Article(id=1288421751050711291, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1288421735473058437, articleNumber=null, orderNo=null, doi=10.3981/j.issn.1000-7857.2025.12.00111, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1766332800000, receivedDateStr=2025-12-22, revisedDate=1770566400000, revisedDateStr=2026-02-09, acceptedDate=null, acceptedDateStr=null, onlineDate=1785113283169, onlineDateStr=2026-07-27, pubDate=1783872000000, pubDateStr=2026-07-13, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1785113283169, onlineIssueDateStr=2026-07-27, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1785113283169, creator=13701087609, updateTime=1785113283169, updator=13701087609, issue=Issue{id=1288421735473058437, tenantId=1146029695717560320, journalId=1146031591421210625, year='2026', volume='44', issue='13', pageStart='1', pageEnd='188', issueExtLink='null', onlineDate='null', pubDate='1783872000000', pubDateStr='2026-07-13', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1785113279455, creator='13701087609', updateTime=1785113348006, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1288422023114240128, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1288421735473058437, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1288422023118434433, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1288421735473058437, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=115, endPage=130, ext={EN=ArticleExt(id=1288421751273009404, articleId=1288421751050711291, tenantId=1146029695717560320, journalId=1146031591421210625, language=EN, title=Oxide porous ceramics and aerogels for thermal insulation applications in extreme thermal environments, columnId=1150494642224591153, journalTitle=Science & Technology Review, columnName=Exclusive, runingTitle=null, highlight=null, articleAbstract=

As aerospace technology advances toward higher speeds and longer flight durations, aircraft face new thermal challenges in extreme environments. Conventional thermal protection systems are no longer sufficient to meet the requirements of these applications. Therefore, there is an urgent need to conduct research on the design and manufacturing of novel thermal protection systems. In line with the trend toward integrating thermal protection and insulation, thermal insulation materials must possess excellent thermal insulation, high temperature resistance, and mechanical properties. Both porous ceramics and aerogels present significant performance trade−offs, making it imperative to optimize their comprehensive properties of these materials to meet the requirements of extreme applications. This article systematically reviews the research progress on oxide porous ceramics and aerogels as high−performance thermal insulation materials, and details their material characteristics, preparation methods, thermal insulation performance, mechanical properties, and high−temperature resistance. Through strategies such as compositional design, fiber reinforcement, and structural regulation, the thermal insulation and mechanical properties of oxide porous ceramics and aerogels can be tailored, endowing them with broad application potential in thermal protection systems for extreme environments.

, authors=Peng WANG1, 2, 3, 4, Yaru CHEN1, 2, 3, Zhiqiang CHENG4, Lijuan ZHANG5, 6, *, Baosheng XU7, Guangwu WEN1, 3, *, authorsList=Peng WANG, Yaru CHEN, Zhiqiang CHENG, Lijuan ZHANG, Baosheng XU, Guangwu WEN, authorCompany=null, correspAuthors=Lijuan ZHANG, Guangwu WEN, authorNote=null, correspAuthorsNote=null, copyrightStatement=All rights reserved. Unauthorized reproduction is prohibited., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1288421755593142555, articleId=1288421751050711291, tenantId=1146029695717560320, journalId=1146031591421210625, language=CN, title=应用于极端热环境的氧化物多孔陶瓷及气凝胶隔热材料, columnId=1150494642375586098, journalTitle=科技导报, columnName=特色专题, runingTitle=null, highlight=null, articleAbstract=

随着航空航天装备向更高速度、更长航时的方向发展,飞行器在极端热环境中面临“新热障”挑战,传统热防护系统已难以满足其应用需求,亟须开展新型热防护系统的设计及制造研究。在防隔热一体化趋势下,隔热材料须兼具优异的隔热性能、耐温性能和力学性能。现有多孔陶瓷和气凝胶等存在显著性能权衡,亟须通过材料设计优化综合性能以满足极端应用场景的要求。系统介绍了氧化物多孔陶瓷及气凝胶作为高性能隔热材料的研究进展,详细阐述了氧化物多孔陶瓷及气凝胶的材料特性、制备方法、隔热性能、力学性能和耐高温性能等。通过组分设计、纤维增强、结构调控等手段,可以对多孔氧化物陶瓷及气凝胶在隔热性能与力学性能上进行调节,使其在极端环境热防护系统中展现出广阔的应用前景。

, authors=王鹏1, 2, 3, 4, 陈亚茹1, 2, 3, 程之强4, 张丽娟5, 6, *, 徐宝升7, 温广武1, 3, *, authorsList=王鹏, 陈亚茹, 程之强, 张丽娟, 徐宝升, 温广武, authorCompany=null, correspAuthors=张丽娟, 温广武, authorNote=

王鹏,副教授,研究方向为超高温陶瓷材料、多孔陶瓷和气凝胶材料,电子信箱:

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张丽娟(通信作者),研究员,研究方向为超高温隔热材料,电子信箱:;
温广武(共同通信作者),教授,研究方向为特种陶瓷与碳材料,电子信箱:
, copyrightStatement=版权所有,未经授权,不得转载。, copyrightOwner=《科技导报》编辑部, extLink=null, articleAbsUrl=null, sourceXml=rSkhIDQvlwGgvHrZkC+F7w==, magXml=EdXmm6ydiV0oxDrobz4xcQ==, pdfUrl=null, pdf=ISH1ro19ac5vzGUBaTAVxQ==, pdfFileSize=8443808, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=tT7V3YlY4xElA2pVaGugrA==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=DLM6EpSkstg5VElT/0gXkg==, mapNumber=null, fund=null)}, authors=[Author(id=1288421757996478770, tenantId=1146029695717560320, journalId=1146031591421210625, articleId=1288421751050711291, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=wangpeng1@sdut.edu.cn, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1288421758113919287, tenantId=1146029695717560320, journalId=1146031591421210625, articleId=1288421751050711291, authorId=1288421757996478770, language=EN, stringName=Peng WANG, firstName=Peng, middleName=null, lastName=WANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, 2, 3, 4, address=1School of Materials Science and Engineering, Shandong University of Technology, Zibo 255000, China
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王鹏,副教授,研究方向为超高温陶瓷材料、多孔陶瓷和气凝胶材料,电子信箱:

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(a) 0.40 wt% PAA–0.010 wt% DTAC;(b) 0.40 wt% PAA–0.015 wt% DTAC;(c) 0.40 wt% PAA–0.020 wt% DTAC;(d) 0.45 wt% PAA–0.020 wt% DTAC;(e) 0.50 wt% PAA–0.020 wt% DTAC;(f) 0.55 wt% PAA–0.020 wt% DTAC

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参数SiO2Al2O3莫来石ZrO2镁铝尖晶石玄武岩
熔点/℃167020541850271521351000~1250
密度/(g·cm−32.653.953.165.683.582.63
硬度/GPa7~996~710~15165~6
热导率/(W·m−1·K−11.420~352.582.0~2.5162.5
), ArticleFig(id=1288421764250186111, tenantId=1146029695717560320, journalId=1146031591421210625, articleId=1288421751050711291, language=CN, label=表1, caption=

氧化物陶瓷材料基本性能参数

, figureFileSmall=null, figureFileBig=null, tableContent=
参数SiO2Al2O3莫来石ZrO2镁铝尖晶石玄武岩
熔点/℃167020541850271521351000~1250
密度/(g·cm−32.653.953.165.683.582.63
硬度/GPa7~996~710~15165~6
热导率/(W·m−1·K−11.420~352.582.0~2.5162.5
), ArticleFig(id=1288421764334072192, tenantId=1146029695717560320, journalId=1146031591421210625, articleId=1288421751050711291, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
材料种类制备方法孔隙率/%密度/(g·cm−3热导率/(W·m−1·K−1参考文献
SiO2多孔陶瓷发泡法90.00~97.000.039~0.079[41]
凝胶注模法83.100.116[42]
SiO2气凝胶溶胶凝胶法0.2000~0.60000.022~0.085[4546]
静电纺丝技术0.046[47]
Al2O3气凝胶溶胶凝胶法0.3300~0.36000.030~0.039[5051]
莫来石多孔陶瓷无压烧结31.94~42.191.078~1.582[52]
发泡法95.900.1800[53]
静电纺丝技术0.02200.035[54]
凝胶注模法55.90~64.691.1090~1.38500.194~0.436[55]
莫来石气凝胶溶胶凝胶法73.30~90.030.1760~0.86000.036~0.220[565759]
静电纺丝技术0.028~0.038[60]
ZrO2多孔陶瓷发泡法73.00~89.000.137~0.254[6162]
ZrO2气凝胶溶胶凝胶法0.220.036[64]
静电纺丝技术0.1500~0.55000.103~0.104[6566]
模板法67.20~71.900.180~0.380[68]
静电纺丝技术0.0016~0.01220.026~0.032[69]
玄武岩多孔陶瓷发泡法0.00890.031[70]
玄武岩气凝胶溶胶凝胶法90.000.027[71]
), ArticleFig(id=1288421764413763969, tenantId=1146029695717560320, journalId=1146031591421210625, articleId=1288421751050711291, language=CN, label=表2, caption=

不同方法制备的氧化物多孔陶瓷及气凝胶的孔隙率、密度和热导率

, figureFileSmall=null, figureFileBig=null, tableContent=
材料种类制备方法孔隙率/%密度/(g·cm−3热导率/(W·m−1·K−1参考文献
SiO2多孔陶瓷发泡法90.00~97.000.039~0.079[41]
凝胶注模法83.100.116[42]
SiO2气凝胶溶胶凝胶法0.2000~0.60000.022~0.085[4546]
静电纺丝技术0.046[47]
Al2O3气凝胶溶胶凝胶法0.3300~0.36000.030~0.039[5051]
莫来石多孔陶瓷无压烧结31.94~42.191.078~1.582[52]
发泡法95.900.1800[53]
静电纺丝技术0.02200.035[54]
凝胶注模法55.90~64.691.1090~1.38500.194~0.436[55]
莫来石气凝胶溶胶凝胶法73.30~90.030.1760~0.86000.036~0.220[565759]
静电纺丝技术0.028~0.038[60]
ZrO2多孔陶瓷发泡法73.00~89.000.137~0.254[6162]
ZrO2气凝胶溶胶凝胶法0.220.036[64]
静电纺丝技术0.1500~0.55000.103~0.104[6566]
模板法67.20~71.900.180~0.380[68]
静电纺丝技术0.0016~0.01220.026~0.032[69]
玄武岩多孔陶瓷发泡法0.00890.031[70]
玄武岩气凝胶溶胶凝胶法90.000.027[71]
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应用于极端热环境的氧化物多孔陶瓷及气凝胶隔热材料
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王鹏 1, 2, 3, 4 , 陈亚茹 1, 2, 3 , 程之强 4 , 张丽娟 5, 6, * , 徐宝升 7 , 温广武 1, 3, *
科技导报 | 特色专题 2026,44(13): 115-130
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科技导报 |特色专题 2026 , 44 (13) : 115 -130
应用于极端热环境的氧化物多孔陶瓷及气凝胶隔热材料
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王鹏1, 2, 3, 4 , 陈亚茹1, 2, 3, 程之强4, 张丽娟5, 6, * , 徐宝升7, 温广武1, 3, *
作者信息
  • 1山东理工大学材料科学与工程学院,淄博 255000
  • 2中材江西电瓷电气有限公司,萍乡 337000
  • 3高温功能陶瓷材料学科与技术中心,淄博 255000
  • 4山东工业陶瓷研究设计院有限公司,淄博 255000
  • 5哈尔滨工业大学复合材料与结构研究所,哈尔滨 150001
  • 6航天特种材料及工艺技术研究所,北京 100074
  • 7北京理工大学先进结构技术研究院,北京 100081
通讯作者:
张丽娟(通信作者),研究员,研究方向为超高温隔热材料,电子信箱:;
温广武(共同通信作者),教授,研究方向为特种陶瓷与碳材料,电子信箱:
作者简介:

王鹏,副教授,研究方向为超高温陶瓷材料、多孔陶瓷和气凝胶材料,电子信箱:

Oxide porous ceramics and aerogels for thermal insulation applications in extreme thermal environments
Peng WANG1, 2, 3, 4 , Yaru CHEN1, 2, 3, Zhiqiang CHENG4, Lijuan ZHANG5, 6, * , Baosheng XU7, Guangwu WEN1, 3, *
Affiliations
  • 1School of Materials Science and Engineering, Shandong University of Technology, Zibo 255000, China
  • 2Sinoma Jiangxi Insulator and Electricity Co., Ltd., Pingxiang 337000, China
  • 3Discipline and Technology Center for High Temperature Functional Ceramics, Zibo 255000, China
  • 4Shandong Industrial Ceramics Research and Design Institute Co., Ltd., Zibo 255000, China
  • 5Center for Composite Materials and Structure, Harbin Institute of Technology, Harbin 150001, China
  • 6Aerospace Institute of Advanced Material and Processing Technology, Beijing 100074, China
  • 7Institute of Advanced Structure Technology, Beijing Institute of Technology, Beijing 100081, China
出版时间: 2026-07-13 doi: 10.3981/j.issn.1000-7857.2025.12.00111
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随着航空航天装备向更高速度、更长航时的方向发展,飞行器在极端热环境中面临“新热障”挑战,传统热防护系统已难以满足其应用需求,亟须开展新型热防护系统的设计及制造研究。在防隔热一体化趋势下,隔热材料须兼具优异的隔热性能、耐温性能和力学性能。现有多孔陶瓷和气凝胶等存在显著性能权衡,亟须通过材料设计优化综合性能以满足极端应用场景的要求。系统介绍了氧化物多孔陶瓷及气凝胶作为高性能隔热材料的研究进展,详细阐述了氧化物多孔陶瓷及气凝胶的材料特性、制备方法、隔热性能、力学性能和耐高温性能等。通过组分设计、纤维增强、结构调控等手段,可以对多孔氧化物陶瓷及气凝胶在隔热性能与力学性能上进行调节,使其在极端环境热防护系统中展现出广阔的应用前景。

隔热材料  /  氧化物陶瓷  /  多孔陶瓷  /  气凝胶  /  制备方法

As aerospace technology advances toward higher speeds and longer flight durations, aircraft face new thermal challenges in extreme environments. Conventional thermal protection systems are no longer sufficient to meet the requirements of these applications. Therefore, there is an urgent need to conduct research on the design and manufacturing of novel thermal protection systems. In line with the trend toward integrating thermal protection and insulation, thermal insulation materials must possess excellent thermal insulation, high temperature resistance, and mechanical properties. Both porous ceramics and aerogels present significant performance trade−offs, making it imperative to optimize their comprehensive properties of these materials to meet the requirements of extreme applications. This article systematically reviews the research progress on oxide porous ceramics and aerogels as high−performance thermal insulation materials, and details their material characteristics, preparation methods, thermal insulation performance, mechanical properties, and high−temperature resistance. Through strategies such as compositional design, fiber reinforcement, and structural regulation, the thermal insulation and mechanical properties of oxide porous ceramics and aerogels can be tailored, endowing them with broad application potential in thermal protection systems for extreme environments.

thermal insulation materials  /  oxide ceramics  /  porous ceramics  /  aerogel  /  preparation methods
王鹏, 陈亚茹, 程之强, 张丽娟, 徐宝升, 温广武. 应用于极端热环境的氧化物多孔陶瓷及气凝胶隔热材料. 科技导报, 2026 , 44 (13) : 115 -130 . DOI: 10.3981/j.issn.1000-7857.2025.12.00111
Peng WANG, Yaru CHEN, Zhiqiang CHENG, Lijuan ZHANG, Baosheng XU, Guangwu WEN. Oxide porous ceramics and aerogels for thermal insulation applications in extreme thermal environments[J]. Science & Technology Review, 2026 , 44 (13) : 115 -130 . DOI: 10.3981/j.issn.1000-7857.2025.12.00111
随着航空航天技术的发展,飞行器在极端环境下面临的高热流、高焓、强氧化及高动压等“新热障”问题日益突出,热防护系统的性能对飞行器的成败具有决定性的作用。飞行器迎风面和机翼处的温度可达1400℃以上(图1[1]),对热防护技术提出了严峻的挑战。在传统热防护系统设计中,防热层与隔热层功能分离,导致系统结构复杂、效率较低且质量增加[25]。因此,“防隔热一体化”逐渐成为发展趋势,从材料、结构和工艺的协同设计出发,通过多尺度优化实现防热与隔热功能在材料层面的协同作用,从而为飞行器性能的突破性提升提供关键支撑。在此背景下,隔热材料已不再仅仅是背衬填充物,而是需要承受高温并承担部分结构载荷的重要材料[67]。这对隔热材料提出了极为严苛的综合性要求:极高的耐温性、极低的热导率,以及足以应对热力耦合环境的力学与抗热震性能。
目前,航空航天领域广泛应用的隔热材料主要包括多孔陶瓷(可重复使用隔热毡和隔热砖(图1(a))和气凝胶等。多孔陶瓷是以陶瓷粉体为原料[89],通过造孔剂法、发泡法、颗粒堆积法、模板法等工艺制备的陶瓷材料,以微米孔为主,开孔与闭孔共存,孔隙率为25%~95%[10]。多孔陶瓷的骨架形态会因制备工艺的不同而有所差异。气凝胶是由纳米颗粒或聚合物分子链交联形成的三维纳米多孔固体材料[1112],在孔隙内填充空气,是目前已知最轻的固态隔热材料,兼具极低密度与热导率的特点。气凝胶的孔隙以纳米孔为主,以闭孔为主导,孔隙率高达90%~99%[1314],骨架为纳米颗粒或纳米纤维交联形成的低密度三维网状结构。多孔材料的传热主要通过固相传导、气相对流及辐射传导3种途径进行[1516]。对于多孔陶瓷,其骨架刚性连续且烧结致密,对固相传导的抑制作用有限,但内部大量闭孔可有效阻隔气相传导,而热辐射的抑制则需依赖遮光剂掺杂或复杂孔型设计。然而,气凝胶凭借极低的密度与连续三维网状结构显著延长了传热路径,大幅削弱固相传热,同时,气凝胶的孔径普遍小于气体分子平均自由程,能强效抑制气相传导,加之纳米级骨架提供了大量固相−气相界面,可显著散射红外辐射,大幅降低辐射传热损失。它们各自的特性决定了其在热防护系统中的不同定位与局限性。柔性陶瓷纤维毡凭借其优异的柔韧性和力学性能,主要应用于低热流区域。柔性陶瓷纤维毡经历了从复合加工纤维绝热瓦、先进柔性可再生表面绝缘材料到拱形可重复使用隔热毡的逐步演进。这一过程充分体现了通过优化纤维组分(如引入硼硅铝纤维)和改进表面涂层技术,不断提升材料耐温极限和抗烧蚀能力的设计理念。隔热砖采用石英纤维等材料作为骨架,结合高纯度陶瓷基体,展现出卓越的高温耐受性、抗烧蚀能力及极低的热导率,常被应用于高热流迎风面。制备过程中精密的工艺控制是实现其稳定多孔结构与性能的关键。气凝胶,特别是SiO2气凝胶,代表了隔热材料在极低热导率方向上的追求,其纳米多孔网络结构赋予了它无与伦比的隔热效率[1718]。然而,其本征脆性和较差的抗热震性能,成为其在承力结构中广泛应用的主要障碍。当前隔热材料体系呈现出明显的性能“权衡”现象:气凝胶虽拥有卓越的隔热潜力,但其力学性能较差;纤维毡与隔热砖在力学性能上表现优异,然而其隔热效率与气凝胶的纳米级多孔结构相比,仍存在进一步提升的空间。
为获得良好的综合性能,当前的隔热材料研究通过组分与微观结构的协同设计,将氧化物陶瓷固有的高熔点、优异抗氧化性,与可控多孔结构带来的轻质、超低热导率特性进行深度融合。以氧化物陶瓷为基体,通过构筑多孔结构,实现极低的热导率和轻量化目标。通过引入纤维增韧或设计层级结构等方法,提高力学性能和抗热震性,力求在隔热性能与力学可靠性之间找到最优平衡点。
本文基于极端环境热防护系统对隔热材料的性能需求,系统论述了多孔氧化物陶瓷及气凝胶隔热材料的研究进展,重点阐述了各种制备方法与其性能的关联,以及各类材料的性能优势和存在的问题。
多孔氧化物陶瓷及气凝胶是指以氧化物为主要成分的多孔陶瓷及气凝胶材料。本文主要介绍以SiO2、Al2O3、ZrO2和MgO等为主要成分的多孔陶瓷及气凝胶[17,19],包括SiO2、Al2O3、ZrO2、莫来石、镁铝尖晶石及玄武岩多孔陶瓷和气凝胶,它们凭借卓越的耐高温特性,被广泛用作热防护系统的隔热材料,其基本性能参数见表1[2028]
SiO2的熔点为1670℃,密度为2.65 g/cm3,展现出良好的耐高温性能和抗氧化性能[29]。此外,相比于其他种类氧化物材料,其较低的热导率(1.4 W/(m·K))使得SiO2材料具有优异的隔热性能。由于SiO2多孔陶瓷及气凝胶在隔热性能方面表现卓越,使其在航空航天领域得到了广泛应用,主要用作保温隔热和绝热密封材料(图2[3031]),如柔性可重复使用表面隔热材料、应变隔离垫、柔性热障材料等[3031]
Al2O3具有2054℃的熔点、9 GPa的硬度,展现出优异的高温承载能力。Al2O3多孔陶瓷及气凝胶被广泛用作航空航天领域的隔热材料[32],如航空发动机燃烧室部件及飞行器大面积防隔热组件等,并且已成功通过卫星发射过程中的振动测试与太空热真空环境测试,验证了其在空间环境中的适应性[33]
莫来石是由SiO2与Al2O3在高温条件下反应生成的稳定化合物[34],其热导率为2.58 W/(m·K),具有优异的隔热性能,以及较低的线膨胀系数和优异的高温物理化学稳定性。莫来石多孔陶瓷及气凝胶被广泛用作航空航天领域的隔热材料。
ZrO2的熔点为2715℃,硬度为10~15 GPa,展现出优异的耐高温和力学性能[35]。ZrO2多孔陶瓷及气凝胶兼具优异的耐高温性能、力学性能、低热导率以及出色的抗氧化特性,已被应用于航空航天领域的隔热系统[16]
铝镁尖晶石是一种以氧化镁(MgO)和氧化铝(Al2O3)为原料合成的尖晶石质耐火材料,其熔点为2135℃,硬度为16 GPa,热导率为16 W/(m·K),兼具优异的高温稳定性、力学性能和隔热性能。此外,它还具备光学各向同性、宽波段透过性、高透过率、高电阻率、优异的抗热震能力和良好的耐腐蚀性,被用作高马赫数航空器的整流罩[22]
玄武岩是一种由SiO2、Al2O3、MgO、CaO及Fe2O3等成分组成的火山岩。玄武岩的密度为2.63 g/cm3,热导率为2.5 W/(m·K),展现出优异的隔热性能。玄武岩纤维材料本身的热导率为0.038~0.042 W/(m·K),抗拉强度为3.0~4.8 GPa,兼具优异的隔热、力学、耐高温、化学稳定性和抗氧化性能[23]。在航空航天领域中,玄武岩纤维毡已被用于制造气动设备废气系统的隔热材料[24]
SiO2具有轻质隔热的优势,Al2O3具有优异高温承载性能,ZrO2具备超高耐温特性,莫来石兼具优异的抗热震性能和力学性能,镁铝尖晶石和玄武岩纤维毡兼具良好的隔热性能和力学性能。氧化物陶瓷在受到机械应力时,容易产生裂纹并迅速扩展,发生突然断裂。当氧化物陶瓷作为隔热材料时,为追求较低的热导率,通常需要极高的孔隙率,而高孔隙率会使陶瓷的力学性能被进一步削弱。在实际使用中需要平衡氧化物多孔陶瓷的隔热性能和力学性能。因此,氧化物陶瓷隔热材料虽然在氧化环境中具有优异的隔热性能,但仍受到其力学性能和使用温度的限制。
溶胶凝胶法是一种常用的湿化学合成方法,通常以金属醇盐作为前驱体,通过水解和缩聚反应形成稳定的溶胶体系,进而聚合成三维网络结构,最终通过干燥和烧结得到多孔陶瓷或气凝胶。溶胶凝胶法通过分子级别的反应实现多组分原子级均匀混合,可精准构筑纳米尺度多孔结构。气凝胶产物形成连续三维纳米网状骨架,孔隙以纳米孔为主,闭孔占主导;多孔陶瓷产物则形成纳米−亚微米级孔隙的刚性骨架。纳米多孔结构赋予材料极高的比表面积和超低热导率,但也导致材料力学强度偏低。在高温下,纳米孔易坍塌,ZrO2、Al2O3等氧化物陶瓷材料易发生相转变,限制了其在超高温热防护环境中的应用。
静电纺丝技术是一种利用静电场将聚合物溶液或熔体拉伸成纳米纤维的方法[36],常用于制备纤维气凝胶和多孔陶瓷。在高压静电场的作用下,聚合物溶液或熔体会带电并克服表面张力,形成喷射流。在飞行过程中,溶剂挥发或熔体固化,最终在平板接收装置上沉积形成无纺布状的纳米纤维膜,将平板接收改为三维装置以构建疏松网络后得到纤维气凝胶[37]。气凝胶的纤维支撑网络构建了超高孔隙率的多级孔体系,大幅增强结构稳定性与抗变形能力。静电纺丝法制备多孔陶瓷可形成“纤维间大孔+纤维内纳米孔”的多级孔结构,通过精准调控纤维形貌与孔分布可提升结构均匀性、力学性能及高温稳定性。然而,在高温热冲击下,静电纺丝法制备的多孔氧化物陶瓷会出现结构塌陷和塑性变形,存在高温稳定性不足的问题。静电纺丝法制备多孔氧化铝陶瓷已实现产业化生产[38],而气凝胶的制备受纤维团聚和孔隙坍塌等问题的限制尚未实现产业化。
发泡法是一种通过物理或化学方法在基体材料内部引入并稳定气泡,从而制备多孔陶瓷的技术[39]。其核心在于热力学、动力学与流变学的平衡,即依赖气体的过饱和度与成核能垒在浆料中引入气泡,随后通过添加稳泡剂来抑制泡孔合并及Ostwald熟化,以实现气泡的稳定。发泡法的优势在于工艺简单,通过调整浆料的固含量及工艺参数,即可实现对多孔陶瓷结构与性能的有效控制。发泡法制备的多孔陶瓷以微米孔为主,多为薄壁球形孔骨架,开孔与闭孔共存,孔隙率最高可达95%。但相比溶胶凝胶法、静电纺丝技术的产物,发泡法制备的多孔陶瓷孔隙尺寸较大且分布不均匀,孔壁厚度不均,导致其力学性能相对较差。
凝胶注模法是一种结合传统注模成型与高分子化学交联的陶瓷胶态成型技术[40],主要用于制备多孔陶瓷。凝胶注模法制备的多孔陶瓷以微米孔为主,相较于发泡法,孔隙结构更易精准控制,骨架结构致密且连接均匀,因此材料力学性能均优于发泡法产物,但是对分散剂和工艺控制的要求十分严格。
模板法是一种基于仿生学的材料合成策略,利用具有特定微观结构的模板获得一种复制或反转模板原始结构的多孔材料,适用于多孔陶瓷及气凝胶的制备。该方法可精确调控孔径尺寸、形状、分布及连通性,能制备出具有特殊功能的多孔结构,如空心球堆积结构、三维互锁结构。该方法工艺流程较为复杂,成本较高,反应过程不易控制。
无压烧结是将成型坯体在常压环境下高温烧结致密化的工艺,其主要过程包括粉末成型与高温烧结,用于多孔陶瓷的制备,制备出的多孔陶瓷以微米孔为主,骨架烧结紧密但孔隙结构精细调控难度大,孔径分布较宽。无压烧结的工艺简单、成本低、易于制备复杂形状部件,能有效保持多孔结构,但难以实现对孔隙结构的精细调控。
多孔氧化物陶瓷及气凝胶的综合性能不仅取决于氧化物基体本身的固有特性,还与孔隙结构、增强纤维类型及纤维基体界面结合状态密切相关,其协同作用共同决定材料的综合性能[1,8]。孔隙结构是调控综合性能的核心因素,孔隙率、孔径尺寸与分布、孔型直接影响材料的隔热性能与力学性能。气凝胶的高孔隙率与纳米级孔径能显著阻断固相传导与气相对流,降低热导率,但过度提高孔隙率会削弱骨架连续性,导致力学强度下降[15];而多孔陶瓷的微米孔与闭孔结构虽隔热性能较差,但力学性能更强。增强纤维的类型与含量能够有效提升材料的力学性能与耐高温性能,莫来石纤维、石英纤维、玄武岩纤维等具有高抗拉强度与优异的耐高温性能,可通过构建连续骨架抑制材料脆性断裂,提升抗热震性能,但纤维的连续分布能够增加固相传热路径,对隔热性能产生轻微影响。纤维与基体的界面结合紧密时,能有效传递应力、分散载荷,避免热冲击下界面分离。若界面结合过弱或热膨胀系数不匹配,则易产生内应力与裂纹,削弱材料整体稳定性。以下将结合上述影响因素,讨论不同种类氧化物多孔陶瓷及气凝胶的隔热性能、耐高温性能和力学性能等。
SiO2多孔陶瓷和气凝胶因其轻质、低导热且结构易于调控的特性,具有优异的隔热性能。当前研究主要聚焦于其力学性能和耐高温性能的提升。Li等[41]通过发泡法制备了SiO2多孔陶瓷,系统地探究了烧结温度、固含量和纳米SiO2添加量对多孔陶瓷的隔热性能和力学性能的影响。如图3[41]所示,随烧结温度的升高,固含量和纳米SiO2添加量的增加,SiO2多孔陶瓷的孔隙率降低,热导率升高,抗压强度上升。该研究制备的SiO2多孔陶瓷的孔隙率为90%~97%,热导率为0.039~0.079 W/(m·K),抗压强度为0.01~0.05 MPa,能够承受1200℃以上的高温,具有优异的耐高温性能。为进一步提升SiO2多孔陶瓷的力学性能,Hu等[42]通过发泡—凝胶注模—冷冻干燥法制备出多孔SiC/SiO2陶瓷,其孔隙率为83.1%,导热率为0.116 W/(m·K),抗压强度最高为4.508 MPa。图4[42]为SiC/SiO2多孔陶瓷的连续骨架,孔隙为微米级闭孔/半闭孔。骨架间连接紧密,提供了高强度支撑,孔隙分布均匀且未破坏骨架的连续性,受力时载荷可通过骨架有效传递,因此力学性能较好。SiO2多孔陶瓷内部孔隙尺寸较大,空气在孔隙内易形成对流换热,同时陶瓷骨架是热导率较高的无机相,热量可通过骨架快速传递,相比于SiO2气凝胶和纤维毡,SiO2多孔陶瓷隔热性能较差。
Cai等[43]采用溶胶凝胶法制备了单分散SiO2气凝胶,其制备流程及实物图如图5[43]所示。单分散SiO2气凝胶的密度为0.206~0.221 g/cm3,热导率低至0.027 W/(m·K),短时耐温极限为900℃。纯SiO2气凝胶主要依靠桥氧键颈状连接(图5图6(a)[43]),这种结构在超高温环境下容易因热冲击而破坏,导致单分散气凝胶的耐高温性能较差。引入陶瓷纤维是进一步提升SiO2多孔陶瓷耐温极限和力学性能的一种有效方法。常用的无机纤维有莫来石纤维[44]和石英纤维,它们具有优异的力学和耐高温性能,而且在凝胶过程中能均匀分散于溶胶中,不易出现团聚和沉淀现象。纤维增强后的气凝胶展现出卓越的力学性能和高温稳定性。例如,Wu等[45]通过引入莫来石纤维,利用溶胶凝胶法制备出的莫来石纤维复合SiO2气凝胶的密度为0.20~0.24 g/cm3,热导率为0.069~0.085 W/(m·K),隔热温差约为600℃,能够承受高达1600℃的高温热冲击,性能显著优于纯SiO2气凝胶[44]。莫来石纤维熔点高达1850℃,将其引入气凝胶后,作为骨架(图6(b) [45])从根本上改善了SiO2气凝胶耐高温性能差的问题。但是由于纤维的连续分布,导致了莫来石纤维复合SiO2气凝胶的热导率上升,隔热性能有所下降。
溶胶凝胶结合真空浸渍法是连续纤维增强多孔复合材料最常用的制备方法。其中,溶胶凝胶法可以通过浸渍的方式将前驱体溶胶掺入纤维骨架中,真空浸渍技术能确保基体充分且均匀地分布在纤维骨架中。以无机纤维作为骨架,气凝胶作为填充,这种“骨架—填充”的复合设计,既借助隔热毡的三维交织结构保障了材料的力学强度,又通过气凝胶的纳米多孔结构阻断了热传导路径,使复合材料兼具优异的力学性能和隔热性能。与纤维掺杂SiO2气凝胶相比,溶胶凝胶结合真空浸渍法制备的气凝胶基陶瓷复合材料(CASS)的耐温极限、隔热性能和抗压强度均大幅提升。Xu等[46]以石英纤维毡为骨架,通过浸渍工艺在石英纤维毡骨架上添加SiO2陶瓷涂层(图6(c)[46])和SiO2气凝胶保温层(图6(d)[46]),成功制备出石英纤维针刺毡增强的SiO2陶瓷气凝胶复合材料。复合材料的密度为0.3~0.6 g/cm3,热导率仅为0.022~0.042 W/(m·K),抗压强度高达14 MPa,但是其耐温极限仅为1100℃。通过溶胶凝胶法与真空浸渍法相结合的方法,得到的SiO2气凝胶具有极为优异的力学性能,为氧化物多孔陶瓷力学性能的提升提供了有益借鉴。
Pan等[47]通过同轴静电纺丝技术制备了核壳BN/SiO2纳米纤维膜,其热导率仅为0.046 W/(m·K),抗拉强度高达7.2 MPa。此外,静电纺丝法与发泡法制备的SiO2多孔陶瓷在隔热效率与力学性能间需要进行平衡,高孔隙有利于SiO2多孔陶瓷的隔热性能,但是会削弱其力学性能。纳米级核壳BN/SiO2纤维交织成“疏松网状”结构,纤维间是大量微米级空隙,纤维细、交织点少,受力时纤维易滑移、断裂,结构难以有效传递应力,导致纤维膜的力学性能较差。在大量孔隙对热传递的阻滞作用下,热导率大幅降低,使得纤维膜具有优异的隔热性能。因此,静电纺丝法制备的隔热材料通常具有优异的隔热性,但力学性能较差。
SiO2多孔陶瓷与气凝胶的固相传热及气相对流均较弱,展现出极低的热导率。其中,由于SiO2多孔陶瓷密度高于气凝胶,使得固相传热较多,热导率范围为0.039~0.210 W/(m·K)[4042],而气凝胶的热导率为0.022~0.085 W/(m·K)[43,4547]。受低密度与高孔隙率影响,二者抗压强度整体偏低,仅为0.01~14.00 MPa[4147]。在耐温性能方面,SiO2气凝胶短时耐温约900℃[43],而SiO2多孔陶瓷因骨架更致密,耐温性能优于气凝胶[45]。纯SiO2多孔陶瓷与气凝胶受熔点限制,耐高温性能并不突出,但与SiC、莫来石等材料复合后,其短时耐温性能可提升至1600℃[45]左右。
Al2O3多孔陶瓷及气凝胶具有耐高温性能好和力学性能好的特点,由于Al2O3材料本身的热导率高,导致了其隔热性能相对较差。当前研究主要通过发泡法、造孔剂法等调控孔隙结构,提升Al2O3多孔陶瓷隔热性能,或者通过引入第二相进行结构设计,提高Al2O3气凝胶的隔热性能。
He等[48]通过发泡法制备了Al2O3多孔陶瓷,通过引入硅溶胶提高泡沫稳定性,多孔陶瓷的孔隙率为63.75%~85.04%,抗压强度为1.30~4.21 MPa,能够承受1450℃以上的高温。为了进一步提升Al2O3多孔陶瓷的抗压强度,Wang等[49]通过发泡法制备了Al2O3多孔陶瓷,研究了分散剂和疏水改性剂对多孔Al2O3陶瓷微观结构、孔隙率及抗压强度的影响。固定分散剂含量,随着疏水改性剂含量增加,陶瓷孔径逐渐减小,孔径分布愈发均匀(图7(a)~(c)[49]),孔隙率逐渐上升,抗压强度逐渐下降;固定疏水改性剂含量,随分散剂含量增加,大尺寸孔数量逐渐增多,孔径分布变得不均匀(图7(c)~(f)[49]),孔隙率逐渐下降,抗压强度逐渐上升。制备的孔隙率为82%、抗压强度为39 MPa的多孔Al2O3陶瓷能够承受1350℃以上的高温。
Zhang等[50]通过溶胶凝胶法结合冷冻干燥制备了高孔隙率和层状结构的Al2O3/SiC复合气凝胶(图8(a)[50]),热导率仅为0.03 W/(m·K),隔热温差为800℃左右,抗压强度为1.56 MPa。在3种热流密度(100、200和400 kW/m2)的氧乙炔火焰测试中,复合气凝胶背面温度均控制在200℃以内,能够满足航天器的工作要求。该Al2O3/SiC复合气凝胶具有优异的隔热性能,但气凝胶层间连接较弱(图8(c)),导致其力学性能较差。为了进一步提升Al2O3气凝胶的耐高温性能和力学性能,Zhang等[51]通过溶胶凝胶法制备了不同酚醛树脂含量的Al2O3−SiO2气凝胶(PAS)(图8(b)[51])。PAS的密度仅为0.33~0.36 g/cm3,热导率为0.039 W/(m·K),隔热温差最高可达1197.4℃,表现出极为优异的隔热性能。此外,PAS 还能够承受1300℃的高温。由图8(d)[51]可以看出,PAS气凝胶呈现出由小颗粒和大片状结构组成的簇状结构,其中小颗粒紧密结合,大量片状结构穿插在小颗粒聚集体中,形成大型互连簇状结构,这些团簇相互连接,构成坚固的结构网络。这种杂化互穿网络显著提升了气凝胶的网络强度,使得PAS气凝胶具有优异的力学性能,抗压强度和应变分别为8.05 MPa和45%。
Al2O3多孔陶瓷的孔隙率在41.71%~85.04%[4849]之间,由于陶瓷本征热导率较高,且孔隙在微米级,固相传导路径难以有效阻断,热导率较高;而气凝胶通过90%以上的高孔隙率和纳米孔结构,大幅降低固相传导占比,同时抑制气相对流,使得热导率显著降低,仅为0.030~0.039 W/(m·K)[5051]。Al2O3多孔陶瓷的骨架颗粒连接致密,气凝胶为层状或簇状纳米结构,颗粒间连接薄弱,使其力学强度远低于多孔陶瓷(1.3~39 MPa[4849]),Al2O3气凝胶仅为1.58~8.05 MPa[5051]。Al2O3多孔陶瓷骨架烧结充分,抗氧化性与结构稳定性强,其短时耐温可达1350℃[49],而Al2O3气凝胶纳米颗粒在高温下易发生烧结团聚,导致孔隙坍塌,耐温极限仅为1300℃[51]
莫来石多孔陶瓷和气凝胶具有热导率低、力学性能好和耐高温性能好的特点。当前主要通过孔隙结构的调控以平衡力学性能及隔热性能,或通过引入纤维提升莫来石气凝胶的力学性能及耐高温性能,以期提高极端热环境下莫来石多孔陶瓷及气凝胶的综合性能。
姚彩玉[52]在制备过程中引入了造孔剂,随着玉米淀粉造孔剂添加量的增多,孔隙率从31.94%提高到42.19%,热导率从1.582 W/(m·K)降至1.078 W/(m·K),抗弯强度从69.70 MPa降至42.52 MPa。该研究还得出,当添加2%(质量分数)的B2O3发泡剂时,莫来石多孔陶瓷孔隙率为42.26%,抗弯强度为51.05 MPa,热导率为1.006 W/(m·K)。在孔隙率相近的情况下,使用玉米淀粉作为造孔剂的莫来石多孔陶瓷,内部呈疏松多孔状,形成孔洞相连的三维晶须结构(图9);而B2O3作为造孔剂使陶瓷内部颗粒连接更紧密,力学性能更好。Ren等[53]通过发泡法制备了Al2O3/莫来石多孔陶瓷,在1200℃烧结后,孔隙率达95.9%时,体积密度为0.18 g/cm3,抗压强度为3.9 MPa,兼具优异的隔热性能和力学性能。图9(d)~(f) [5253]表明烧结温度升高会引起收缩,使气泡尺寸略有减小,尺寸大于40 μm的气泡占比逐渐降低,而尺寸小于20 μm的气泡占比呈上升趋势。Guo等[54]通过静电纺丝法制备了密度为0.02195 g/cm3的莫来石纤维膜,其热导率为0.035 W/(m·K),能够承受1300℃的高温,展现出优异的隔热性能。在莫来石纤维的基础上,Liu等[55]通过凝胶注模法制备了莫来石纤维多孔陶瓷(图10(a)),其密度为1.109~1.385 g/cm3,热导率为0.194~0.436 W/(m·K)。如图10(b)[55]所示,纤维与基体材料之间形成了紧密的连接,使莫来石纤维多孔陶瓷能够有效抵抗应力。随着纤维含量(质量分数)从5%增加到25%,孔隙率逐渐从64.69%降至55.95%,烧结后陶瓷的抗压强度从1.25 MPa提升至6.42 MPa。
You等[56]首先通过溶胶凝胶法制备了Al2O3纳米棒/SiO2前驱体气凝胶,随后通过高温烧结转化为莫来石气凝胶。该莫来石气凝胶的密度为0.176~0.244 g/cm3,热导率为0.0375~0.0551 W/(m·K),抗压强度为0.369 MPa。Al2O3纳米棒/SiO2气凝胶的亚微米骨架结构(图11(a))有助于在高温下保持孔隙结构的稳定性。热处理过程中非晶球状颗粒的形成和骨架的粗化也起到了加强内部结构和增强骨架连接的作用(图11(b)),使得莫来石气凝胶能够承受1300℃的高温热冲击,兼具优异的隔热性能和耐高温性能。为了进一步提高莫来石多孔陶瓷的力学性能和耐温极限,Peng等[57]通过溶胶凝胶法制得硅铝溶胶,再将莫来石纤维毡浸渍在硅铝溶胶中,经过超临界干燥和烧结得到莫来石纤维增强Al2O3/SiO2气凝胶复合材料(MFAS)。MFAS的密度为0.37~0.39 g/cm3,热导率为0.036~0.044 W/(m·K), 能够承受1500℃的高温热冲击,隔热温差高达1120℃。将气凝胶颗粒引入纤维毡后,气凝胶颗粒主要聚集在纤维连接处(图11(c)、(d)[57]),增强了内部结构,抗压强度达1.4 MPa,有效提升了材料的力学性能。为了进一步提高耐温极限,Tian等[58]通过溶胶凝胶法得到有机硅溶胶,在真空辅助下将其浸渍到莫来石刚性纤维陶瓷瓦(RFC)中,最后经过常压干燥得到有机硅/莫来石刚性纤维陶瓷瓦复合材料。通过浸渍有机硅溶胶,复合材料的热导率和抗压强度分别为0.091W/(m·K)和2.6 MPa,比RFC降低了0.02 W/(m·K)和1.7 MPa。复合材料的隔热温差为800℃,并且能够承受2000℃高温热冲击。Chang等[59]也以溶胶凝胶结合浸渍工艺制备了莫来石纤维增强Al2O3/SiO2气凝胶复合材料。与Peng等[57]的研究不同的是,该研究采用了通过5次浸渍工艺制备了有机硅/莫来石刚性纤维陶瓷瓦复合材料,其密度为0.32~0.86 g/cm3、孔隙率为73.30%~90.03%、热导率为0.12~0.22 W/(m·K),能够承受1400℃的高温热冲击。冷冻干燥后,纤维全部紧密结合在基体上(图11(d)[59]),使得复合材料的抗压强度达4.25 MPa。浸渍工艺使复合材料的抗压强度有所提升,但使纤维表面附着了过多的气凝胶颗粒,导致热导率有所提升,隔热性能下降;此外,在高温下热应力倾向于集中在纤维与基体接触区,容易导致接触区纤维脆化(图11(f) [59])。Cheng等[60]首先以静电纺丝法制得莫来石纤维气凝胶,再将其浸渍在硅铝溶胶中,经干燥烧结后得到纳米纤维−纳米片二元协同结构的莫来石气凝胶,能够承受80%的应变,最大的抗压强度为0.17 MPa,热导率为0.028~0.038 W/(m·K),能够承受1300℃的高温热冲击。
莫来石多孔陶瓷存在三维晶须结构或颗粒堆积骨架,孔隙率为31.94%~42.19%[52],微米级孔隙导致热导率变化范围较大,为0.194~1.582 W/(m·K)[5255]。莫来石气凝胶为纳米纤维/纳米片二元结构或纤维气凝胶复合网络结构,孔隙尺寸均匀且以纳米孔为主,传热路径更曲折,隔热性能更稳定,热导率为0.028~0.220 W/(m·K)[5659]。较致密的陶瓷骨架使莫来石多孔陶瓷的抗压强度较高,最高可达69.70 MPa[52],而莫来石气凝胶的抗压强度仅为0.17~2.60 MPa[5659]。依托于莫来石的高熔点,莫来石多孔陶瓷及气凝胶均具有优异的耐高温性能,其中气凝胶因纤维增强抑制了纳米孔坍塌,短时耐温极限略高于多孔陶瓷,高达1500℃[57]
ZrO2多孔陶瓷和气凝胶具有隔热性能好的特点,但是ZrO2高温下的相变使得ZrO2多孔陶瓷和气凝胶的高温稳定性较差。通过引入第二相(如Y2O3、SiO2)、结构设计,能够有效抑制其相变,提升其在高温下的力学性能,解决ZrO2多孔陶瓷和气凝胶高温稳定性差的问题。
Lang等[61]通过球磨发泡法制备了孔隙率为73%~89%、抗压强度为0.4~7.6 MPa的多孔氧化钇稳定氧化锆(YSZ)陶瓷,相比搅拌发泡工艺,球磨发泡法效率更高,制备的多孔陶瓷孔隙分布更均匀、强度更高。Meng等[62]通过发泡–凝胶注模工艺制备了多孔YSZ陶瓷。如图12[62]所示,随着浆料固相含量增加,陶瓷孔隙率降低,抗压强度和热导率呈上升趋势。YSZ多孔陶瓷抗压强度为0.69~3.66 MPa,室温热导率为0.137~0.254 W/(m·K),在高温下表现出良好的隔热性能。Xu等[63]将莫来石纤维引入ZrO2多孔陶瓷,采用真空辅助过滤制备了ZrO2/莫来石复合纤维纸。厚度为5 mm、莫来石纤维质量分数为7%的复合纸在加热180 s后,热表面温度约为1370℃,冷面平均温度保持在269.7℃左右。Li等[64]通过溶胶凝胶法制备了ZrO2−SiO2溶胶,然后将前驱体溶胶渗入莫来石纤维中,最后经超临界干燥获得莫来石纤维掺杂ZrO2/SiO2气凝胶(QFZSA)复合材料(图13(a)[64])的密度仅为0.22 g/cm3,抗压强度高达5.5 MPa,热导率低至0.036 W/(m·K),能够承受1300℃的高温热冲击。如图13(b)、(c)[64]所示,在1000℃热处理后复合材料内部显示出10~100 μm的大孔径。由于气凝胶矩阵与石英纤维之间的收缩不匹配,产生了内在应力和裂纹,削弱了复合材料的耐高温性能。
Guo等[65]通过静电纺丝法制备了ZrO2/SiO2复合气凝胶,其密度仅为0.15~0.55 g/cm3,热导率为0.104 W/(m·K),抗拉强度仅为1.6 kPa,能够承受1300℃的高温热冲击。该ZrO2/SiO2复合气凝胶具有优异的隔热性能,超轻质多孔结构能够有效抑制热传导,截留的非晶碳能够提升红外吸收率,并且次晶结构能保护碳在1100℃不被氧化,削弱热辐射,接近于零的泊松比与热膨胀系数,能够规避热应力导致的结构坍塌。为进一步提高ZrO2多孔陶瓷的隔热性能、耐高温性能和力学性能,Wen等[66]通过溶胶凝胶法制得前驱体溶液,再通过离心纺丝技术成功制备出由中空连续YSZ纤维组装而成的层状毡。中空YSZ毡的密度仅为0.38 g/cm3,拉伸强度为439.56 kPa,热导率为0.103 W/(m·K),能够承受1600℃的高温热冲击。空心结构能够有效减少空气含量并增加热辐射面积,从而增强了这些纤维的隔热性能和耐高温性能。Wang等[67]通过溶剂热法合成了用于复合材料基体的SiBCN−ZrO2前驱体溶胶,然后将溶胶浸渍到碳纤维预制体,经烧结后得到了碳纤维/SiBCN−ZrO2复合材料,结合了气凝胶的固有隔热性和碳纤维的结构完整性。复合材料的密度仅为0.25~0.26 g/cm3,抗压强度高达3.19 MPa,热导率仅为0.075 W/(m·K),能够承受1000℃以上的高温热冲击。
ZrO2气凝胶内部为纳米多孔网络,热导率为0.075~0.104 W/(m·K)[6567];多孔陶瓷以微米级气泡或纤维堆积孔隙为主,骨架相对致密,传热路径比气凝胶短,热导率为0.137~0.254 W/(m·K)[62]。ZrO2多孔陶瓷骨架为刚性颗粒堆积或中空纤维组装,抗相变收缩能力强,力学稳定性优于ZrO2气凝胶;ZrO2气凝胶骨架由纳米颗粒或短纤维交联形成,缺乏连续承载结构,力学强度低,仅为0.17~5.50 MPa[6367]。ZrO2在高温下易发生相变,伴随体积收缩,多孔陶瓷通过中空纤维结构或稳定相掺杂抵抗收缩,短时耐温性能高达1600℃[66];气凝胶需进行相变抑制,否则纳米孔易坍塌,影响耐温性能。
镁铝尖晶石多孔陶瓷具有力学性能和耐高温性能好的特点,但是其隔热性能相对较差。通过模板法和静电纺丝技术等优化其孔隙结构,可有效提升其隔热性能,解决镁铝尖晶石多孔陶瓷隔热性能较差问题。
Chen等[68]利用主要成分为MgAl2O4的镁铝尖晶石空心球作为造孔剂,再加入Al2O3粉末作为基体,采用模板法制备的镁铝尖晶石多孔陶瓷的孔隙率为67.2%~71.9%,热导率为0.18~0.38 W/(m·K),抗压强度为6.1~17.1 MPa,可以承受1700℃以上的高温。如图14[68]所示,在烧结后,镁铝尖晶石空心球的颈部生长而得以增强基体,增加了空心球体与基体之间的连接面,内部的互锁结构阻碍了裂纹传播,从而提升了镁铝尖晶石多孔陶瓷的力学性能。相比于凝胶注模法,模板法制备的镁铝尖晶石多孔陶瓷孔隙更大更均匀,其隔热性能与力学性能均得到显著提升。Wang等[69]通过静电纺丝法制备了镁铝尖晶石纤维,其密度为1.6~12.2 mg/cm3,热导率仅为0.0263~0.0316 W/(m·K),抗压强度为30 kPa,能够承受1600℃以上的高温。
凝胶注模法制备的镁铝尖晶石多孔陶瓷具有优异的耐高温性能和力学性能,但隔热性能较差;静电纺丝法制备的镁铝尖晶石多孔陶瓷具有优异的耐高温性能和隔热性能,但其力学性能较差;模板法制备的镁铝尖晶石多孔陶瓷兼具优异的隔热性能、耐高温性能和力学性能。
玄武岩多孔陶瓷和气凝胶具有轻质和热导率低的特点,当前主要围绕如何进一步发挥其轻质特性和提升其隔热效率展开研究。Song等[70]通过发泡法制备了玄武岩纤维/聚乙烯醇纤维复合泡沫陶瓷(图15(a)),其密度仅为0.0089 g/cm3,热导率仅为0.031 W/(m·K),具有优异的隔热性能。其低密度和半开放式三维结构(图15(b)[70])使材料能够捕获大量空气,有效抑制了热传递,提高了隔热性能。为了进一步提高玄武岩多孔陶瓷的隔热性能,郑王波[71]通过溶胶凝胶法结合冷冻干燥制备了玄武岩/SiO2气凝胶(图15(c)),进一步提高了材料的隔热性能。该复合气凝胶的孔隙率为90%,抗压强度为0.62 MPa,热导率为0.0268 W/(m·K),具有优异的耐高温性能。气凝胶的加入一方面有效阻断纤维之间的传热,另一方面纤维之间毫米级、微米级的孔洞被气凝胶微纳米级的孔洞所代替(图15(d) [71]),有效限制了热量在空气中的传导,使得玄武岩/SiO2气凝胶具有优异的隔热性能。
玄武岩多孔陶瓷和气凝胶利用玄武岩纤维的优异力学性能和高温稳定性,通过与其他材料复合实现对微观结构的控制,提高材料孔隙率,可降低材料热导率。玄武岩/SiO2气凝胶的热导率仅为0.0268 W/(m·K)[71]。多孔陶瓷依托玄武岩纤维本身的高抗拉强度,纤维交织形成的网络具有一定承载能力;气凝胶中纤维为骨架,气凝胶颗粒填充孔隙,虽隔热性增强,但纤维间连接被气凝胶颗粒弱化,整体力学强度低于纯纤维多孔陶瓷。玄武岩多孔陶瓷和气凝胶均依托玄武岩纤维的耐高温特性,使用温度范围相近。
不同方法制备氧化物多孔陶瓷及气凝胶的孔隙率、密度和热导率数据如表2所示。SiO2、Al2O3、莫来石、ZrO2、镁铝尖晶石及玄武岩等多孔陶瓷和气凝胶均展现出低密度、高孔隙率、低热导率的显著特性。其中,SiO2和玄武岩制备的多孔陶瓷及气凝胶在隔热性能方面尤为突出,明显优于其他种类的氧化物材料。在众多制备方法中,采用发泡法制备的多孔氧化物陶瓷孔隙率高、热导率低,其隔热性能显著优于其他方法制备的氧化物多孔陶瓷。溶胶凝胶法制备的氧化物气凝胶凭借其高孔隙率和低热导率,在隔热性能上优于其他方法制备的氧化物气凝胶。耐高温性能方面,在引入纳米SiO2后,SiO2多孔陶瓷能够承受1200~1250℃的高温[4041];在经过石英骨架增强后,SiO2气凝胶能够承受900℃左右的高温[43];在Al2O3多孔陶瓷中引入硅溶胶后,其能够承受1000~1450℃的高温[4849];在Al2O3气凝胶中引入SiO2溶胶后,能够承受1000~1300℃的高温[5051];莫来石多孔陶瓷能够承受1300℃左右的高温[53];莫来石气凝胶能够承受1300~1500℃的高温[57,60];ZrO2气凝胶在与SiO2气凝胶复合后最高可承受1300℃的高温[64];中空Y2O3稳定ZrO2气凝胶纤维毡能够承受1600℃的高温[66];镁铝尖晶石多孔陶瓷能够承受1700℃的高温[69]。力学性能方面,上述氧化物多孔陶瓷的抗压强度在几到十几兆帕不等,其中镁铝尖晶石多孔陶瓷的抗压强度高达17.1 MPa[68]。氧化物多孔陶瓷的抗压强度虽然较低,但经过纤维掺杂或结构设计后,其力学性能可以得到显著改善。
多孔氧化物陶瓷的制备方法、微观结构与性能之间存在紧密协同的关系,成为超高温热防护隔热领域的研究焦点。溶胶凝胶法构建纳米多孔骨架以实现低热导率,但力学强度不足;静电纺丝技术借纤维网络增强韧性,却面临高温稳定性的难题;发泡法、模板法、无压烧结和凝胶注模法则在大孔构筑、结构仿生、工艺流程、孔隙调整上各具优势,通过纤维掺杂、真空浸渍、结构设计等多尺度手段,可以实现多孔氧化物陶瓷及气凝胶的隔热与承载功能的协同提高。
SiO2多孔陶瓷与气凝胶隔热性能卓越,经改性后耐高温性能与力学性能均得到显著提升;Al2O3多孔陶瓷及气凝胶的隔热性能与力学性能较为平衡,抗压缩性能优异;ZrO2气凝胶经过Y2O3稳定后具有优异的高温稳定性;莫来石多孔陶瓷与气凝胶的综合性能均衡;镁铝尖晶石多孔陶瓷高温稳定性与力学性能优异;玄武岩多孔陶瓷具低密度、低热导及低成本特点。
当前各体系多孔氧化物陶瓷及气凝胶仍存在诸多问题。例如,当SiO2与热膨胀系数差异显著的材料进行复合时,在高温下,由于热膨胀的差异会在界面处产生巨大的热应力,易产生界面分离现象,从而导致隔热性能降低。Al2O3多孔陶瓷的断裂韧性较差,限制了其进一步的应用;ZrO2多孔陶瓷及气凝胶的高温相变问题限制了其应用;莫来石多孔陶瓷与气凝胶的烧结温度较高,为1200~1450℃;镁铝尖晶石的成本较高及玄武岩多孔陶瓷的生产效率有待提高。未来发展需进一步优化制备工艺与结构设计,推动多孔陶瓷及气凝胶从单一隔热向“隔热–承载”方向发展,通过引入中间层、调控内部多孔结构、复合增强等手段解决,进一步提高材料的隔热性能和力学性能。
  • 国家自然科学基金项目(51802176)
  • 山东省自然科学基金项目(ZR2023ME035)
  • 山东省博士后创新项目(SDCX−ZG−202400297)
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2026年第44卷第13期
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doi: 10.3981/j.issn.1000-7857.2025.12.00111
  • 接收时间:2025-12-22
  • 首发时间:2026-07-27
  • 出版时间:2026-07-13
补充材料
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出版历史
  • 收稿日期:2025-12-22
  • 修回日期:2026-02-09
基金
国家自然科学基金项目(51802176)
山东省自然科学基金项目(ZR2023ME035)
山东省博士后创新项目(SDCX−ZG−202400297)
作者信息
    1山东理工大学材料科学与工程学院,淄博 255000
    2中材江西电瓷电气有限公司,萍乡 337000
    3高温功能陶瓷材料学科与技术中心,淄博 255000
    4山东工业陶瓷研究设计院有限公司,淄博 255000
    5哈尔滨工业大学复合材料与结构研究所,哈尔滨 150001
    6航天特种材料及工艺技术研究所,北京 100074
    7北京理工大学先进结构技术研究院,北京 100081

通讯作者:

张丽娟(通信作者),研究员,研究方向为超高温隔热材料,电子信箱:;
温广武(共同通信作者),教授,研究方向为特种陶瓷与碳材料,电子信箱:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
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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