting and freezing temperatures were measured through differential scanning calorimetry analysis and found to be 13.3 and 7.1°C, respectively. The melting and crystallization heats were determined to be 77.3 and ?77.0 kJ/kg, and the mean particle diameter was 0.64 μm. The thermal cycling tests of the microcapsules were performed for 400 heating/cooling cycles, and the results indicate that the synthesized microcapsules have good thermal reliabilities. Air stability test proved that the thermal properties and physical form of microcapsules were not affected by air. We recommend the prepared thermal, air, and chemically stable caprylic acid microcapsules for thermal energy storage applications as novel microPCM with latent heat storage capacities and properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Development of pentadecane/diatomite and pentadecane/sepiolite nanocomposites fabricated by different compounding methods for thermal energy storage

Global warming is one of the most important consequences of excess energy consumption. Phase change materials (PCMs) have prominent advantages in thermal energy storage owing to their high latent heat capacities and small temperature variations during the phase change process. However, leakage is a major problem that limits the use of PCMs. Leakage may occur in encapsulated PCMs or in composites where the PCM is attached to the surface of a supporting material or within the pores of that material. In this study, pentadecane/diatomite and pentadecane/sepiolite nanocomposites were fabricated by using unmodified and microwave‐irradiated diatomite and sepiolite samples and by using different compounding processes, such as direct impregnation, vacuum impregnation, and ultrasonic‐assisted impregnation methods. The microstructures and the chemical and thermal properties of the composites were characterized by scanning electron microscopy, Fourier‐transform infrared spectroscopy, and differential scanning calorimetry. Subsequently, the thermal reliability and stability and the thermal conductivity of the PCM composites were also investigated. A melting temperature of 9.25°C and a latent heat capacity of 58.73 J/g were determined for the pentadecane/diatomite composite that was prepared with the direct impregnation method using a microwave‐treated diatomite sample. The pentadecane/sepiolite composite prepared in the melting temperature range 7.98°C to 8.53°C and latent heat capacity range 41.05 to 46.02 J/g. The results of the thermal analysis indicate that fabricated diatomite‐based or sepiolite‐based PCM composites have good potential as thermal energy storage materials.     

Synthetic and physical characterization of phase change materials microencapsulated by complex coacervation for thermal energy storage applications

This paper presents a comprehensive study of encapsulated phase change materials (PCMs). In order to investigate some synthesis parameters, microencapsulated paraffin with gelatin/gum Arabic wall system was prepared by the complex coacervation method and the performance of these microcapsules was evaluated by optical microscopy and differential scanning calorimetry. Further investigations were carried out on the impact of physical parameters on the melting time by studying the constrained melting transformation of an encapsulated PCM in a spherical shell subjected to a constant temperature media. Results indicate successful production of PCM microcapsules with high melting enthalpy (116 kJ/kg), and the effects of diameter and thermal conductivity on melting time of PCMs were demonstrated. Copyright © 2014 John Wiley & Sons, Ltd.     

Analysis of an encapsulated phase change material‐based energy storage system for high‐temperature applications

The capability of an encapsulated phase change material (EPCM)‐based thermal energy storage (TES) system to store a large fraction of latent energy at high temperatures was examined. A 3‐dimensional simulation of a prototype heat exchanger was conducted employing sodium nitrate as the phase change material (PCM). The k‐ω SST model was used to capture the turbulent flow of the HTF, while the melting front was tracked using the enthalpy‐porosity method. The results show that the use of metal deflectors yields a nearly constant heat transfer coefficient over the capsule's surface. Despite this, the presence of the void in the capsule and natural convection within the molten PCM influenced the storage characteristics of the system affecting the shape of the isotherms and melting front. Furthermore, the EPCM capsules consecutively undergo the same heat transfer starting from the capsule closest to the inlet. The EPCM capsules store 80% of the energy lost by the HTF. The 17.7 kg of sodium nitrate stores 14.5 MJ of energy where 20% of the energy stored is via latent heat. Of the energy released by the heat transfer fluid, 80% was absorbed by the EPCM capsules with the remaining energy going into the test section walls. A total of 14.5 MJ of energy was stored by the 17.7 kg of NaNO₃, of which 20% is attributed to the latent heat. The fraction of energy stored as latent heat would be larger if a smaller operating temperature range was used. Thus, an EPCM‐based latent heat TES system is capable of storing a large fraction of the supplied energy and presents efficient means of storing thermal energy for high‐temperature applications. Additionally, the strong agreement between the numerical and experimental works demonstrates that the numerical methods employed can predict the behavior of an EPCM capsule not only within a single capsule but on the system scale as well. Therefore, the applied numerical methods can be used for further design and optimization of EPCM‐based latent heat TES systems.     

Phase change microcapsules with lead tungstate shell for gamma radiation shielding and thermal energy storage

Novel microencapsulated phase change materials (MEPCMs) composed of the lead tungstate (PbWO₄) shell and paraffin core were designed for shielding of gamma radiation as well as thermal energy storage. Such MEPCMs were prepared via self‐assembly methods and in‐situ precipitation. The PbWO₄ shell with excellent photon attenuation can give the resulting MEPCMs an acceptable gamma radiation shielding capability. The chemical composition and structure of microcapsules samples were studied by X‐ray diffractometer (XRD) and Fourier‐transform infrared spectroscopy (FTIR). The effects of different core/shell mass ratios on the surface morphology and microstructure of the MEPCMs were determined by scanning electron microscopy (SEM), energy‐dispersive spectrometer (EDS), and transmission electronic microscopy (TEM). It was confirmed that the microcapsules exhibit a distinct core‐shell structure and a perfect spherical shape. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to present thermal stability and thermal‐storage capability of MEPCMs. A high‐purity germanium gamma spectrometer to measure the attenuation coefficient of the microcapsules for gamma rays showed that the MECPMs has good γ‐rays‐shielding property. The multifunction microcapsules in this study have great potential applications for building energy conservation as well as wearable personal protection in nuclear energy engineering.     

Microencapsulation of coco fatty acid mixture for thermal energy storage with phase change material

Thermal energy storage systems provide several alternatives for efficient energy use and energy conservation. Microcapsules of natural coco fatty acid mixture were prepared to be used as phase change materials for thermal energy storage. The coacervation technique was used for the microencapsulation process. Several alternatives for the capsule wall material were tried. The microcapsules were characterized according to their geometric profiles, phase transition temperatures, mean particle sizes, chemical stabilities, and their thermal cycling. The diameters of microcapsules prepared in this study were about 1 mm. Coco fatty acid mixtures have kept their geometrical profiles even after 50 thermal cycles for melting and freezing operations in temperature range from 22 to 34°C. It was found that gelatin+gum Arabic mixture was the best wall material for microencapsulating coco fatty acid mixtures. Copyright © 2005 John Wiley & Sons, Ltd.     

相变储能建筑材料的研究进展

相变储能建筑材料是相变材料与建材基体复合制备的一种新型储能建筑材料。本文分析了相变材料的筛选和改进方法及其封装技术的研究现状,介绍了相变材料与建材基体复合工艺,系统阐述了相变储能建筑材料的作用机理和应用现状,并指出了相变储能建筑材料在实际应用中存在的一些问题,最后展望了相变储能建筑材料的发展前景。     

储热材料的研究进展及其应用

综述了储热材料的研究进展和实际应用.介绍了储热材料的分类以及各类材料的性能、储能机理和优缺点;介绍了一些新型的相变材料,并结合实例探讨了储热材料在太阳能利用、建筑节能等领域的应用;指出了储热材料的研究方向和未来的发展趋势.     

Development and evaluation of graphite nanoplate (GNP)‐based phase change material for energy storage applications

In this study, arachidic acid (AA)/graphite nanoplate (GNP) composite material is proposed as a novel phase change material (PCM). In order to examine the influence of GNP loading into the base material (AA), composite PCMs were prepared with three different fractions (0.5, 1.0 and 2.0 in wt%). The thermal, chemical and morphological characteristics of the samples were introduced in terms of differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared, and X‐ray diffraction analyses. Moreover, the thermal conductivity values of samples in the liquid state were measured by means of 3ω method. It was found that, for GNP fractions of 0.5, 1, and 2 wt. %, the thermal conductivity of composite PCMs have been increased by 15, 30 and 43% in comparison to the pure AA. Results also revealed that the GNP loading into the pure AA led to a reduction in the degree of subcooling and a small diminution in the latent heat values. Considering the thermal cycling tests, it was also obtained that the proposed composite PCMs remained stable even at the highest GNP loading. Conduction‐dominated inward solidification process was simulated for one‐dimensional spherical computational domain. For this particular case, it was found that the increments of 15, 30 and 45% in thermal conductivity tend to increase the effectiveness by 3.5, 6.4 and 8.7%, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

柱状颗粒填充床的储能性能分析

填充床储能是一种很有发展前景的热能储存技术,它具有可降低存储成本和提高太阳能热系统开发效率等优点。研究人员多采用球形的储能单元,而圆柱体在储能填充床换热中有其独特的优势,因此基于圆柱形和拉西环形两种柱状颗粒,建立了一种潜热储能填充床的三维模型,采用数值模拟的方法分别研究两种柱状颗粒组成的填充床的储能性能,分析了储能填充床的直径比对其性能的影响。研究表明,填充床直径比越大,其储能性能越好。同时研究了圆柱形储能单元高度和拉西环形储能单元孔径对储能性能的影响。结果表明,在研究范围内,由高度为3 mm的圆柱形储能单元和孔半径1.50 mm的储能单元分别组成的填充床储能速率最高。     

Electrospun ultrafine composite fibers of binary fatty acid eutectics and polyethylene terephthalate as innovative form‐stable phase change materials for storage and retrieval of thermal energy

In this study, four fatty acids of lauric acid (LA), myristic acid (MA), palmitic acid (PA), and stearic acid (SA) were selected to prepare six binary fatty acid eutectics of LA‐MA, LA‐PA, LA‐SA, MA‐PA, MA‐SA, and PA‐SA; thereafter, electrospun ultrafine composite fibers with the binary fatty acid eutectics encapsulated in the supporting matrices of polyethylene terephthalate (PET) were prepared as innovative form‐stable phase change materials for storage and retrieval of thermal energy. The morphological structures and thermal energy storage properties of the ultrafine composite fibers were characterized by scanning electron microscope (SEM) and differential scanning calorimeter (DSC), respectively. The SEM results indicated that the fibers had the cylindrical morphology with diameters of 1–2 µm; some had smooth surfaces, while others had wrinkled surfaces with grooves. The DSC results indicated that the phase transition temperatures of binary fatty acid eutectics were lower than those of individual fatty acids; the enthalpy values associated with melting and crystallization for the eutectics encapsulated in the composite fibers were considerably reduced, whereas there were no appreciable changes on the phase transition temperatures. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhanced thermal conductivity of copper-doped polyethylene glycol/urchin-like porous titanium dioxide phase change materials for thermal energy storage

A composite phase change material (PCM) of copper-doped polyethylene glycol (PEG) 2000 impregnated urchin-like porous titanium dioxide (TiO₂) microspheres (PEG/TiO₂) was successfully synthesised. The urchin-like porous TiO₂ structures contain hollow cavities that can provide a high PEG loading capacity of up to 80 wt%. Copper nanoparticles were uniformly dispersed on the outer and inner surfaces of the 0.8PEG/TiO₂ as additives to enhance the thermal conductivity of the composite PCM. The latent heat of the Cu/PEG/TiO₂ porous composite PCM reached 133.8 J/g, and the thermal conductivity was 0.58 W/(mK), which was 152.2% higher than that of TiO₂ and 38.1% higher than 0.8PEG/TiO₂. Moreover, the Cu/PEG/TiO₂ porous composite PCM has excellent thermal stability and reliability.     

Polyurethane/graphite nano-platelet composites for thermal energy storage

In this work new polyurethane-based phase change materials containing segments of poly(ethylene glycol) with average molar mass of 8000 g/mol with and without chain extender and modified with graphite nano-platelets have been fabricated and characterized. Structure, morphology and phase behaviour of these solid-solid phase change materials were investigated, as well as the thermal stability and conductivity. The heat of phase transition was in the range of 118.0–164.5 J/g for polyurethane without chain extender and 128.0–148.5 J/g for polyurethane with chain extender. The highest heat of phase transition and crystallinity were found for system modified with 0.3% of graphite nano-platelets in polyurethane without chain extender. Modulated differential scanning calorimetry results showed some changes in the phase transition behaviour and the crystallinity of the polyurethane matrix due to graphite nano-platelets confinement effect. Enhancements in the thermal stability in polyurethane modified with graphite nano-platelets, attributed to the barrier effect, were found based on thermogravimetric analysis data. The thermal conductivity increased with an increase of graphite nano-platelets content for both polyurethane systems, with and without chain extender, which is important for modern thermal energy storage applications.     

Alternative storage options for solar thermal systems

The efficient implementation of solar systems in buildings depends on the storage of energy yielded, as it can both increase the solar system's autonomy and make it a feasible solution for zero energy buildings, and make storage vessels more compact, reducing precious space requirements. This is of particular important in places with reduced time of sunshine, where solar systems are less effective, because of the deviation between solar radiation and the demand. The traditional storage options use water, which is practical, safe and low‐cost, especially when the storage requirements are small. However, when larger storage is needed, limits concerning the use of water exist, mainly due to the need for larger installation space and the increased thermal losses. The use of phase change materials (PCM) for thermal energy storage seems an upcoming technology. The main idea is the substitution of water with PCM, which feature larger specific energy storage capacity compared to other conventional materials. In the context of the specific paper, a combined solar thermal system used for the preparation of domestic hot water (DHW) and space heating (Solar Combi System) with two different types of storage is studied, for two Greek cities. The aim is to find out which is the most efficient way of storing energy with respect to the autonomy of the system, for a solar combi system. This is being achieved by determining the comparative autonomy of PCM and water storage system for various climates. It was proven that using PCM is advantageous, as it can extend the autonomy duration of the solar system for 2 to 8 hours, depending on the season and the climatic conditions. However, it was also seen that in solar combi systems used throughout the whole year, PCM are inefficient during summer period.     

Developing microencapsulated 12‐hydroxystearic acid (HSA) for phase change material use

Phase change materials (PCM) have an increasingly more important role as a thermal energy storage (TES) media. However, leakage problem of PCM causes limitation during their integration in TES systems. Therefore, the encapsulation of PCMs is attracting research interest to extend usage of PCMs in real TES applications in recent years. In this study, hydroxystearic acid (HSA) was encapsulated with polymethyl methacrylate (PMMA) and different PMMA comonomer shells via emulsion polymerization method for the first time in literature. HSA with high melting temperature range (74–78°C) can widen the scope of using PCMs, and the encapsulated form can make it more versatile. The chemical structures, morphologies, and thermophysical properties of capsules were determined by FT‐IR, SEM, DSC, TGA, and thermal infrared camera. Among the produced HSA capsule candidates, PMMA‐HEMA is the most promising with latent heat of 48.5 J/g with melting range of 47 to 85°C. SEM analysis indicated that the capsules have spherical shape with compact surface at nano‐micro (100–440 nm) size range; however, some capsules exhibited agglomeration.     

Fatty acid/poly(methyl methacrylate) (PMMA) blends as form-stable phase change materials for latent heat thermal energy storage

Fatty acids such as stearic acid (SA), palmitic acid (PA), myristic acid (MA), and lauric acid (LA) are promising phase change materials (PCMs) for latent heat thermal energy storage (LHTES) applications, but high cost is the most drawback which limits the utility area of them in thermal energy storage. The use of fatty acids as form-stable PCM will increase their feasibilities in practical LHTES applications due to reduced cost of the energy storage system. In this regard, a series of fatty acid/poly(methyl methacrylate) (PMMA) blends, SA/PMMA, PA/PMMA, MA/PMMA, and LA/PMMA were prepared as new kinds of form-stable PCMs by encapsulation of fatty acids into PMMA which acts as supporting material. The blends were prepared at different mass fractions of fatty acids (50, 60, 70, 80, and 90% w/w) to reach maximum encapsulation ratio. All blends were subjected to leakage test by heating the blends over the melting temperature of the PCM. The blends that do not allow leakage of melted PCM were identified as form-stable PCMs. The form-stable fatty acid/PMMA (80/20 wt.%) blends were characterized using optic microscopy (OM), viscosimetry, and Fourier transform infrared (FT-IR) spectroscopy methods, and the results showed that the PMMA was compatible with the fatty acids. In addition, thermal characteristics such as melting and freezing temperatures and latent heats of the form-stable PCMs were measured by using differential scanning calorimetry (DSC) technique and indicated that they had good thermal properties. On the basis of all results, it was concluded that form-stable fatty acid/PMMA blends had important potential for some practical LHTES applications such as under floor space heating of buildings and passive solar space heating of buildings by using wallboard, plasterboard or floor impregnated with a form-stable PCM due to their satisfying thermal properties, easily preparing in desired dimensions, direct usability without needing an add encapsulation and eliminating the thermal resistance caused by shell and thus reducing cost of LHTES system.     

固-液相变贮能材料的研究进展

固-液相变贮能材料具有贮能密度大、相变温度恒定、体积变化小等优点，已成为能源开发利用和材料科学研究的新热点。综述了固-液相变贮能材料的研究现状，介绍了其分类及各类材料贮能性能，并总结了其应用上的缺陷及解决方法。     

Phase change characteristics of ethylene glycol solution‐based nanofluids for subzero thermal energy storage

Nanofluids, particularly water‐based nanofluids, have been extensively studied as liquid–solid phase change materials (PCMs) for thermal energy storage (TES). In this study, nanofluids with aqueous ethylene glycol (EG) solution as the base fluid are proposed as a novel PCM for cold thermal energy storage. Nanofluids were prepared by dispersing 0.1–0.4 wt% TiO₂ nanoparticles into 12, 22, and 34 vol.% EG solutions. The dispersion stability of the nanofluids was evaluated by Turbiscan Lab. The liquid–solid phase change characteristics of the nanofluids were also investigated. Phase change temperature (PCT), nucleation temperature, and half freezing time (HFT) were investigated in freezing experiments. Subcooling degree and HFT reduction were then calculated. Latent heat of solidification was measured using differential scanning calorimetry. Thermal conductivity was determined using the hot disk thermal constant analyzer. Experimental results show that the nanoparticles decreased the PCT of 34 vol.% EG solution but minimally influenced the PCT of 12 and 22 vol.% EG solutions. For all nanofluids, the nanoparticles decreased the subcooling degree, HFT, and latent heat but increased the thermal conductivity of the EG solutions. The mechanism of the improvement of the phase change characteristics and decrease in latent heat by the nanoparticles was discussed. The nanoparticles simultaneously served as nucleating agent that induced crystal nucleation and as impurities that disturbed the growth of water crystals in EG solution‐based nanofluids. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal properties and crystallization kinetics of pentaglycerine/graphene nanoplatelets composite phase change material for thermal energy storage

Solid-solid phase change materials (SSPCMs) used in thermal energy storage (TES) system attract much attention in recent days. Here, graphene nanoplatelets (GnPs) were introduced into pentaglycerine (PG) with mass ratios of 1 wt%, 2 wt%, and 4 wt% to obtain PG/GnPs PCMs. The structure and thermal property of PG/GnPs PCMs were characterized by SEM, XPS, FT-IR, POM, DSC, thermal conductivity tester, and heat transfer performance test system. The effect of GnPs on the crystallization kinetic of PG was investigated by isoconversional method. The results indicated that PG and GnPs were uniformly mixed together by physical reaction. GnPs reduced the subcooling and enhanced the thermal conductivity of the PG/GnPs. The heat transfer rate of PG/GnPs was improved during to the high thermal conductivity. Crystallization kinetic results presented that the activation energy increases with the GnP content. In summary, GnPs improved the thermal behaviors of PG.     

Characterization of granular phase changing composites for thermal energy storage using the T‐history method

The present article reports on the characterization of granular phase changing composites using the T‐history method. Further modifications and improvements of the method are employed to handle granular materials undergoing phase change over a temperature range. The accuracy of the T‐history method is shown to be limited by the assumption of temperature‐independent specific heats and the difficulty of determining the limits of solid and liquid phases. The concept of enthalpy and its relationship with temperature has been employed in the analysis to overcome these difficulties. Enthalpy–temperature and apparent heat capacity curves similar to those obtained using DSC have been developed. These characteristic curves are necessary for accurate design, modeling, and optimization of latent heat thermal energy storage systems. Experiments have been also carried out to measure the transient temperature distribution inside a cylindrical packed bed using phase changing granulates. Analysis of temperature variation along the bed shows good agreement with the measured phase change characteristics. Copyright © 2009 John Wiley & Sons, Ltd.