Thermal properties of 3-hydroxy fatty acids and their binary mixtures as phase change energy storage materials

In the present work, we describe the chemical synthesis of 3-HFAs as prominent derivatives of fatty acids and assess if they could be applied as phase change materials (PCM). In addition, 3-HFAs were obtained by depolymerization of a bacterial biopolymeric material, polyhydroxyalkanoate. Thermal properties of 3-hydoxyoctanoic, decanoic, and dodecanoic acids are reported for the first time. These materials showed the potential to be applied as PCM in temperature range from 33°C to 66°C. In order to expand the temperature range for application of 3-HFAs as PCM, eutectic mass ratios of three kinds of binary mixtures of 3-HFAs were calculated, and their properties were predicted using the Schröder-van Laar equation. Thermal properties of these mixtures were validated by differential scanning calorimetry (DSC) analysis. These results showed that eutectics considerably expanded the scope of applications of 3-HFAs as PCMs. 3-HFAs originating from biotechnologically obtained polyhydroxyalkanoates also showed potential to be applied in development of PCMs.     

节能建筑用蓄热材料的释热性能实验研究

相变材料在发生相变的过程中吸收或者释放热量，在太阳能利用、建筑节能和空调采暖方面有着广阔的应用前景。通过实验研究了可用于节能建筑的相变材料——硫酸钠水合盐体系相变材料的释热性能，研究了不同增稠剂和成核剂对其放热性能的影响，对节能建筑用相变建材的研究有参考价值。     

High-temperature phase change materials for thermal energy storage

The development of energy saving technologies is very actual issue of present day. One of perspective directions in developing these technologies is the thermal energy storage in various industry branches. The review considers the modern state of art in investigations and developments of high-temperature phase change materials perspective for storage thermal and a solar energy in the range of temperatures from 120 to 1000 °C. The considerable quantity of mixes and compositions on the basis of fluorides, chlorides, hydroxides, nitrates, carbonates, vanadates, molybdates and other salts, and also metal alloys is given. Thermophysical properties of potential heat storage salt compositions and metal alloys are presented. Compatibility of heat storage materials (HSM) and constructional materials have found its reflection in the present work. Data on long-term characteristics of some HSMs in the course of repeated cycles of fusion and solidification are analyzed. Article considers also other problems which should be solved for creation of commercial high-temperature heat storage devices with use of phase change materials.     

Form-stable phase change materials for thermal energy storage

The present paper considers the state of investigations and developments in form-stable phase change materials for thermal energy storage. Paraffins, fatty acids and their blends, polyethylene glycol are widely used as latent heat storage component in developing form-stable materials while high-density polyethylene (HDPE), styrene-butadiene-styrene (SBS) triblock copolymer, Eudragit S, Eudragit E, poly (vynil chloride) (PVC), poly (vynil alcohol) (PVA) and polyurethane block copolymer serve as structure supporting component. A set of organic and metallo-organic materials with high transition heat in solid-solid state is considered as perspective for-stable materials to store thermal energy. Another perspective class of form-stable materials are the materials on the basis of such porous materials as expanded perlite and vermiculite impregnated with phase change heat storage materials. The technology of producing new form-stable ultrafine heat storage fibers is developed. It opens availability to produce the clothers with improved heat storage ability for extremely cold regions. The perspective fields of application of form-stable materials are discussed. The further directions of investigations and developments are considered.     

用于储存太阳能的相变蓄热器蓄热性能研究

利用计算流体力学软件Fluent的凝固/熔化模型,模拟了用于储存太阳能的两种相变蓄热器的蓄热过程,得到了蓄热过程中相变区的温度云图,分析了两种蓄热器的蓄热能力和传热方式。研究结果表明,合理增加内管数量可以提高相变过程中的对流换热强度和蓄热能力。     

Recent progress in thermal energy storage materials

本文结合储热材料的分类、特点、应用及存在的问题对储热材料的最新研究进展进行了综述,主要包括有机相变储热材料、熔融盐类相变储热材料、合金相变储热材料及复合类储热材料。探讨了储热材料成分组成、制备工艺及性能特点,进一步介绍了其最新研究进展,并对储热材料的下一步研究进行了展望,提出开发高性能纳微复合结构储热材料是未来研究的重点。     

Fatty acid eutectic/polymethyl methacrylate composite as form-stable phase change material for thermal energy storage

This work is focused on the preparation and characterization of fatty acid eutectic/polymethyl methacrylate (PMMA) form-stable phase change material (PCM). Capric acid (CA), lauric acid (LA), myristic acid (MA) and stearic acid (SA) were selected to prepare binary fatty acid eutectic for the sake of decreasing the phase change temperature. Using the method of self-polymerization, CA–LA, CA–MA, CA–SA and LA–MA eutectics acting as the heat-absorbing materials and PMMA serving as the supporting material were compounded in the ratio of 50/50 wt.%. The relations between mass fraction of LA–MA eutectic and latent heat and compressive strength of LA–MA/PMMA composite were discussed, and the feasible maximum mass fraction of LA–MA eutectic was determined to be 70%. CA–LA/PMMA, CA–MA/PMMA, CA–SA/PMMA and LA–MA/PMMA composites were examined to investigate their potential application in building energy conservation. Scanning electron microscope and polarizing optical microscope observations showed that fatty acid eutectic was coated by PMMA thus the composite remained solid when the sample was heated above the melted point of the fatty acid. Fourier-transform infrared results indicated that fatty acid and PMMA had no chemical reaction and exhibited good compatibility with each other. According to the differential scanning calorimetry results, phase change temperatures of CA–LA/PMMA, CA–MA/PMMA, CA–SA/PMMA and LA–MA/PMMA composites were 21.11 °C, 25.16 °C, 26.38 °C and 34.81 °C and their latent heat values were determined to be 76.3 kJ/kg, 69.32 kJ/kg, 59.29 kJ/kg and 80.75 kJ/kg, respectively. Moreover, thermal stability and expansibility of the form-stable PCMs were characterized by thermogravimetric analysis and volume expansion coefficient respectively, and the results indicated that the composites were available for building energy conservation.     

Hexamethylene dilauroyl, dimyristoyl, and dipalmytoyl amides as phase change materials for thermal energy storage

Hexamethylene dilauroyl, dimyristoyl, and dipalmytoyl amides have been produced as solid-liquid phase change materials via condensation of hexamethylene diamine with the respective acyl chlorides (lauroyl chloride, myristoyl chloride, and palmytoyl chloride) and were characterized by FT-IR, NMR, DSC, and TG analysis. Hexamethylene dilauroyl, dimyristoyl, and dipalmytoyl amides crystallized due to structural symmetry and flexibility of long alkyl groups. They were characterized by DSC and FT-IR spectroscopy before and after thermal cycling to determine their thermal reliability. Phase change enthalpies were found 110.1 and −103.3 J g⁻¹ for hexamethylene dilauroyl amide (N,N′-hexamethylene didodecanamide), 116.9 and −110.4 J g⁻¹ for hexamethylene dimyristoyl amide (N,N′-hexamethylene ditetradecanamide), and 144.5 and −140.5 J g⁻¹ for hexamethylene dipalmytoyl amides (N,N′-hexamethylene dihexadecanamide) by DSC. The endurance of hexamethylene dilauroyl, dimyristoyl, and dipalmytoyl amides was studied by TG analysis.     

Phase change performance assessment of salt mixtures for thermal energy storage material

The phase transition performance of the CaCl₂ · 6H₂O–Ca(NO₃)₂ · 4H₂O composite salt system with nucleating and thickening agents was investigated in this paper. The CaCl₂ · 6H₂O–Ca(NO₃)₂ · 4H₂O composite salt system was prepared by adding Ca(NO₃)₂ · 4H₂O (12 wt%) to CaCl₂ · 6H₂O. Different nucleating agents including SrCl₂ · 6H₂O, SrCO₃, BaCl₂, BaCO₃, Na₂B₄O₇ · 10H₂O, H₃BO₃ and NH₄Cl were used to address the problems of phase segregation and supercooling phenomena during the phase change process. The results show that the single nucleating agent SrCl₂ · 6H₂O or the mixture of nucleating agents with 2 wt% SrCl₂ · 6H₂O, 1 wt% BaCl₂ and 0.5 wt% of thickening agent carboxyl methyl cellulose is the most suitable for this system. The latent heat remained constant at about 116 J/g before and after adding the agents. Density functional theory was used to further investigate the microstructure‐related reason for the salt–water separation and supercooling phenomena. It can be deduced that the hydrogen bond is the vital factor involved during the phase transition. The aim of adding thickener was to form more hydrogen bonds which encapsulated the hydrated species and made it difficult to lose the hydrated waters. The main purpose of adding nucleating agent was to break the metastable state among microscopic species. The results of this work indicate that the CaCl₂ · 6H₂O–Ca(NO₃)₂ · 4H₂O salt mixture has potential as a thermal energy storage material. Copyright © 2017 John Wiley & Sons, Ltd.     

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.     

Review of mathematical modeling on latent heat thermal energy storage systems using phase-change material

Mathematical modeling of a latent heat thermal energy storage system (LHTES) was used for the optimum material selection and to assist in the optimal designing of the systems. In this paper, two types of models are mainly discussed, on the basis of first law and second law of thermodynamics. The important characteristics of different models and their assumptions used are presented and discussed, the experimental validation of some models are also presented.     

Low temperature latent heat thermal energy storage: Heat storage materials

Heat-of-fusion storage materials for low temperature latent heat storage in the temperature range 0–120°C are reviewed. Organic and inorganic heat storage materials classified as paraffins, fatty acids, inorganic salt hydrates and eutectic compounds are considered. The melting and freezing behaviour of the various substances is investigated using the techniques of Thermal Analysis and Differential Scanning Calorimetry. The importance of thermal cycling tests for establishing the long-term stability of the storage materials is discussed. Finally, some data pertaining to the corrosion compatibility of heat-of-fusion substances with conventional materials of construction is presented.     

State-of-the-art of phase-change thermal storage at middle-low temperature

相变蓄热技术由于蓄热密度大,温度恒定,在国内外得到广泛的研究与应用,尤其在能源供给不连续的情况下,应用的尤其广泛.相变储热系统作为解决能源供应时间与空间矛盾的有效手段,是提高能源利用率的重要途径之一.本文从相变材料的选取,相变过程数值模拟,相变蓄热装置3个方面对中低温相变蓄热的研究进行了综述.首先介绍了中低温相变材料的种类及其循环稳定性,导热能力强化,其次总结了适用于中低温相变蓄热的数值模拟方法和理论,然后介绍了不同的相变储热器,最后指出了中低温相变蓄热的研究目标和方向.     

Verification of hydrothermal stability of adsorbent materials for thermal energy storage

This paper presents an experimental protocol for the cycling stability of adsorbent materials for thermal energy storage (TES) applications under hydrothermal conditions. Two different aging conditions were identified, namely, cycle and shelf test. The former one mimicking the cycling between desorption and adsorption conditions, while the latter one keeping a constant temperature for long time under constant water vapor pressure. A flexible experimental setup was then designed and realized to contemporarily perform both aging condition under selectable operating conditions. The protocol defines different characterization methods to compare the fresh and the aged samples. The measurement of the water vapor adsorption equilibrium isobars represents the main parameter to directly highlight possible degradation phenomena. Subsequently, X‐ray diffraction patterns (XRD), nitrogen physisorption, and scanning electron microscopy coupled to energy dispersive x‐ray (SEM–EDX), are used to evaluate structural, textural, morphological, and elemental composition variation that can help in identifying the causes of possible degradation. The proposed protocol was employed to validate the stability of a commercial adsorbent, AQSOA Z02, that proved a quite stable behavior both under cycle and shelf investigated conditions.     

金属基相变材料的研究进展及应用

金属基相变材料由于具有储能密度高、热稳定性好、热导率高等优点,在潜热热能储存系统中具有极大的优势。本文回顾了金属基相变材料的发展历程,归纳了金属基相变材料的性能参数,总结了各种热物性的测量方法,探讨了金属基相变材料与容器材料的相容性问题,分析了金属基相变材料在太阳能热发电、工业余热回收和电力削峰填谷中的应用前景。金属基相变材料的高温腐蚀性是目前限制其在热控制中应用的主要因素。为了实现金属基相变材料的广泛应用,需要重点解决金属基相变材料的封装问题。     

Encapsulated phase change materials for thermal energy storage: Experiments and simulation

In the present study, encapsulated phase change materials (PCMs) were used for the storage of thermal energy. Both experiments and simulation were performed to evaluate the characteristics of encapsulated PCMs. Tests were conducted in a packed bed to determine the performance of the encapsulated PCM. In the preparation of encapsulated PCMs, the coacervation technique was used. The performance of the encapsulated PCM was evaluated in terms of encapsulation ratio, hydrophilicity, and energy storage capacity. The experiments were designed, based on surface response method, to optimize the processing conditions. It was found that a higher coating to paraffin ratio led to a higher paraffin encapsulation ratio. The hydrophilicity value of encapsulated paraffin depended mainly on the ratio of paraffin to coating. The higher the ratio, the lower was its product hydrophilicity. When the paraffin to coating ratio was constant, the higher concentration of HCHO led to a lower hydrophilicity of the product. The encapsulated paraffin has shown large energy storage and release capacity (20–90 J g^?1) during its phase changes depending on different ratios of paraffin to coating. Thermal cyclic test showed that encapsulated paraffin kept its geometrical profile and energy storage capacity even after 1000 cycles of operation. In the experiments and simulation of fluid heating process in encapsulated PCM charged packed bed, results showed that Eulerian granular multiphase model in FLUENT 4.47 is suitable for simulation of such a system. Copyright © 2002 John Wiley & Sons, Ltd.     

高温熔盐相变蓄热材料

高温蓄热技术是太阳能热动力发电系统的关键技术之一,通常利用相变材料(PCM)固液相变时的熔化潜热来蓄热。在轨道的日照期,聚能器将截取的太阳能聚集到吸热器圆柱形腔内,被吸收转化成热能,其中一部分热能传递给循环工质以驱动热机发电,其余的热能被封装在单元换热管上多个小容器内的PCM吸收储存起来,此时PCM部分或全部变为液态。在轨道的阴影期,小容器内的PCM部分或全部变为固态,储存的能量被释放出来,使出口的循环工质温度仍能维持在循环所要求的最低峰值温度上。保证空间站处于阴影期时热机仍能连续工作,保证连续供电。太阳能利用中…     

Sizing phase-change energy storage units for air-based solar heating systems

A simple method for sizing phase-change energy storage (PCES) units for air-based solar heating systems is presented. An effective heat capacity for the phase change unit is obtained as a function of its mass, latent heat, specific heat, and melting temperature. The effective heat capacity can then be used, along with any convenient design method for systems with sensible heat stores, such as the f-chart method, to estimate the thermal performance of the system utilizing PCES.