Article(id=1154428298718339987, tenantId=1146029695717560320, journalId=1146119893612605453, issueId=1154428293831975813, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1669392000000, receivedDateStr=2022-11-26, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1753166754655, onlineDateStr=2025-07-22, pubDate=1708358400000, pubDateStr=2024-02-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1753166754655, onlineIssueDateStr=2025-07-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1753166754655, creator=13701087609, updateTime=1753166754655, updator=13701087609, issue=Issue{id=1154428293831975813, tenantId=1146029695717560320, journalId=1146119893612605453, year='2024', volume='42', issue='2', pageStart='143', pageEnd='284', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1753166753490, creator=13701087609, updateTime=1753694636757, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1156642396780745248, tenantId=1146029695717560320, journalId=1146119893612605453, issueId=1154428293831975813, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1156642396780745249, tenantId=1146029695717560320, journalId=1146119893612605453, issueId=1154428293831975813, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=181, endPage=188, ext={EN=ArticleExt(id=1154428299183907732, articleId=1154428298718339987, tenantId=1146029695717560320, journalId=1146119893612605453, language=EN, title=Preparation and properties of expanded vermiculite-based composites, columnId=null, journalTitle=Renewable Energy Resources, columnName=null, runingTitle=null, highlight=null, articleAbstract=

In this study, the Capricpalmitic acid (CAPA) binary eutectic PCM was vacuum impregnated into the expanded vermiculite (EVM) to prepare CAPA/EVM composite phase change thermal storage material. FTIR, DSC, TG, and thermal cycling were used to assess the chemical compatibility, heat storage performance, thermal stability, and thermal reliability of CAPA/EVM. The results showed that CAPA was stably loaded in the layered pores of EVM through physical interaction, and CAPA/EVM had excellent chemical compatibility. The Melting and solidification phase transition temperatures of CAPA/EVM were 23.61 and 20.41 °C, respectively. The latent heat of melting and solidification phase transition were 67.22 and 64.87 J/g, respectively. The amount of CAPA encapsulated in EVM could reach 52.22%, and it had favorable thermal stability at working temperature. In addition, the CAPA/EVM maintained great thermal reliability after 100 thermal cycles, indicating its potential application in the building energy conservation field.

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文章以癸酸棕榈酸(CAPA)二元共晶物作为相变材料,膨胀蛭石(EVM)作为支撑材料,采用真空浸渍法制备癸酸−棕榈酸/膨胀蛭石复合相变储热材料(CAPA/EVM)。通过 FTIR,DSC,TG,热循环等测试方法对癸酸−棕榈酸/膨胀蛭石复合相变储热材料的化学兼容性、储热性能、热稳定性及可靠性进行系统研究。结果表明:膨胀蛭石通过物理作用吸附癸酸−棕榈酸二元共晶物至其层状孔隙结构,且二者化学兼容性良好;癸酸棕榈酸/膨胀蛭石复合相变储热材料的融化和凝固相变温度分别23.61,20.41℃,熔化和凝固相变潜热分别为67.22,64.87 J/g;膨胀蛭石中癸酸−棕榈酸的封装量可达52.22%,在工作温度下具有良好的热稳定性;癸酸−棕榈酸/膨胀蛭石复合相变储热材料经过100次热循环后仍保持良好的热可靠性,在建筑节能领域具有广阔的应用前景。

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刘松阳(1984-),男,博士,讲师,硕士生导师,研究方向为节能建筑材料、矿物基太阳能储热材料。E-mail:
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Solar Energy Materials and Solar Cells, 2016, 155: 9-13., articleTitle=Preparation of stearic acid/ modified expanded vermiculite composite phase change material with simultaneously enhanced thermal conductivity and latent heat, refAbstract=null)], funds=[Fund(id=1154428332763504723, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154428298718339987, awardId=LJKZ0405, language=CN, fundingSource=辽宁省教育厅面上项目(LJKZ0405), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1154428328049106980, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154428298718339987, xref=1, ext=[AuthorCompanyExt(id=1154428328053301285, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154428298718339987, companyId=1154428328049106980, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 Department of Civil Engineering Liaoning Petrochemical University Fushun 113001 China), 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articleId=1154428298718339987, language=EN, label=Table 1, caption=Comparison of thermal properties between pure PCM and CA-PA binary eutectic PCM, figureFileSmall=null, figureFileBig=null, tableContent=
参数 CA PA CA-PA 预测值 CA-PA 实验值
相变温度 $/℃$ 31.10 62.43 26.05 23.84
相变潜热/J $\cdot {\mathrm{g}}^{-1}$ 139.50 182.20 141.80 130.20
), ArticleFig(id=1154428332499263568, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154428298718339987, language=CN, label=表 1, caption=单一相变材料与癸酸-棕榈酸二元共晶相变材料热性能的比较, figureFileSmall=null, figureFileBig=null, tableContent=
参数 CA PA CA-PA 预测值 CA-PA 实验值
相变温度 $/℃$ 31.10 62.43 26.05 23.84
相变潜热/J $\cdot {\mathrm{g}}^{-1}$ 139.50 182.20 141.80 130.20
), ArticleFig(id=1154428332553789521, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154428298718339987, language=EN, label=Table 2, caption=Comparison of thermal properties of EVM-based composite phase change heat storage materials in references and this work, figureFileSmall=null, figureFileBig=null, tableContent=
储热材料 融化相变温度 ℃ 融化相变潜热 装载量
癸酸–硬脂酸/膨胀蛭石 [ 18 ] 24.54 76.32 41.38
硬脂酸/膨胀蛭石[ 19 ] 66.40 77.60 38.91
本文实验 23.61 67.22 52.22
), ArticleFig(id=1154428332612509778, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154428298718339987, language=CN, label=表 2, caption=本文实验和文献中膨胀蛭石基复合相变储热材料热性能比较, figureFileSmall=null, figureFileBig=null, tableContent=
储热材料 融化相变温度 ℃ 融化相变潜热 装载量
癸酸–硬脂酸/膨胀蛭石 [ 18 ] 24.54 76.32 41.38
硬脂酸/膨胀蛭石[ 19 ] 66.40 77.60 38.91
本文实验 23.61 67.22 52.22
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膨胀蛭石基复合相变储热材料的制备及性能研究
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白瑞雪 1 , 刘松阳 1 , 王梦晴 1 , 高卫 1
可再生能源 | 2024,42(2): 181-188
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可再生能源 | 2024, 42(2): 181-188
膨胀蛭石基复合相变储热材料的制备及性能研究
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白瑞雪1, 刘松阳1 , 王梦晴1, 高卫1
作者信息
  • 1 辽宁石油化工大学 土木工程学院 辽宁 抚顺 113001

通讯作者:

刘松阳(1984-),男,博士,讲师,硕士生导师,研究方向为节能建筑材料、矿物基太阳能储热材料。E-mail:
Preparation and properties of expanded vermiculite-based composites
Ruixue Bai1, Songyang Liu1 , Mengqing Wang1, Wei Gao1
Affiliations
  • 1 Department of Civil Engineering Liaoning Petrochemical University Fushun 113001 China
出版时间: 2024-02-20
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文章以癸酸棕榈酸(CAPA)二元共晶物作为相变材料,膨胀蛭石(EVM)作为支撑材料,采用真空浸渍法制备癸酸−棕榈酸/膨胀蛭石复合相变储热材料(CAPA/EVM)。通过 FTIR,DSC,TG,热循环等测试方法对癸酸−棕榈酸/膨胀蛭石复合相变储热材料的化学兼容性、储热性能、热稳定性及可靠性进行系统研究。结果表明:膨胀蛭石通过物理作用吸附癸酸−棕榈酸二元共晶物至其层状孔隙结构,且二者化学兼容性良好;癸酸棕榈酸/膨胀蛭石复合相变储热材料的融化和凝固相变温度分别23.61,20.41℃,熔化和凝固相变潜热分别为67.22,64.87 J/g;膨胀蛭石中癸酸−棕榈酸的封装量可达52.22%,在工作温度下具有良好的热稳定性;癸酸−棕榈酸/膨胀蛭石复合相变储热材料经过100次热循环后仍保持良好的热可靠性,在建筑节能领域具有广阔的应用前景。

癸酸-棕榈酸  /  膨胀蛭石  /  复合相变储热材料  /  建筑节能

In this study, the Capricpalmitic acid (CAPA) binary eutectic PCM was vacuum impregnated into the expanded vermiculite (EVM) to prepare CAPA/EVM composite phase change thermal storage material. FTIR, DSC, TG, and thermal cycling were used to assess the chemical compatibility, heat storage performance, thermal stability, and thermal reliability of CAPA/EVM. The results showed that CAPA was stably loaded in the layered pores of EVM through physical interaction, and CAPA/EVM had excellent chemical compatibility. The Melting and solidification phase transition temperatures of CAPA/EVM were 23.61 and 20.41 °C, respectively. The latent heat of melting and solidification phase transition were 67.22 and 64.87 J/g, respectively. The amount of CAPA encapsulated in EVM could reach 52.22%, and it had favorable thermal stability at working temperature. In addition, the CAPA/EVM maintained great thermal reliability after 100 thermal cycles, indicating its potential application in the building energy conservation field.

capric acid-palmitic acid  /  expanded vermiculite  /  composite phase change energy storage material  /  building energy conservation
白瑞雪, 刘松阳, 王梦晴, 高卫. 膨胀蛭石基复合相变储热材料的制备及性能研究. 可再生能源, 2024 , 42 (2) : 181 -188 .
Ruixue Bai, Songyang Liu, Mengqing Wang, Wei Gao. Preparation and properties of expanded vermiculite-based composites[J]. Renewable Energy Resources, 2024 , 42 (2) : 181 -188 .
现代工业的快速发展、人口的激增和化石燃料消耗的急剧增加导致全球能源短缺 [ 1 ] 。燃烧化石燃料会向大气中释放大量 ${\mathrm{{CO}}}_{2}$ ,据英国石油公司发布的《世界能源统计年鉴》数据显示,2021 年全球碳排放量高达 339 亿 $\mathrm{t}$ ,大量的碳排放引起温室效应、极端天气频发和荒漠化加剧等问题。面对能源问题和环境问题的双重压力, 开发清洁能源和提高能源利用效率是急需解决的问题 [ 2 ]
太阳能作为一种丰富、廉价的天然可再生能源, 可以替代部分传统能源达到节能目的。但由于太阳能的波动性和不连续性使其利用效率较低。 为了扩大其应用范围, 以相变材料 (PCM) 为基础的储能技术受到了广泛关注。相变材料是一种通过改变形态吸收或释放大量能量而保持自身温度不变的新型功能材料, 可以将环境中多余的能量储存并在需要的时候释放, 提供稳定的热源, 被广泛应用于建筑节能、热回收、温度控制、电池热管理、太阳能蓄热等领域 [ 3 ] 。在众多相变材料中,脂肪酸作为一种典型的有机相变材料, 因其无毒、热效率较高、不可燃、过冷度较低等优点而受到广泛关注 [ 4 ] 。然而绝大多数单一脂肪酸熔点较高,其应用范围受到极大限制。研究表明,将两种或两种以上的相变材料混合成多元共晶相变材料, 可以获得具有合适相变温度的相变材料, 并保持相对较高的潜热。周孙希 [ 5 ] 制备出相变温度为 ${1.0}^{\circ }\mathrm{C}$ 的十四烷-正新酸二元共晶相变材料, 可应用于冷链物流保鲜领域。苗扬 [ 6 ] 将癸酸和肉豆蔻酸混合制备癸酸-肉豆蔻酸共晶相变材料, 混合后的复合相变材料相变温度为 ${24.5}^{\circ }\mathrm{C}$ ,低于单一的癸酸和肉豆蔻酸相变材料, 在建筑节能应用方面有很大的潜力。
相变材料具有较高的储热能力, 但在固态向液态转变的过程中容易发生泄漏, 限制了其广泛应用 [ 7 ] 。为了克服这一问题,采用矿物基多孔结构材料与相变材料相结合是一种有效提高封装性能的方法。目前常见的矿物支撑基体有硅藻土、 高岭土、膨润土等。膨胀蛭石(EVM)具有吸附性好、比表面积大等特性,拥有独特的单元层结构和丰富的孔道层孔隙, 是隔热、吸附重金属离子和催化剂负载等领域较为理想的载体。Yang Z [ 8 ] 通过物理浸渍法制备石蜡/膨胀蛭石复合相变材料, 经过 100 次热循环后仍然具有良好的结构形态,可以有效防止相变材料的泄漏。Wen R [ 9 ] 以膨胀蛭石作为基体, 采用真空浸渍法吸附月桂酸, 成功制备了化学兼容性和稳定性良好的月桂酸/ 膨胀蛭石复合相变储热材料。大量研究表明,膨胀蛭石是可以应用于蓄热系统中的一种较好的候选材料。
本文利用膨胀蛭石良好的吸附和封装特点, 在真空条件下吸附癸酸-棕榈酸二元共晶相变材料, 制备一种可应用于建筑节能领域的复合相变储热材料。通过扫描电镜(SEM)、傅里叶红外光谱 (FT-IR)、X 射线衍射 (XRD)、差示扫描量热 (DSC)、热重分析(TG)和热循环等表征手段,研究了癸酸-棕榈酸/膨胀蛭石复合相变储热材料的结构和热性能等综合性能。
癸酸(Capric Acid, CA, ${\mathrm{C}}_{10}{\mathrm{H}}_{20}{\mathrm{O}}_{2},\mathrm{{AR}}$ ),上海麦克林生化科技有限公司;棕榈酸(Palmitic Acid, $\left.{\mathrm{{PA}},{\mathrm{C}}_{16}{\mathrm{H}}_{32}{\mathrm{O}}_{2},\mathrm{{AR}}}\right)$ ,国药集团化学试剂有限公司; 膨胀蛭石(Expanded Vermiculite, EVM),产地为河北灵寿,主要化学组成为 ${\mathrm{{SiO}}}_{2}\left({{66.86}\%}\right),{\mathrm{{Al}}}_{2}{\mathrm{O}}_{3}$ (15.68%), MgO(14.00%)。
通过 Schroeder [ 10 ] 方程及 DSC 测试确定癸酸- 棕榈酸二元共晶相变材料的最佳组成配比, 并预测其相变温度和相变潜热。
$\left\{\begin{array}{l}\ln {x}_{\mathrm{{CA}}}= \frac{\Delta {H}_{\mathrm{{CA}}}}{R}\left({\frac{1}{{T}_{\mathrm{{CA}}}}- \frac{1}{{T}_{\mathrm{m}}}}\right)\\\ln {x}_{\mathrm{{PA}}}= \frac{\Delta {H}_{\mathrm{{PA}}}}{R}\left({\frac{1}{{T}_{\mathrm{{PA}}}}- \frac{1}{{T}_{\mathrm{m}}}}\right)\end{array}\right.$
$\Delta {H}_{\mathrm{m}}= {T}_{\mathrm{m}}\left({\frac{{x}_{\mathrm{{CA}}}\Delta {H}_{\mathrm{{CA}}}}{{T}_{\mathrm{{CA}}}}+ \frac{{x}_{\mathrm{{PA}}}\Delta {H}_{\mathrm{{PA}}}}{{T}_{\mathrm{{PA}}}}}\right)$
式中: ${x}_{\mathrm{{CA}}},{x}_{\mathrm{{PA}}}$ 分别为癸酸和棕榈酸的摩尔分数; $\Delta {H}_{\mathrm{{CA}}},\Delta {H}_{\mathrm{{PA}}},\Delta {H}_{\mathrm{m}}$ 分别为癸酸、棕榈酸和癸酸-棕榈酸摩尔融化潜热, $\mathrm{J}/\mathrm{{mol}};{T}_{\mathrm{{CA}}},{T}_{\mathrm{{PA}}},{T}_{\mathrm{m}}$ 分别为癸酸、棕榈酸和癸酸-棕榈酸融化温度, $\mathrm{K};R$ 为摩尔气体常数,记为 ${8.315}\mathrm{\;J}/\left({\mathrm{{mol}}\cdot \mathrm{K}}\right)$
通过 MATLAB 求解上述公式,二元共晶相变材料中癸酸与棕榈酸的质量比值约为 81.8 : 18.2 。 表 1 为单一相变材料和癸酸-棕榈酸二元共晶相变材料的预测和实验的热性能相关数据。从 表 1 中可以看出, 二元共晶相变材料的相变温度和潜热误差分别为 ${2.21}{}^{\circ }\mathrm{C}$${11.60}\mathrm{\;J}/\mathrm{g}$ ,一般认为脂肪酸的相变温度和潜热预测值与实际值的偏差应在 ${5}^{\circ }\mathrm{C}$${30.00}\mathrm{\;J}/\mathrm{g}$ [ 11 ] ,可见实验值和预测值吻合较好, 预测配比成功。
本文采用熔融共混法制备癸酸-棕榈酸二元共晶相变材料。按照癸酸:棕榈酸为 81.8;18.2 的质量配比称取相应样品,将其置于 ${80}^{\circ }\mathrm{C}$ 的恒温水浴锅中直至融化。以 ${1200}\mathrm{r}/\mathrm{{min}}$ 的转速磁力搅拌 ${30}\mathrm{\;{min}}$ 使二者充分混合,玻璃棒搅拌 ${15}\mathrm{\;{min}}$ 后冷却至室温, 研磨得到癸酸-棕榈酸二元共晶相变材料备用。采用真空浸渍法制备癸酸-棕榈酸/膨胀蛭石复合相变储热材料。通过泄漏试验[ 12 ],根据复合相变材料中癸酸-棕榈酸的泄漏率确定癸酸-棕榈酸和膨胀蛭石最佳质量配比为 6:4, 按照该比例称取两种材料并混合均匀倒入锥形瓶内, 静置于 80°C水浴锅中使癸酸-棕榈酸融化,抽真空至 $-{0.1}\mathrm{{MPa}}$ 并在 ${80}^{\circ }\mathrm{C}$ 温度下保持 ${30}\mathrm{\;{min}}$ ,关闭真空泵恢复大气压力使癸酸-棕榈酸渗透于膨胀蛭石中,80°C超声加热 $5\mathrm{\;{min}}$ 。冷却至室温后在 ${50}^{\circ }\mathrm{C}$ 烘箱中热过滤 ${12}\mathrm{\;h}$ 以去除过量的癸酸-棕榈酸,得到癸酸-棕榈酸/膨胀蛭石复合相变储热材料(以下简称为复合相变储热材料)。
用热循环实验考察复合相变储热材料的长期可靠性。将复合相变储热材料置于滤纸上, 放入 50°C烘箱中 ${10}\mathrm{\;{min}}$ ,取出后置于室温下 ${10}\mathrm{\;{min}}$ , 此过程为一次热循环,共进行 100 次热循环。
采用全自动比表面积测定仪 (BET, ASAP 2020)测试膨胀蛭石的比表面积(BET 法)和孔径分布情况,按标准测试程序在低温下(77.35K) 获得膨胀蛭石的氮气吸-脱附等温线。使用傅里 叶 红 外 光 谱 仪 (FT -IR, Nicolet 5700 spectrophotometer) 记录样品 波长内的透射光谱,并进行化学结构分析。样品的晶体结构用 X 射线衍射仪 (XRD, Bruker D8 Advance) 的连续扫描模式进行测试,扫描速度为 , 扫描值为 。采用扫描电子显微镜(SEM, FEI quantum-200 )观察样品的微观形貌。在 0~ 的恒定 下以 的升温速率对样品的相变温度和相变潜热进行差式扫描量热 (DSC, TADSC-Q20) 分析, 每次样品用量约为 5 。采用同步热分析仪(TG, SDT Q600)分析样品的热稳定性,测试在恒定氩气流下以 的速度在室温~400°C内进行。
图 1 为膨胀蛭石的 ${\mathrm{N}}_{2}$ 吸-脱附曲线和对应的孔径分布图。横坐标采用比压 $\left({P/{P}_{0}}\right)$ 表示压力,其中 $P$${\mathrm{N}}_{2}$ 的真实压力, ${P}_{0}$${\mathrm{N}}_{2}$ 在测量温度下的饱和蒸汽压,纵坐标表示恒温条件下 ${\mathrm{N}}_{2}$ 在膨胀蛭石上的吸附量。
图 1 中可以看出, 膨胀蛭石属于典型的 IV 型等温线,在中压段出现毛细凝聚而引起吸附量上升, 毛细凝聚填满后由于稍大孔的强相互作用而继续吸附形成多分子层, 吸附等温线继续上升且接近垂直。曲线中可以明显观察到 III型回滞环, 在相对较高压力处无明显的饱和吸附平台, 证明膨胀蛭石是一种存在非均匀平行板狭缝或裂缝状孔的片状颗粒结构。膨胀蛭石的比表面积和孔容分别为 ${14.37}{\mathrm{\;m}}^{2}/\mathrm{g}$${0.02}{\mathrm{\;{cm}}}^{3}/\mathrm{g}$ 。从孔径分布图中可以看出,膨胀蛭石孔径集中在 $1 \sim {10}\mathrm{\;{nm}}$ , 表明存在较大比例的微孔和介孔,为癸酸-棕榈酸的吸附提供了大量的吸附位点和运输途径, 提高了膨胀蛭石的封装容量和储热性能, 可作为相变材料理想的多孔封装基体。
图 2 为膨胀蛭石和复合相变储热材料的微观形貌和 EDS 能谱。
图 2(a)中可以看出,膨胀蛭石呈现出典型的层状形貌, 大量的孔隙紧密堆积堆叠在一起, 较高的比表面积和孔隙比有助于吸附熔融状态的癸酸-棕榈酸二元共晶相变材料。由 图 2(c)可见,真空浸渍后膨胀蛭石的层空间被癸酸-棕榈酸占据, 片层变厚, 这可能是由于膨胀蛭石基体毛细作用与表面张力之间的协同作用, 使得癸酸- 棕榈酸能有效地包覆膨胀蛭石。此外, 图 2(b)2 (d)分别为膨胀蛭石和复合相变储热材料的 EDS 能谱图, 碳含量由初始的 8.13%增加至 38.29%, 表明癸酸-棕榈酸成功吸附于膨胀蛭石上。膨胀蛭石能够有效封装癸酸-棕榈酸二元共晶相变材料并保留了良好的形态特征, 可以作为一种良好的支撑相变材料的基体。
图 3 为癸酸-棕榈酸、膨胀蛭石和复合相变储热材料的 XRD 和 FT-IR 谱图。
图 3(a)可见, 癸酸-棕榈酸的特征衍射峰主要表现在 ${6.0},{11.4},{21.4},{23.5}^{\circ }$${40.2}^{\circ }$ ,这与之前的研究结果一致 [ 13 ] 。膨胀蛭石在 ${8.9},{27.0},{28.7}{}^{\circ }$ 处有标准的主相位反射峰,在 24.0 °有一个弱而宽的峰,说明膨胀蛭石具有不完全结晶度 [ 14 ] 。复合相变储热材料的 XRD 谱图包括癸酸-棕榈酸二元共晶相变材料和膨胀蛭石所有特征峰, 这意味着癸酸-棕榈酸与膨胀蛭石结合后二者晶体结构仍未改变。同时可以观察到,复合相变储热材料的峰值强度低于癸酸-棕榈酸二元共晶物, 这一现象表明由于膨胀蛭石孔隙对癸酸-棕榈酸结晶生长的限制作用, 使得复合材料中癸酸-棕榈酸的晶粒尺寸变小 [ 15 ] 。XRD 分析表明,癸酸-棕榈酸二元共晶相变材料和膨胀蛭石封装基体之间仅涉及物理作用, 没有发生化学反应, 表现出良好的晶体结构稳定性。
图 3(b)为癸酸-棕榈酸、膨胀蛭石和复合相变储热材料的 FT-IR 测试曲线。位于 ${2.918}{\mathrm{\;{cm}}}^{-1}$${2850}{\mathrm{\;{cm}}}^{-1}$ 的吸收峰分别表示癸酸-棕榈酸二元共晶相变材料脂肪酸中 $-{\mathrm{{CH}}}_{3}$$-{\mathrm{{CH}}}_{2}$$\mathrm{C}- \mathrm{H}$ 拉伸振动。波数为 ${1701}{\mathrm{\;{cm}}}^{-1}$ 处的峰是由于碳基(C= 0 ) 的拉伸振动引起的。此外, ${1466}{\mathrm{\;{cm}}}^{-1}$ 处的特征峰表明 $-{\mathrm{{CH}}}_{3}$ 发生了剪切弯曲振动。而红外谱中出现 ${1297},{936}{\mathrm{\;{cm}}}^{-1}$ 的峰分别对应脂肪酸中 $-\mathrm{{OH}}$ 官能团平面内外的弯曲振动。 ${723}{\mathrm{\;{cm}}}^{-1}$ 处的峰值代表了 $-\mathrm{{OH}}$ 官能团平面内的摆动振动。膨胀蛭石的图谱中, ${1015}{\mathrm{\;{cm}}}^{-1}$ 的红外峰归因于 $\mathrm{{Si}}- \mathrm{O}-$ $\mathrm{{Si}}$$\mathrm{{Si}}- \mathrm{O}- \mathrm{{Al}}$ 官能键的拉伸振动,对于 ${444}{\mathrm{\;{cm}}}^{-1}$ 处的峰值则是因为 $\mathrm{{Si}}- \mathrm{O}- \mathrm{{Mg}}$ 的弯曲振动 [ 16 ] 。在复合相变储热材料光谱中, 癸酸-棕榈酸二元共晶相变材料和膨胀蛭石的主要吸收峰均出现于复合相变储热材料的红外光谱中, 且未出现新的化学键, 表明癸酸-棕榈酸被成功负载于膨胀蛭石孔隙中,二者兼容性良好,具有良好的化学稳定性。
相变温度和相变潜热是评价相变储热材料热性能非常重要的指标。 图 4 为癸酸-棕榈酸二元共晶相变材料和复合相变储热材料的 DSC 测试曲线, 癸酸-棕榈酸二元共晶相变材料的融化和凝固相变温度分别为 ${23.84},{20.64}^{\circ }\mathrm{C}$ ,融化和凝固相变潜热分别为 ${130.20},{127.90}\mathrm{\;J}/\mathrm{g}$ 。而复合相变储热材料的融化温度和融化潜热分别为 ${23.61}^{\circ }\mathrm{C}$${67.22}\mathrm{\;J}/\mathrm{g}$ ,凝固温度和凝固潜热分别为 ${20.41}^{\circ }\mathrm{C}$${64.87}\mathrm{\;J}/\mathrm{g}$ 。与癸酸-棕榈酸二元共晶相变材料对比,复合相变储热材料相变温度微小的降低可能是癸酸-棕榈酸与膨胀蛭石孔隙表面之间的弱吸引相互作用 [ 17 ] ,而相变潜热的降低则与膨胀蛭石中癸酸-棕榈酸二元共晶相变材料的含量有关。
本文实验和文献中膨胀蛭石基复合相变储热材料的热性能对比见 表 2
表 2 可知, 本文实验研究制备的复合相变储热材料融化相变温度处于 16~28 °C的人体舒适温度,同时在装载能力上也具有一定优势,有望与水泥砂浆、混凝土等建筑材料复配制备建筑节能材料, 运用于建筑围护结构中以达到太阳能蓄热和调温作用。
图 5 为癸酸-棕榈酸、膨胀蛭石和复合相变储热材料的 TG 曲线。
图 5 可知, 癸酸-棕榈酸二元共晶相变材料在温度达到 ${120}^{\circ }\mathrm{C}$ 左右时表现出良好的热稳定性。在此之后,质量快速损失,在 ${250}^{\circ }\mathrm{C}$ 时失重率达到了 98.76%,质量几乎完全损失。膨胀蛭石在 400 °C内仅发生少量自由水和层间水的蒸发,重量损失可以忽略不计。复合相变储热材料在 110~ 210 ℃质量急剧下降,由于癸酸-棕榈酸二元共晶相变材料的挥发, 因此复合相变储热材料中癸酸-棕榈酸装载量达到了 52.22%。由于复合相变储热材料的分解温度明显高于工作温度 $\left({{80}^{\circ }\mathrm{C}}\right)$ , 可以得出结论, 本文实验研究所制备的复合相变储热材料在工作温度下具有良好的热稳定性。
复合相变储热材料在长期使用过程中需要保持良好的可靠性。因此, 本文研究了复合相变储热材料 100 次热循环实验后的化学可靠性和热可靠性,结果见 图 6
图 6(a) 为复合相变储热材料的 100 次热循环前后的 XRD 谱图, 可以看到, 二者的衍射峰没有明显的区别, 这表明复合相变储热材料的晶体结构不受热循环的影响。 图 6(b)为复合相变储热材料经过 100 次热循环后的 SEM 图像,显示膨胀蛭石同样被癸酸-棕榈酸覆盖, 表明热循环实验对复合相变储热材料形貌并无明显影响。由 图 6(c) 可以看出,复合相变储热材料的 FT-IR 光谱热循环前后特征峰无明显差异,证实了复合相变储热材料结构的稳定性。 图 6(d)为复合相变储热材料热循环 100 次前后的 DSC 曲线, 循环后的融化相变温度和相变潜热分别为 ${23.74}^{\circ }\mathrm{C}$${66.14}^{\circ }$ $\mathrm{J}/\mathrm{g}$ ,与循环前相比分别降低 ${0.13}^{\circ }\mathrm{C}$${1.08}\mathrm{\;J}/\mathrm{g}$ ,变化率仅为 0.5% 和 1.6%,表明复合相变储热材料具有良好的储热稳定性。实验结果表明,复合相变储热材料在长期应用下表现出良好的热可靠性。
本文采用真空浸渍法制备了形态稳定的癸酸-棕榈酸/膨胀蛭石复合相变储热材料。利用 SEM, XRD, FT-IR, DSC, TG, 热循环等测试方法对样品的微观形貌、晶体结构、化学相容性、储热能力、热稳定性、热可靠性进行了研究和分析,主要结论如下。
①癸酸-棕榈酸与膨胀蛭石复合后的癸酸- 棕榈酸/膨胀蛭石复合相变储热材料没有新物质产生, 由于膨胀蛭石基体孔隙毛细作用与表面张力之间的协同作用, 使得癸酸-棕榈酸成功包覆膨胀蛭石,且膨胀蛭石可以保持较好的层状形貌。 癸酸-棕榈酸/膨胀蛭石复合相变储热材料具有良好的晶体结构和化学结构稳定性。
②癸酸-棕榈酸/膨胀蛭石复合相变储热材料融化和凝固相变温度分别为 ${23.61},{20.41}^{\circ }\mathrm{C}$ ,熔化和凝固相变潜热分别为 ${67.20},{64.87}\mathrm{\;J}/\mathrm{g}$ 。癸酸-棕榈酸/膨胀蛭石复合相变储热相变材料中CA-PA 的装载量达到了 52.22%,在工作温度下热稳定性良好。
③癸酸-棕榈酸/膨胀蛭石复合相变储热相变材料经过 100 次热循环后, 其晶体结构、微观形貌、化学结构、融化相变温度和潜热均无明显变化,具有良好的可靠性,能保证在建筑工程中维持自身性能基本稳定, 具有制备新型建筑节能材料以改善建筑蓄热、隔热性能的应用潜力。
  • 辽宁省教育厅面上项目(LJKZ0405)
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  • 接收时间:2022-11-26
  • 首发时间:2025-07-22
  • 出版时间:2024-02-20
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  • 收稿日期:2022-11-26
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辽宁省教育厅面上项目(LJKZ0405)
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    1 辽宁石油化工大学 土木工程学院 辽宁 抚顺 113001

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刘松阳(1984-),男,博士,讲师,硕士生导师,研究方向为节能建筑材料、矿物基太阳能储热材料。E-mail:
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2种不同金属材料的力学参数

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种数
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Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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