Preparation and properties of novel ceramic composites based on microencapsulated phase change materials (MEPCMs) with high thermal stability

Ceramic composites are widely used in medium/high temperature thermal energy storage (TES) and catalysis. Due to the high latent heat of phase change materials (PCMs), it is an effective method to improve the TES capacity by combining PCMs with ceramic materials. However, PCMs are easy to leak after being heated, so they need to be microencapsulated. Furthermore, for porous ceramic catalytic composites, the leakage of PCMs will block the pores, which seriously hinders their application. In this paper, a novel microencapsulated phase change material (MEPCM) with thermal expansion void was prepared using “double-layer coating, sacrificing inner layer” method. Based on that, two kinds of ceramic composites have been prepared. One is a TES material which composed of alumina, glass frit (GF) and MEPCMs. Thermal analysis results showed that the composite can still maintain stable heat storage performance after 200 melting-solidification cycles with little latent heat loss. Another is a multifunctional porous composite phase change material (CPCM) by loading Ce and Mn as catalyst via solution combustion synthesis (SCS) method, which can be used in low temperature SCR catalysis and other catalytic fields (100–300 °C). Based on MEPCMs with thermal expansion void, the two ceramic composites show great potential in energy storage and catalysis.     

(准)共晶系相变储能材料的研究进展

节能技术的发展是当今非常现实的问题,这些技术的发展方向之一是各行业的热能储存。相变储能材料由于其较大的潜热和恒温性,被广泛应用于潜热储能系统和热管理系统中。然而,单一相变材料的相变温度和潜热比较固定,难以同时满足多种储能应用对各种潜热、相变温度等性质的要求。因此,人们开展了关于二元或多元共晶相变体系的研究。本文介绍了近年来国内外（准）共晶相变储能材料及其复合材料的研究进展,探讨了（准）共晶相变储能材料的理论设计机理,指出了（准）共晶相变储能材料存在的不同问题并提出建议,最后指出了（准）共晶系相变储能材料在实际应用领域的局限,提出未来在寻找新型相变储能材料,建立传热理论模型,对（准）共晶系复合相变储能材料的力学性能、耐老化性能、储能密度低和高温条件下的耐久性差等方面需要进一步探索。     

纳米材料/十四酸混合相变蓄热材料的制备与特性

选用纳米金属Cu和碳素材料石墨烯纳米片（GnPs）为改性剂分别添加至十四酸（MA）中,制备出Cu质量分数为1%、2%、3%和4%的Cu/MA混合相变蓄热材料及GnPs质量分数为1%、2%和3%的GnPs/MA混合相变蓄热材料,并对混合相变材料性能进行表征。结果表明：Cu/MA固态和液态热导率随Cu质量分数增加呈线性提高,1%（质量）GnPs/MA固态热导率较纯MA显著提高101.51%,随GnPs质量分数增加,热导率增幅减缓;FT-IR谱图表明Cu与MA及GnPs与MA间的混合均为物理作用;DSC结果显示添加Cu或GnPs可降低MA的过冷度和相变潜热,且随质量分数增加,相变潜热逐渐降低;4%（质量）Cu/MA和3%（质量）GnPs/MA放热时间相比于纯MA分别减少了23.4%和38.7%;4%（质量）Cu/MA和3%（质量）GnPs/MA在经历300次快速热循环试验后,晶体结构和相变温度基本保持不变,相变潜热分别降至168 J·g^-1和181 J·g^-1左右,仍满足蓄放热要求,两种材料均具有良好的热循环稳定性。     

Latentwärmespeicher: Speichermaterialien,Wärmeübertragung und Anwendungen

Phase change materials (PCMs) can absorb/release heat during the phase change. They are frequently used in thermal storage systems due to their large latent heat und isothermal nature. This paper provides an overview of the various inorganic and organic PCMs. Techniques for improving their thermophysical properties and the corrosion of metallic construction materials by inorganic PCMs are discussed. Finally, typical applications for latent‐heat storage systems are presented.     

新型建筑用二元复合定型相变材料的制备及性能评价

针对建筑节能领域,提出了一种由十二醇（LA,C₁₂H₂₆O）和硬脂酸（SA,C₁₈H₃₆O₂）组成的具有适宜相变温区且相变潜热较高的二元相变材料LA-SA,并以膨胀珍珠岩和陶粒为多孔吸附材料制备出复合定型相变材料,探究了不同吸附材料对于定型相变材料热物性的影响。二元相变材料LA-SA的最优配比为质量分数82%十二醇+18%硬脂酸,其熔融相变温度为21.3℃,相变潜热为205.9 kJ/kg,且热稳定性能良好。以膨胀珍珠岩和陶粒为吸附材料,通过真空吸附法制备出了两种建筑用定型相变材料,并对其进行了SEM、FTIR、TG及DSC性能表征,结果表明：LA-SA与两种吸附材料的复合过程仅为物理吸附且复合良好,吸附后的定型相变材料的相变潜热有一定的降低;相比于陶粒,膨胀珍珠岩对相变材料的吸附率较高,且对相变材料热性能影响较小;LA-SA/膨胀珍珠岩熔融相变温度为22.7℃,相变潜热为165.3 kJ/kg,可应用于建筑节能材料的制备。     

二维纳米片基复合相变储热材料研究进展

相变材料（PCMs）作为潜热储存和释放的介质,能够解决热能供需矛盾,从而缓解能源危机。纯相变材料具有能量密度高、温度范围广、能量输出稳定性强等优点,但其热导率低和在相变过程发生渗漏的缺点阻碍了其广泛的应用和发展。通过将PCMs与二维纳米片复合,PCMs热导率低和渗漏问题被有效解决。通过在导热机理方面进行详细阐述的基础上,综述了近几年来有关碳基二维纳米片、六方氮化硼（h-BN）纳米片、二硫化钼等复合储热材料的研究进展,为高性能二维纳米片基复合PCMs的设计提供一定的研究思路。     

无机芯微胶囊相变材料的研究进展

综合了近几年对无机芯相变微胶囊的报道,针对微胶囊相变材料（MCPCM）做了总结与概括,从其制备方法和应用领域进行了系统研究,并探讨了现存的问题以及需改进的方面。得到以下结论：微胶囊相变材料（MCPCM）是采用微胶囊封装技术对固-液型相变材料包覆封装的具有核壳结构的复合材料,可广泛地应用在太阳能光热储存、工业余热回收和传热流体领域。无机相变材料具有高储热密度、相变温度恒定、低成本等优点,因此无机芯微胶囊相变材料具有更好的应用空间。但目前采用的微胶囊相变材料也有其自身的缺点,如聚合物导热系数低,相变温度范围小等,有待于进一步研究。     

Preparation and thermal characterization of expanded graphite/paraffin composite phase change material

Expanded graphite (EG)/paraffin composite phase change materials (PCMs), with mass fraction of EG varying from 0 to 10 wt.%, were prepared and characterized. Polarizing optical microscope investigation showed that compact EG networks formed gradually with increase in the mass fraction of EG. These networks provided thermal conduction paths which enhanced the thermal conductivity of the composite PCMs, e.g., an addition of 10 wt.% EG resulting in a more than 10-fold increase in the thermal conductivity compared to that of pure paraffin. Thermal characterization of the composite PCMs with a differential scanning calorimeter (DSC) revealed the effect of the porous EG on the phase change behavior of paraffin. The shifts in the phase change temperatures were observed. The maximum deviation of the melting/freezing points of the composite PCMs from that of pure paraffin was 1.2 °C whereas that of the peak melting/freezing temperature was 5.6 °C. The DSC investigation also showed an anomaly in the latent heat of the paraffin in the composite PCMs in that it first increased and then decreased with increase in the EG fraction. Heat storage/retrieval tests of the composite PCMs in a latent thermal energy storage system showed that the heat storage/retrieval durations for EG(10)/paraffin(90) composite were reduced by 48.9% and 66.5%, respectively, compared to pure paraffin, which indicated a great improvement in the heat storage/retrieval rates of the system.     

组合相变材料强化固液相变传热可视化实验

采用高清相机和红外热像技术，对组合相变材料融化-凝固循环过程与传热特性开展了可视化实验研究。以填充三种石蜡的相变蓄热腔体为研究对象，追踪了腔体内固液相界面的动态演化过程和温度分布的变化规律。在此基础上，考察了相变材料布置顺序对蓄热腔体热性能的影响，分析了组合相变材料蓄热腔体的相变行为及强化传热特性。结果表明，相变温度较高的相变材料应靠近加热壁面布置；组合相变材料蓄热腔体存在多个固液相界面现象，不同相变材料可同时融化/凝固；与单一相变材料相比，组合相变材料的应用改善了蓄热腔体各单元相变速率的均匀性，提高了平均相变速率；组合相变材料虽然降低了蓄热腔体的显热蓄热量，但减小了温度变化速率，增强了系统的稳定性，并显著增加了潜热蓄热量，有效提高了相变蓄热腔体的总蓄热量。     

Cu含量对Al-Cu-Si合金相变储热性能的影响

Al-Cu-Si基相变材料具有成本低、相变潜热高、抗氧化性能高等优势,是最具潜力的太阳能储存材料之一。而Cu含量对其储热性能特别是体积潜热有重要影响,但相关研究未见报道。通过差示扫描量热仪和激光热导分析仪研究了Al-Cu-Si合金的相变温度、质量潜热和体积潜热随Cu含量变化的关系,以及比热容、热扩散率和热导率等随温度变化的关系。研究结果表明,在Cu含量35%～55%时,Al-Cu-Si合金相变温度为512.5～604.2℃,质量潜热为354.4～458.1 J?g^-1,体积潜热为1524.1～1763.8 J?cm^-3。质量潜热和体积潜热均随着Cu含量的增加呈现出“双峰型”的变化趋势,Cu含量42%时质量潜热最大,为458.1 J?g^-1;Cu含量48%时体积潜热最大,为1763.8 J?cm^-3。Al-Cu-Si合金的热导率随着Cu含量的增加而降低,且在500℃时Al-Cu-Si合金的热导率为91.4~137.5 W?m^-1?K^-1。综合研究表明,Al-Cu-Si合金在太阳能储热领域具有很高的应用价值。     

多熔点相变材料堆积蓄热床蓄热性能分析

对采用多种不同熔点相变材料（PCM）构成的堆积蓄热床进行了数值分析。热水作为换热流体（HTF）自上而下流经蓄热床,熔化相变材料、蓄积相变潜热。石蜡作为相变材料被注射入聚碳酸酯球壳内形成相变胶囊,根据熔点高低依次排放在蓄热床的不同位置,熔点越高距离热水进口越近。假定流场稳定,采用一维Schumann模型计算HTF温度,相变模拟采用显热容法。分别对两种排列方式下采用2种、3种以及4种相变材料的蓄热床的蓄热过程进行了基于热力学第一及第二定律的性能分析,并将结果与单相变材料蓄热床进行比较。基于热力学第一定律分析结果表明,采用多种相变材料构成的蓄热堆积床蓄热速度更快,能量效率更高。基于热力学第二定律分析表明,平均熔点更高的蓄热床能够储存更高的火用。结果表明采用多熔点相变材料构成的堆积蓄热床能够显著地缩短蓄热时间,改进蓄热性能。     

相变热界面材料导热增强及定形改善的研究进展

将相变时伴随潜热的相变材料（phase change material, PCM）特别是潜热值较大的固-液PCM引入热界面材料（TIM）领域,有望获得兼具储热和导热双功能的新型热界面材料——相变热界面材料（phase change thermal interface material, PCTIM）。然而,鉴于固-液相变材料的热导率普遍较低且存在液相流动泄漏问题,使得增强热传导并同时提升固-液相变材料的定形性成为研制高性能相变热界面材料（PCTIM）的关键。本文系统评述了国内外研究者在提升相变热界面材料热导率以及改善其定形性方面的策略及其研究进展。文中指出,目前强化PCTIM导热的手段主要有添加高导热填料、促使填料有序结构化以及使用低熔点金属等。在改善定形性方面,已运用的策略主要包括使用柔性载体负载固-液PCM以在保证一定柔性的基础上克服其液相泄漏问题,使用固-固PCM来取代固-液PCM来彻底避免液相泄漏问题的出现,以及将固-液PCM封装在微米级或纳米级胶囊内,旨在牺牲借助液相PCM增加柔性的功能,而且通过提高PCTIM的潜热值来提升其抗热流冲击性能。文章指出,当前已研制的PCTIM热...     

Polymeric phase change composites for thermal energy storage

This article describes a group of thermal energy storage (TES) composites that combine TES and structural functionality. The composites are encapsulations of low melt temperature phase change materials (PCM) such as paraffin waxes in polymer matrices. Room temperature cured bisphenol‐A epoxy and styrene–ethylene–butylene–styrene (SEBS) polymers are chosen as matrix materials because of their excellent chemical and mechanical properties. The polymeric network structure in the composite encapsulates the PCMs, which transform from the solid to the liquid phase. The PCMs provide the energy storage function via the solid–liquid latent heat effect. The resulting composite exhibits dry‐phase transition in the sense that fluid motion of the PCM, when in the liquid phase, is inhibited by the structure of the polymer matrix. The polymer matrix is formulated to provide structural functionality. The latent heat, thermal conductivity and contact conductance, and structural moduli of composites having various PCM‐to‐matrix volume fractions are measured. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1240–1251, 2004     

脂肪酸相变材料的研究进展及应用

中长链脂肪酸及其混合物具有良好的热物性、热稳定性和化学稳定性,是非常廉价易得的一类有机相变材料.综述了脂肪酸固-液相变材料在潜热蓄热领域的发展现状,主要介绍了常用脂肪酸相变材料及其低共熔混合物的热物性和热稳定性特点,指出了其强化传热方式,总结了国内外脂肪酸复合相变材料的制备方法.     

Photocrosslinked biobased phase change material for thermal energy storage

A series of novel photocrosslinked biobased shape‐stabilized phase change materials (PCMs) based on octadecanol, eicosanol and docosanol have been prepared by UV technique for the purpose of thermal energy storage applications. Epoxidized soybean oil was reacted with acrylic acid to form acrylated soybean oil (ASO). The structure and composition, cross‐section morphology, thermal stability performances and phase change behaviors of ASO and UV‐cured PCMs were examined by using Attenuated total reflection fourier transform infrared spectroscopy, thermogravimetric analysis system (TGA), scanning electron microscopy, and differential scanning calorimetry. The results indicate that the UV‐cured biobased PCMs possess perfect phase change properties and a suitable working temperature range. The heating process phase change enthalpy is measured between 30 and 68 J/g, and the freezing process phase change enthalpy is found between 18 and 70 J/g. The decomposition of UV‐cured PCMs started at 260 °C and reached a maximum of 430 °C. All the biobased UV‐cured PCMs improved latent heat storage capacity in comparison with the pristine ASO sample. With the obtained results we conclude that, these materials promise a great potential in thermal energy storage applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43757.     

石蜡的聚烯烃定形包覆研究

低熔点石蜡为芯材,聚苯乙烯、聚丙烯和聚乙烯3种高分子材料作支撑材料,以加热熔融的方法制备了3种定形复合相变材料,确定了3种高分子材料对潜热为222.01 kJ/kg的17℃石蜡的最大包裹量分别为w(石蜡)=46%、51%、73%。用差示扫描量热仪对3种定形复合相变材料进行了测定,分析了所制备的定形复合相变材料的相变温度、相变潜热、热稳定性等性能。结果表明,石蜡经过高分子材料包覆之后,其相变温度有所降低,相变焓值有所提高,而且该定形相变材料可以加工成粉体材料,进一步拓展了产品的应用领域。     

圆管内氧化石墨烯MPCM悬浮液对流传热实验研究

由于氧化石墨烯(GO)的高热导率特性,将其添加至相变微胶囊颗粒内,以提高以其为基材制备的悬浮液的热导率,从而进一步强化传热。分别测试了纯水、5wt%相变微胶囊悬浮液(MPCMS)、5wt%和10wt%复合氧化石墨烯的相变微胶囊悬浮液(GO-MPCMS)的传热特性,分析讨论了壁面热流密度、雷诺数(Re)等参数的影响。结果表明,由于相变过程的影响,圆管壁面和流体温度分布呈现上升、平直、上升的变化规律;相同实验条件下,当工质为悬浮液时壁面温度与流体温度比纯水低;颗粒浓度和GO均对传热产生较大影响,相同质量分数(5wt%)时,添加GO时可使稳定后的局部努塞尔数(Nu_x)进一步提升8个百分点,颗粒质量分数由5wt%增至10wt%时,Nu_x又增加了20个百分点;与纯水相比,同时考虑GO和微胶囊颗粒的影响,相同实验条件下,相变微胶囊悬浮液平均努塞尔数(Nu)可提升1.0～2.0倍。     

Synthesis and characterization of polyethylene glycol acrylate crosslinking copolymer as solid–solid phase change materials

A kind of crosslinking copolymer as solid–solid phase change material (PCM) is synthesized by copolymerization. The scope of PCM applications is often severely limited by their heat stablility and phase transition state. The solid–solid phase change materials we obtained retain basic state during phase change transitions. The crosslinking polymer is heat stable under 300° and the latent heat of crystalline and latent heat of melting is on the average of 120 J/g and 140J/g, respectively. The property of thermal stability and heat storaged is related to crosslinking density of the gel. The property of thermal stability and high latent heat may expand the scope of PCMs applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39755.     

人体血液灌注和代谢产热对低温手术过程的影响

使用有限元方法研究了人体血液灌注和代谢产热对低温手术过程中组织温度场的影响.结果表明：一旦引入上述两种因素的影响后,即相当于在经典的传热方程中增加了非线性热源项;该热源项的出现,明显减慢了低温手术过程中冷刀附近组织的降温速率,增加了局部位置组织经历的温度梯度;不仅减慢了冷刀周围组织冻结面的生长速度,而且减小了手术过程中冰球的最大半径.该结果对低温手术的临床应用具有参考价值.     

组合式相变材料最佳相变温度的热力学分析

采用组合式相变材料的蓄热系统较单一相变材料具有更为优越的传热和热力学性能,而相变温度对于蓄热系统性能具有重要的影响。为了使结果更具普适性,以热力学有效能分析为基础并忽略具体换热器形式和传热过程,推导了使用不同相变材料数时每种相变材料最佳相变温度的理论公式,并根据最佳相变温度计算了有效能利用率随着相变材料数的变化,结果表明当PCMs数增加到4种时,理论最大有效能利用率已达80%以上,比使用单一相变材料的理论最大有效能利用率高50%左右。以573.15 K热能蓄能为例,计算了使用1~4种相变材料时相应的最佳相变温度与最大有效能利用率,并以此为依据给出了实际最佳相变材料组合。