Preparation and Properties of Paraffin/PMMA Shape-stabilized Phase Change Material for Building Thermal Energy Storage

The composite phase change material(PCM) consisting of phase change paraffin(PCP) and polymethyl methacrylate(PMMA) was prepared as a novel type of shape-stabilized PCM for building energy conservation through the method of bulk polymerization. The chemical structure, morphology, phase change temperature and enthalpy, and mechanical properties of the composite PCM were studied to evaluate the encapsulation effect of PMMA on PCP and determine the optimal composition proportion. FTIR and SEM results revealed that PCP was physically immobilized in the PMMA so that its leakage from the composite was prevented. Based on the thermo-physical and mechanical properties investigations, the optimal mass fraction of PCP in the composite was determined as 70%. The phase change temperature of the composite was close to that of PCP, and its latent heat was equivalent to the calculated value according to the mass fraction of PCP in the composite. For estimating the usability in practical engineering, thermal stability, reliability and temperature regulation performance of the composite were also researched by TG analysis, thermal cycling treatments and heating-cooling test. The results indicated that PCP/PMMA composite PCM behaved good thermal stability depending on the PMMA protection and its latent heat degraded little after 500 thermal cycling. Temperature regulation performance of the composite before and after thermal cycling was both noticeable due to its latent heat absorption and release in the temperature variation processes. The PCP/PMMA phase change plate was fabricated and applied as thermal insulator in miniature concrete box to estimate its temperature regulation effect under the simulated environmental condition. It can be concluded that this kind of PCP/PMMA shape-stabilized PCM with the advantages of no leakage, suitable phase change temperature and enthalpy, good thermal stability and reliability, and effective temperature regulation performance have much potential for thermal energy storage in building energy conservation.     

Preparation and characterization of CA-MA eutectic/silicon dioxide nanoscale composite phase change material from water glass via sol-gel method

This work mainly involved the preparation of a nano-scale form-stable phase change material(PCM) consisting of capric and myristic acid(CA-MA) binary eutectic acting as thermal absorbing material and nano silicon dioxide(nano-SiO_2) serving as the supporting material. Industrial water glass for preparation of the nano silicon dioxide matrix and CA-MA eutectic mixture were compounded by single-step sol-gel method with the silane coupling agent. The morphology, chemical characterization and form stability property of the composite PCM were investigated by transmission electron microscopy(TEM), scanning electron microscopy(SEM), Fourier-transform infrared(FT-IR) spectroscopy and polarizing microscopy(POM). It was indicated that the average diameter of the composite PCM particle ranged from 30-100 nm. The CA-MA eutectic was immobilized in the network pores constructed by the Si-O bonds so that the composite PCM was allowed no liquid leakage above the melting temperature of the CA-MA eutectic. Differential scanning calorimetry(DSC) and thermogravimetric analysis(TGA) measurement were conducted to investigate the thermal properties and stability of the composite PCM. From the measurement results, the mass fraction of the CA-MA eutectic in the composite PCM was about 40%. The phase change temperature and latent heat of the composite were determined to be 21.15 ℃ and 55.67 J/g, respectively. Meanwhile, thermal conductivity of the composite was measured to be 0.208 W·m~(-1)·K~(-1) by using the transient hot-wire method. The composite PCM was able to maintain the surrounding temperature close to its phase change temperature and behaved well in thermalregulated performance which was verified by the heat storage-release experiment. This kind of form-stable PCM was supposed to complete thermal insulation even temperature regulation by the dual effect of relatively low thermal conductivity and phase change thermal storage-release properties. So it can be formulated that the nanoscale CA-MA/SiO_2 composite PCM with the form-stable property, good thermal storage capacity and relatively low thermal conductivity can be applied for energy conservation as a kind of thermal functional material.     

太阳能蓄热石蜡类相变材料循环稳定性

研究了石蜡54号~56号、56号~58号、58号~60号相变材料的热稳定性,其相变温度在50~60℃之间.利用差示扫描量热(DSC)技术测定了经过1次、100次、200次、300次反复热循环的相变材料的相变温度和相变潜热,实验结果表明:随着热循环次数的增加,相变材料的相变温度和相变潜热的变化很小. 更多还原     

聚苯乙烯包覆石蜡相变微胶囊的制备及性能分析

采用悬浮聚合法制备以聚苯乙烯为壁材,58#石蜡为芯材的相变微胶囊。考察了乳化时间、交联剂二乙烯基苯（DVB）的配比、聚合时间以及芯壁比对微胶囊性能的影响,采用傅立叶红外光谱仪、场发射扫描电镜、差示扫描量热仪、热重分析等手段对微胶囊的化学结构、表观形貌、储热性能以及热稳定性等进行了表征。结果表明,乳化时间对微胶囊的热性能影响不大;单体St与交联剂DVB的质量比为6∶1制备的微胶囊的形貌较佳,缩皱和碎屑明显减少;聚合时间为3 h制备的微胶囊形貌较好、大小相对均一、相变潜热和芯材石蜡质量分数相对较高;而随着芯壁比的增大,芯材石蜡质量分数相继增大,其中芯壁比为3∶1制备的微胶囊相变潜热增大到125.2 J/g,芯材石蜡质量分数高达80.9%,且热稳定性好。     

CaCl2·6H2O/EG复合相变材料的制备与性能研究

为了改善六水氯化钙的蓄放热性能,以六水氯化钙为相变材料（PCM）、膨胀石墨（EG）为载体、六水氯化锶为成核剂,采用物理吸附法制备六水氯化钙/膨胀石墨复合相变材料,研究复合相变材料的热物理特性. 采用步冷曲线法,研究复合相变材料的过冷度、蓄/放热性能和热循环稳定性;采用扫描电镜、差示扫描量热法、热流计导热仪,对复合相变材料的显微形貌、相变潜热、相变温度、比热容和导热系数进行测定. 结果表明：在六水氯化钙中添加质量分数为10%的膨胀石墨和质量分数为2%的六水氯化锶,复合相变材料的相变潜热为151.6 J/g,导热系数提升至3.328 W/(m·K),过冷度保持在2 °C以内. 相变材料的导热系数及过冷度得到显著改善.     

ZCNTs/EP 复合材料的制备及其介电、导热性能

以环氧树脂 (epoxy resin, EP) 作为基体, 在多壁碳纳米管 (multi-walled carbon nanotubes, MWCNTs) 表面通过原位生长 2-甲基咪唑锌盐 (ZIF-8), 得到 ZIF-8/MWCNTs (ZCNTs) 复合材料。通过改变 EP 基体中 ZCNTs 含量, 制备 ZCNTs/EP 系列复合材料, 并对其介电、导热性能进行研究。研究结果表明, 当填料 ZCNTs 质量分数为 0.3%,频率为 10² Hz 时, ZCNTs/EP 复合材料的介电常数为 8.19; 频率为 10² ～ 10⁷ Hz 时介电损耗始终低于 0.025。同时,ZCNTs/EP 的导热系数达到 0.467 W/(m·K), 比纯 EP 的导热系数提高了 116%, 显著提升了 ZCNTs/EP 复合材料的导热性能。     

棕榈酸/石蜡复合相变储能材料

将石蜡(PW)与棕榈酸(PA)熔融超声共混,制备出了一系列PA/PW复合材料。采用瞬态热丝法(SHW,Short-Hot-Wire)测量PA/PW复合材料的导热系数,用差示扫描量热仪(DSC,Differential Scanning Calorimetric)分析复合材料的相变温度(T)和相变潜热(L),采用红外光谱仪(FTIR,Fourier Transform Infrared)对复合物的组成进行表征。复合材料的红外吸收光谱图表明,PW和PA只是简单的物理混合,未生成新物质。复合相变材料的导热系数大致随温度的升高而降低,而在30和50℃左右时由于固-固和固-液相变的作用,导热系数测量值出现了一定程度的升高。复合材料的Ts-s(固-固相变温度)都比PW的略高;与纯PW相比,除PA的质量分数w=35%之外,其他比例复合材料的Ts-l(固-液相变温度)都较纯PW的低;除w=35%的Ls-l(固-液相变潜热)比纯PW的低之外,其他比例复合材料的Ls-l都比纯PW的Ls-l高。     

Characterization and thermal conductivity of modified graphite/fatty acid eutectic/PMMA form-stable phase change material

We prepared and characterized a form-stable composite phase change material (PCM) with higher thermal conductivity. Capric acid(CA)-myristic acid(MA) eutectic as core, poly-methyl methacrylate (PMMA) as supportive matrix and modified graphite (MG) powders serving as the thermal conductance improver were blended by bulk-polymerization method. The composite PCMs with different MG mass fraction (2%, 5%, 7%, 10% and 15%) were characterized by FT-IR, SEM, DSC technique and mechanical tests. Thermal conductivities of the composites were measured by transient hot-wire method. The results indicate that MG powders have been successfully inserted into the CA-MA/PMMA matrix without any chemical reaction with each other. The MG/CA-MA/PMMA composites maintain good thermal storage performance while the thermal conductivity has been enhanced significantly. The composite PCM added with 15 wt% MG powders increases approximately as 195.9% in thermal conductivity. Moreover, the thermal conductivity improvement of the composite PCMs is also verified by the melting-freezing experiment, which is profitable for the heat transfer efficiency in latent heat thermal energy storage system.     

套管式太阳能相变蓄热器强化传热数值模拟

因太阳能相变蓄热技术节约资源、保护环境, 符合我国目前的能源发展要求, 而受到研究人员的关注。而太阳能具有间歇性、不稳定等特点增加了其利用的难度。通过有限元数值分析方法对套管式相变蓄热器进行模拟, 探究相变材料(phase change materials, PCM) 在太阳能相变蓄热器中的作用。结果表明, 添加膨胀石墨可大幅度提升太阳能蓄热器的蓄放热效率。相比于传统石蜡蓄热, 在入口速度、环境温度等初始条件相同时, 添加质量分数为20%的膨胀石墨的石蜡蓄热时长缩短了91.11%, 起到强化传热的效果。该研究为研制太阳能热水器、高效换热器及建筑节能和其他领域的热能储存等提供重要参考。     

Preparation of palygorskite-based phase change composites for thermal energy storage and their applications in Trombe walls

Palygorskite/paraffin phase-change composites were prepared by the combination of purified palygorskite clay and sliced paraffin. Then, this composite was used in the Trombe wall to improve its energy storage ability. Further, its energy storage ability was compared to that of ordinary concrete wall through contrastive test. The experiments show that palygorskite clay is a type of clay mineral with strong adsorption ability, and the purity of natural palygorskite clay can reach up to 97.1% after certain purification processes. Paraffin is well adsorbed by palygorskite, and the test results show that the optimal adsorption ratio is palygorskite: paraffin = 2:1 (mass ratio). Palygorskite/paraffin phase change composites can be obtained by using palygorskite as the adsorbing medium to adsorb paraffin. The composite materials exhibit good heat storage (release) performance, which can store heat with increasing environment temperature and release heat with decreasing temperature. This property not only increases the inertia to environment temperature change, but also promotes the energy migration in different time and space, thus achieving a certain energy-saving effect. The application of palygorskite/paraffin phase change composite materials to the Trombe wall can significantly reduce the fluctuation of indoor temperature and enhance the thermal inertia of indoor environment. From the aspect of energy storage effect, the Trombe wall fabricated using PCMs is significantly superior to the concrete wall with the same thickness.     

有机相变储热复合材料的储/放热性能研究

以高孔隙率泡沫石墨材料作为骨架在真空环境下吸附石蜡,制备而成新型有机相变储热复合材料。利用HotDisk热常数分析仪和差示扫描量热仪(DSC)研究了其热性能,结果证明复合材料的导热能力得到了极大强化。对分别填充了复合材料和纯石蜡的以水作为热媒的储热槽进行了实验研究,重点考察了两者在储热和放热过程中的温度均匀性、储能速率及泡沫石墨对石蜡相变的影响,同时就泡沫石墨的孔隙率大小对复合材料导热性能和储能速率的影响规律进行了对比分析。研究表明,复合材料的相变温度区间基本不变,导热性能提高了21倍,相变时间缩短了56%以上,相变界面移动加快,储热槽的储热、放热性能和储能密度有了很大提高;不同孔隙率会影响复合材料的导热系数、储能速率和储能容量,在提高储能速率和保证储能容量两者之间,选择孔隙率为91%的泡沫石墨作为复合材料骨架应是一最佳值。     

膨胀珍珠岩/有机羧酸复合相变储能材料试验研究

用膨胀珍珠岩多孔基体与有机羧酸进行物理复合,制备建筑储能材料,通过SEM分析了复合储能材料的微观结构,通过DSC测试其相变温度、相变焓.结果表明:辛酸、月桂酸和豆蔻酸与膨胀珍珠岩的最佳吸附量约为55%、45%、40%,膨胀珍珠岩/辛酸复合相变储能材料有合适的相变温度,膨胀珍珠岩/豆蔻酸复合储能材料有较高的相变焓.     

Convective heat transfer characters of nanoparticle enhanced latent functionally thermal fluid

The latent heat of the microencapsulated phase change material (MPCM) increases the effective thermal capacity of latent functionally thermal fluid. However, researchers found that the heat transfer performance of such fluids was diminished due to the reduction of the low thermal conductivity of MPCM. For this reason, the nanoparticle enhanced latent functionally thermal fluids were formulated and the heat transfer behaviors of these fluids in a vertical circular tube at the laminar regime were conducted. The result showed that slurries containing 0.5% TiO₂ nanoparticles by mass and 5%–20% MPCM by mass exhibited improved heat transfer rates in comparison with the conventional latent functionally thermal fluid and that the enhancement increased with the increasing MPCM concentration and up to 18.9% of the dimensionless wall temperature was reduced. Supported by the National Natural Science Foundation of China (Grant No. 50076020)     

泡沫铜/石蜡复合相变材料融化过程的换热特性

为了研究强化相变蓄热器的换热情况,搭建了矩形腔体内填充泡沫金属/石蜡的实验台,在恒壁温条件下,进行了泡沫金属/石蜡复合相变材料的融化蓄热实验。根据实验数据绘制了不同加热温度下石蜡内部温度随时间变化曲线,分析了腔体内自然对流对温度分布的影响、传热温差对蓄热时间的影响。结果表明,泡沫金属的高导热性能强化了石蜡在腔体内的融化过程,距离加热面较近的石蜡融化后产生的自然对流加速了剩余固态石蜡的融化;而且传热温差越大,自然对流越明显,蓄热时间越短。     

复合相变蓄热材料太阳能通风井性能

针对太阳能通风井道蓄热单元的技术需求,制备了复合相变蓄热材料,并将其应用于通风井壁,建立了基于复合相变蓄热材料的太阳能通风井测试系统,并测试了其运行性能。结果表明：添加5%碳纳米管制备的复合相变材料,其导热系数为0.65 W/m·K,是添加前的2.03倍,相变潜热为107 J/g,是添加前的0.718倍。应用上述材料的太阳能通风井测试系统在10：00-21：00时段通风量为55.0~103.9 m³/h,其中在17：00风速和风量达到最大,为良好的自然通风提供了保障。     

凝固浴对蓄热调温聚丙烯腈纤维性能的影响

以聚酰胺石蜡相变微胶囊(MEPCM)为相变材料,硫氰酸钠(NaSCN)水溶液为溶剂,通过湿法纺丝工艺制备MEPCM质量分数为16.7%的蓄热调温聚丙烯腈纤维,考察了凝固浴中NaSCN质量分数对纤维性能的影响。随着NaSCN质量分数的增大,纤维的线密度增大,断裂强度、热收缩率和沸水收缩率下降,断裂伸长率和钩接强度先增大后减小。通过实验分析确定最佳NaSCN质量分数为10%,在此条件下制备的蓄热调温聚丙烯腈纤维强度为1.35cN/dtex,热焓值为26.0J/g,MEPCM在纤维中的热效率达到78.4%,具有良好的物理机械性能和较好的蓄热调温性能。     

Compressive Mechanical Properties of Normalized 10# Low Carbon Steel

Compressive mechanical properties of 10# low carbon steel with normalizing heat treatment are studied.A Gleeble system is adopted to analyze the quasi-static properties and thermal softening effects of heat treated 10# steel,while a Hopkinson bar apparatus is used to investigate its dynamic characteristics under different strain rates.The results show that yield stress of heat treated 10# steel is more than that of untreated one at room temperature.When the specimens are tested at different temperatures,yield stresses decrease with increasing temperature except 573 K.Moreover,the influence of strain rate on yield stress are verified,which shows that the yield stress increases sharply from 500 s-1 to 1 890 s-1,while it changes a little from 1 890 s-1 to 4 850 s-1.The results indicate that yield stress is mainly influenced by hardening effect at low strain rate and controlled by both thermal softening effect and strain rate hardening effect at high strain rate.     

石墨改性聚全氟乙丙烯导热复合材料的性能

研究了新型耐腐蚀换热器的制作材料,旨在避免烟气余热回收时,因烟气温度低于其酸露点温度而产生的低温腐蚀.采用石墨填充聚全氟乙丙烯(fluorinated ethylene propylene,FEP),并添加一定量的碳纤维,制备出导热性能较好、抗冲击且耐腐蚀的石墨改性FEP导热材料.通过导热性能、力学性能及耐腐蚀性能研究,确定了适用于制作烟气余热回收系统中换热器的复合材料中石墨的填充质量分数.实验表明,石墨的质量分数越高,导热复合材料的热导率越大,但其拉伸强度、断裂伸长率和冲击强度会随着石墨填充质量分数升高逐渐降低.     

石墨烯修饰的碳纳米纤维制备及其电热转换

为提高碳纳米纤维(CNF)的电热转换效率,改善其综合导热系数,采用静电纺丝法将氧化石墨烯(GO)添加到聚丙烯腈(PAN)纤维中,经过预氧化和碳化处理后制得具有三维导热网络的CNF/rGO复合纤维膜以提高其热传输效率,并考察不同石墨烯含量和碳化温度对CNF/rGO复合纤维膜导热性能的影响。结果表明:采用rGO修饰CNF复合薄膜可以有效提升其综合导热系数,改善其电热转换效率;CNF/rGO复合纤维膜的导热系数随着氧化石墨烯含量的增加而升高,随着碳化温度的升高而下降,当氧化石墨烯质量分数为20%、碳化温度为1100℃时,CNF/rGO复合纤维膜的导热系数为0.216 W/(m·K),比纯CNF提升了127%;当氧化石墨烯质量分数为5%、碳化温度为1000℃、电压为21 V、电流为0.51 A时,CNF/rGO复合纤维膜的表面温度最高可达251.9℃;但是,GO含量和碳化温度的升高会导致CNF/rGO复合纤维膜的力学性能下降。     

Structural characteristics and properties of PU-modified TDE-85/MeTHPA epoxy resin

Diglycidyl-4,5-epoxycyclohexane-1,2-dicarboxylate (TDE-85)/methyl tetrahydro-phthalic anhydride (MeTHPA) epoxy resin was modified by polyurethane(PU), and its structural characteristics and properties were studied by infrared spectrum analysis (IR), scanning electronic microscopy (SEM), mechanics testing and thermogravimetric analysis (TG). The results indicate that epoxy polymeric network I and polyurethane polymeric network II are formed in the PU-modified TDE-85/MeTHPA epoxy resin. Meanwhile the PU-modified TDE-85/MeTHPA resins have heterogeneous structure. The miscibility between epoxy (EP) and polyurethane (PU) as well as the phase size are dominantly determined by the mass fraction of polyurethane prepolymer (PUP) in the EP/PU blends. With the increase of PUP mass fraction, the tensile strength, impact strength and thermal stability of the PU-modified TDE-85/MeTHPA epoxy resin all firstly exhibit increasing tendency, and decrease after successively reaching their maxima. When the number-average molecular mass of PPG is 1 000 and the mass fraction of PUP is 15%, the tensile strength, impact strength and thermal stability of materials obtained, compared with TDE-85/MeTHPA epoxy resin, are improved obviously.