壳管式潜热蓄能系统换热特性

针对目前石蜡潜热蓄能系统效率低下的特点,构建了石蜡/膨胀石墨混合相变材料的潜热蓄能系统,研究了其蓄/放热特性,并与纯石蜡相变材料系统进行了对比分析,讨论了不同换热流体流量下的蓄/放热过程的时间周期。用焓法处理相变区域,对该潜热蓄能系统的整体蓄热过程进行数值模拟。研究结果表明,对于石蜡／膨胀石墨复合相变材料,其导热性能较纯石蜡有很大提高,但由于添加了膨胀石墨而减弱了蓄热中石蜡的对流换热。流量提高对蓄/放热速率有明显的改善。焓法模型能全面反映蓄能系统的换热与流动特性,数值计算的结果与实验数据吻合较好。     

癸酸-石蜡/膨胀石墨定形相变材料的制备及性能

通过物理吸附法将癸酸-石蜡（CA-PC）二元低共熔混合物与膨胀石墨（EG）复合形成癸酸-石蜡/膨胀石墨定形相变材料,实验结果显示,CA与PC、CA-PC与EG的最佳质量配比分别为8.1∶1.9和7∶1。利用扫描电子显微镜（SEM）和傅里叶红外光谱仪（FTIR）分析了定形相变材料的微观形貌和结构特点,发现CA-PC/EG的FTIR曲线上同时存在二元低共熔混合物和膨胀石墨的特征吸收峰,表明二元低共熔混合物与膨胀石墨之间没有发生化学反应,二者依靠表面张力和毛细力作用在一起,并且CA-PC二元低共熔混合物依靠物理作用被有效包封于EG的孔隙中,经过1000次加速冷热循环后,基本没有液态二元复合相变材料泄漏。通过差示扫描量热仪（DSC）得到CA-PC/EG的熔化温度和凝固温度分别为27.04℃和22.26℃,熔化潜热和凝固潜热分别为144.4J/g和133.7J/g,且EG的高导热性促进了CA-PC的蓄放热速率。同时,根据热重分析（TG）与蓄放热实验结果发现其拥有优良的热可靠性和耐热性能。因此,该CA-PC/EG定形相变材料是一种良好的低温储能材料。     

Thermal characterization of erythritol/expanded graphite composites for high thermal storage capacity

Expanded graphites (EGs) with various interlayer distances were combined with molten erythritol and then erythritol/EG composites as phase change materials (PCMs) and the composites were prepared by a simple blending and impregnating method. The effects of the additives of various interlayer distances of EGs on thermal behaviors were investigated by a thermal equilibrium technique. The latent heat and thermal cycling stability were evaluated by DSC traces. The results revealed that both the thermal conductivity and latent heat increased with increasing EG interlayer distance. In particular, erythritol/EG composites having the largest EG interlayer distance showed thermal conductivity of 3.56 W/m K and a latent heat value of 90 mass% of pure erythritol. The thermal cycling tests were performed 5 times and the latent heat of the erythritol/EG composites were constant from the third cycle onwards, demonstrating excellent thermal cycling stability.     

硬脂醇/膨胀石墨复合相变材料的制备及储热性能

相变储热技术是解决热量在时空上分配不平衡问题的有效手段之一,研制高性能的复合相变材料（phase change material, PCM）成为当前研究者关注的重点。硬脂醇（stearyl alcohol, SAL）等有机PCM目前主要存在热导率偏低以及循环稳定性较差等问题而限制了实际应用。以SAL作为PCM,膨胀石墨（expanded graphite, EG）为高导热多孔基质,采用吸附定形工艺制备了16种SAL/EG复合PCMs[EG含量为7%、14%、21%、28%（质量）;样品密度为700kg/m³、800kg/m³、900kg/m³、1000kg/m³]。对复合PCMs样品的微观结构、储热能力、导热性能、循环稳定性及充放热性能进行研究与分析。结果表明：SAL完全填充于EG的多孔网络。当样品密度为900kg/m³,EG质量分数为28%的水平热导率最高,其值为28.58W/(m ? K),相比于纯SAL[0.38W/(m ? K)]提高了74倍,该值大约是相对应垂直热导率[5.99W/(m ? K)]的4.8倍。另外在构建的充放热性能试验台上研究了样品中心位置的储/放热性能,结果显示样品密度为900kg/m³,EG质量分数为28%的样品充放热速率最大,固-液潜热吸热和放热阶段所经历的时间分别为53min和20min。与此同时验证了样品的导热性能和熔化-凝固特性,说明SAL/EG复合PCMs具有稳定可靠的储/放热性能。     

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。     

高导热膨胀石墨/棕榈酸定形复合相变材料的制备及储热性能研究

采用棕榈酸(palmitic acid, PA)作为相变材料,膨胀石墨(expanded graphite, EG)作为添加基质,通过“熔融共混-凝固定形”工艺制备了PA/EG定形复合相变材料以提高相变材料的综合性能。预测并制备了21种不同配比的定形复合相变材料,对其形貌结构和孔隙率进行了微观表征与理论分析,并在此基础上对样品进行了传热性能分析、热物性测试、热稳定性研究和储热性能分析。SEM形貌分析显示所使用工艺可使棕榈酸能较好地被吸附于膨胀石墨的孔隙结构并使之均匀分布;DSC测试结果表明定形复合相变材料[70%(质量) PA]的焓值为193.01 J/g,纯PA的焓值为275.35 J/g,对应于熔点分别为61.08℃和59.53℃。EG的添加,可有效提高相变材料的热导率。当样品密度为900 kg/m³,EG含量为30%(质量)时,定形复合相变材料的热导率为14.09 W/(m·K),相比于纯PA[0.162 W/(m·K)]提高约87倍;对制备的样品进行50次循环稳定性实验,EG含量为24%(质量)和30%(质量)的样品形态均未出现明显变化,表现出良好的充放热循环稳定性。     

多孔SiC陶瓷/石蜡复合相变材料定型封装及热性能研究

以微米级SiC粉为原料,采用冷冻干燥工艺制备具有连贯层状孔结构的SiC陶瓷。以多孔SiC陶瓷为基体,石蜡为相变芯材,通过真空浸渍法制备多孔SiC陶瓷/石蜡复合相变材料,研究了石蜡在层状多孔SiC陶瓷内的浸渗行为及复合材料的储热性能。结果表明,层片状多孔SiC陶瓷的显微形貌对石蜡的浸渗过程及储热性能有明显影响。当石蜡负载量为21.7%(质量分数)时,复合相变材料熔融温度为59.6 ℃,凝固温度为53.9 ℃,相变潜热为28.4 J/g,室温下的热导率为2.4 W·(m·K)^-1。复合相变材料吸热峰和放热峰强度随着石蜡负载量减少而降低,当温度为200 ℃时,多孔SiC陶瓷/石蜡复合相变材料失重为5%(质量分数),表明材料具有良好的热稳定性。复合相变材料在100 ℃热处理30 min后陶瓷基体未发生形变,经100次热循环后具有稳定的相变潜热和良好的定型能力。     

Improving the thermal conductivity and shape-stabilization of phase change materials using nanographite additives

Improvements in the thermal conductivity and shape-stability of paraffin phase change materials (PCMs) by adding exfoliated graphite nanoplatelets (xGnP) or graphene were compared. The composite PCMs were fabricated by mixing paraffin with xGnP or graphene in hot toluene, followed by solvent evaporation and vacuum drying. A larger increase in thermal conductivity was observed for paraffin/xGnP, with a 10 wt.% xGnP loading producing a more than 10-fold increase. Graphene shows a lower electrical percolation threshold and offers a much larger increase in the electrical conductivity of paraffin than xGnP. However, its thermal conductivity increase is much lower. Despite the excellent thermal conductivity of single-flake graphene, the large density of nanointerfaces due to the small size of the graphene flakes significantly impedes heat transfer. We also found that graphene is much more effective than xGnP as a shape-stabilizing filler. At 2 wt.% graphene loading, paraffin maintains its shape up to 185.2 °C, well above the operating temperature range of paraffin PCMs, while the paraffin/xGnP counterpart is shape-stable up to 67.0 °C only. Small amounts of graphene and xGnP can be used in combination as a low-cost and effective improver for both the heat diffusion and shape-stabilization of paraffin PCMs.     

Preparation,thermal properties and thermal reliability of eutectic mixtures of fatty acids/expanded vermiculite as novel form-stable composites for energy storage

This paper deals with the preparation, characterization, thermal properties and thermal reliability of novel form-stable composite phase change materials (PCMs) composed of eutectic mixtures of fatty acids and expanded vermiculite for thermal energy storage. The form-stable composite PCMs were prepared by incorporation of eutectic mixtures of fatty acids (capric–lauric, capric–palmitic and capric–stearic acids) within the expanded vermiculite by vacuum impregnation method. The composite PCMs were characterized by SEM and FTIR techniques. Thermal properties of the composite PCMs were determined by differential scanning calorimeter (DSC) method. DSC results showed that the melting temperatures and latent heats of the prepared composite PCMs are in the range of 19.09–25.64 °C and 61.03–72.05 J/g, respectively. The thermal cycling test including 5000 heating and cooling process was conducted to determine the thermal reliability of the composite PCMs. The test results showed that the composite PCMs have good thermal reliability and chemical stability. Furthermore, thermal conductivities of the composite PCMs were increased by adding 10 wt% expanded graphite. Based on all results, the prepared form-stable composites can be considered as promising PCMs for low temperature thermal energy storage applications due to their satisfactory thermal properties, good thermal reliability, chemical stability and thermal conductivities.     

电驱动PEG/EG复合相变材料的制备与性能

以聚乙二醇（PEG）为相变组分，膨胀石墨（EG）为支撑材料，采用真空浸渍的方法制备了PEG/EG电热转换相变储能材料。改变复合相变材料中EG的质量分数，探究其在电热转换与热能存储效率、定形效果、相变焓值、储放热速率等方面的作用。结果表明，EG不仅能够提高复合相变材料的导热性能，还赋予其导电性能。当EG质量分数为5%时，PEG/EG复合相变材料具有良好的电热转换性能，在外加电压为7 V时，其电热转换与热能存储效率达到80.6%。同时，复合相变材料表现出良好的定形效果、较高的相变焓值（152.2 J/g）和优异的导热性能，与纯PEG相比，其储热所用时间减少了73%，储放热速率大幅提高。因此，PEG/EG复合相变材料在电驱动热能存储系统和能量转换与存储等领域具有广阔的应用前景。     

Preparation and thermal energy storage properties of poly(n‐butyl methacrylate)/fatty acids composites as form‐stable phase change materials

This work is focused on the preparation, characterization, and determination of thermal energy storage properties of poly(n‐butyl methacrylate) (PnBMA)/fatty acid composites as form‐stable phase change material (PCM). In the composite materials, the fatty acids act as latent heat storage material whereas PnBMA serves as supporting material, which prevents the leakage of the melted fatty acids. The maximum encapsulation ratio for all fatty acids was found to be 40 wt%. The composites that do not allow PCM leakage in melted state were identified as form‐stable PCMs. The compatibility of fatty acids with PnBMA is investigated by optical microscopy (OM) and Fourier Transform Infrared (FT‐IR) spectroscopy. Thermal properties and thermal reliability of the form‐stable composite PCMs were determined using differential scanning calorimetry (DSC). DSC analysis revealed that the form‐stable composite PCMs had melting temperatures between 29.62°C and 53.73°C and latent heat values between 67.23 J/g and 87.34 J/g. Thermal stability of the composite PCMs was studied by thermal gravimetric (TG) analysis and the results indicated that the form‐stable PCMs had good thermal stability. In addition, thermal cycling test showed that the composite PCMs had good thermal reliability with respect to the changes in their thermal properties after accelerated 5,000 thermal cycling. On the basis of all results, it was also concluded that the prepared form‐stable composite PCMs had important potential for many thermal energy storage applications such as solar space heating of buildings by using wallboard, plasterboard or floors integrated with PCM. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Expanded Vermiculite/Paraffin Composite as a Solar Thermal Energy Storage Material

A solar thermal energy storage material was prepared from expanded vermiculite (EVM) and paraffin by vacuum impregnation. Samples were characterized by thermogravimetric and differential scanning calorimetry (TG‐DSC), X‐ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), scanning electron microscopy (SEM), petrographic analysis, and thermal conductivity measurements. The results indicated that EVM existed as a phlogopite structure in the EVM/paraffin composite. The composite latent heat was 137.6 J/g at the freezing temperature of 52.5°C and 135.5 J/g at the melting temperature of 48.0°C, when the paraffin content was 67%. The phlogopite structure of EVM benefited paraffin heat transfer because the composite exhibited a thermal conductivity of 0.545 W·(m·K)^?1 higher than that of paraffin. Morphology and structural changes of EVM during composite preparation were investigated. The composite exhibited excellent thermal stability and has potential application in solar thermal energy storage and solar heating.     

纳米复合相变蓄热材料的制备与特性

相变蓄热材料（phase change materials,PCMs）是相变蓄热技术研究的基础。针对普通相变蓄热材料热导率低的缺点,采用纳米技术改善石蜡的相变传热性能,从而提高其热导率及热扩散系数。通过纳米颗粒-石蜡复合材料熔化过程测试和纳米颗粒沉降过程观察,确定铜纳米颗粒和Hitenol BC-10分别作为实验用纳米颗粒和分散剂,在制备稳定的纳米铜颗粒-石蜡复合相变材料的基础上,对其热物性进行了实验研究。结果表明纳米铜颗粒的添加使得石蜡热导率增幅最大,实验测得固态纳米铜-石蜡热导率提高7.9%,液态提高3.8%,而固、液态热扩散系数则分别提高了20.6%和16%。     

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。     

Preparation and properties studies of paraffin/high density polyethylene composites and phase-change coatings

The form-stable paraffin/high density polyethylene (HDPE) composites and phase-change coatings were prepared and characterized in this study. The paraffin acts as thermal absorbing material and HDPE serves as the supporting material, which provides structural strength and prevents the leakage of melted paraffin. Scanning electronic microscope (SEM) showed that the paraffin is dispersed uniformly into porous network of HDPE. Differential scanning calorimeter (DSC) determined the melting temperature and heat storage capacity of the composite piece to be 49.6 °C and 150.88 kJ/kg, respectively. Moreover, results indicated that the composite pieces showed better thermal stability than composite powders after 6 temperature cycling experiments. The phase-change coatings with 40 wt% composites as functional filler showed good adhesion strength and shock resistance, and could decrease the surface temperature obviously comparing with nude Al alloy plates.     

正十八烷/OBC/EG复合定型相变材料制备及热物性

针对正十八烷相变易泄漏的问题,采用烯烃嵌段共聚物（olefin block copolymer,OBC）作为封装结构,制备复合定型相变材料。并通过添加膨胀石墨（expanded graphite,EG）,改善其热导率低的问题。研究结果表明,当OBC的质量分数为20%时,复合相变材料未发现明显泄漏,定型效果较好,此时复合相变材料的相变焓为166.87 J/g,相较纯十八烷（227.40 J/g）下降26.62%。针对添加有不同质量分数EG的复合相变材料,其热导率随EG含量的增加而增大。其中当EG质量分数为5%时,复合相变材料热导率为4.179 W/(m?K),较纯相变材料热导率[0.24 W/(m?K)提高了约16倍,即EG能够有效提高复合相变材料的导热性能。此外,5%含量下的复合相变材料相变焓约为149.54 J/g,且在经历50次循环后,相变温度和相变焓均未有明显变化,即制备的复合相变材料具有较好的热稳定性。因此,该复合相变材料在建筑节能方面具有应用潜力。     

石蜡与石蜡/膨胀石墨熔化性能的实验研究

为改善相变储能过程中石蜡(PA)的熔化性能,向PA中添加少量膨胀石墨(EG)制备了4种配比的石蜡/膨胀石墨复合相变材料(PA-EG)。通过热物性分析筛选出合适配比的PA-EG,并对其和PA在水平管壳式相变储能单元中的熔化过程进行了实验研究。根据相变材料的温度场变化以及加权法计算得到的熔化分数变化,对比分析了添加EG前后PA的熔化性能,并探究了加热温度对相变材料熔化性能的影响。结果表明,PA-EG3的热导率比PA高了7倍,且两者的相变温度和潜热相差不大。PA-EG3熔化过程中的自然对流效应弱于PA,但是较高的热导率能够显著改善相变储能单元中下部的熔化,使得其整体熔化速度快于PA。当加热温度为80℃时,PA-EG3的熔化过程比PA缩短了78.16%。此外,降低加热温度会使PA和PA-EG3的完全熔化时间都显著增加,但相同条件下PA-EG3的增加幅度更小。     

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     

石蜡/膨胀石墨定形相变材料的性能

以石蜡为相变材料,利用膨胀石墨多孔网络结构,通过物理吸附法制备出石蜡/膨胀石墨复合相变材料,并通过模压法制成定形相变材料板块。采用差示扫描量热分析仪(DSC)、扫描电子显微镜(SEM)、偏光显微镜(POM)和Hot Disk 热常数分析仪等对复合相变材料进行了结构和性能的表征与测量,建立了冷/热循环实验系统以分析材料的蓄/放热性能等。结果表明:石蜡质量分数为80%的定形相变材料相变温度为27.27℃,相变焓为156.6 kJ·kg^-1。制备的定形相变材料具有相变过程形状稳定、热导率高、储热密度大等特点,并具有良好的稳定性和较长的使用寿命。     

膨胀石墨/三水乙酸钠复合相变材料储热的性能

以三水乙酸钠（SAT）为基材,添加具有多孔网状结构的膨胀石墨（EG）制备复合相变材料。使用扫描电子显微镜、温度数据采集仪、差示扫描量热仪、Hot Disk热常数分析仪等对材料进行结构观察及相关热物性测试,研究膨胀石墨对三水乙酸钠的热物性影响。结果表明,膨胀石墨不能减小三水乙酸钠的过冷度,但可大幅提高材料热导率,对材料潜热值、相变温度影响较小,能减轻三水乙酸钠的相分离现象且能提高其循环稳定性。对于基材为三水乙酸钠的相变材料,膨胀石墨添加量为7%时,复合材料吸附情况最好。当复合材料配比为7% EG+1%十二水磷酸氢二钠+SAT时,相比于纯SAT相变材料,过冷度减小约49℃,热导率提高将近1倍,相变潜热影响幅度3.14%,相变温度基本不变;50次循环后,相变潜热影响幅度保持在1.4%以内,循环稳定性较好,具有较好的应用前景。