Preparation and Properties Regulation of Tubular Halloysite Doped Cordierite Ceramics

doi:10.16552/j.cnki.issn1001-1625.2025.0816

Abstract

Abstract:

Cordierite ceramics are ideal materials for lithography square mirrors and laser reflectors due to their low thermal expansion coefficient， excellent chemical stability and high mechanical properties. In order to meet the more stringent application requirements in related fields， it is necessary to modulate the key parameters such as thermal expansion coefficient and elastic modulus by means of doping modification. Tubular halloysite has excellent thermal stability and mechanical properties due to its unique tubular structure， showing its good potential as a dopant. In this paper， cordierite ceramics doped with tubular halloysite were prepared by solid phase sintering with tubular halloysite powder as dopant. The effect of tubular halloysite doping on the composition， microstructure， mechanical properties and thermal expansion properties of cordierite ceramics was studied. The results show that doping tubular halloysite can promote the densification of cordierite ceramics to a certain extent. With the increase of tubular halloysite doping mass fraction， the density of cordierite ceramics increases and the open porosity decreases. The 10.0% tubular halloysite-doped cordierite ceramics have the highest elastic modulus， and the 20.0% tubular halloysite-doped cordierite ceramics have the highest hardness. Compared with pure cordierite ceramics， the average thermal expansion coefficient of cordierite ceramics doped with 2.5% tubular halloysite decreases from 1.40×10^-6 K^-1 to 0.65×10^-6 K^-1 at room temperature （25 ℃） to 160 ℃.

Key words: cordierite, tubular halloysite, doping modification, microstructure, thermal expansion, mechanical property

CLC Number:

TQ174

PAN Honghai, ZHANG Wen, WANG Honglei, ZHOU Xingui. Preparation and Properties Regulation of Tubular Halloysite Doped Cordierite Ceramics[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(2): 603-612.

Figures/Tables 8

Fig.1 Schematic diagram of process flow

Fig.2 Density and open porosity of cordierite ceramics doped with different proportions of tubular halloysite

Fig.3 XRD patterns and local amplification of raw materials and cordierite ceramics doped with different proportions of tubular halloysite

Fig.4 SEM images of cordierite ceramics doped with different proportions of tubular halloysite

Fig.5 Elastic modulus and hardness of cordierite ceramics doped with different proportions of tubular halloysite

Fig.6 Thermal expansion coefficient of cordierite ceramics doped with different proportions of tubular halloysite

Fig.7 Crystal structure diagram of α-cordierite

Fig.8 Octahedral flattening mechanism of cordierite［40］

References 43

[1]	AL-HARBI O A， ÖZGÜR C， KHAN M M. Fabrication and characterization of single phase cordierite honeycomb monolith with porous wall from natural raw materials as catalyst support［J］. Ceramics International， 2015， 41（3）： 3526-3532. DOI URL
[2]	焦永峰，洑义达，陆婵娟. 堇青石基红外陶瓷的研究现状［J］. 硅酸盐通报， 2008， 27（4）： 782-785+807.
	JIAO Y F， FU Y D， LU C J. Research actuality of cordierite base infrared ceramics［J］. Bulletin of the Chinese Ceramic Society， 2008， 27（4）： 782-785+807 （in Chinese）.
[3]	张竞文，毕娟. 激光辐照下反射镜热变形特性分析［J］. 长春理工大学学报（自然科学版）， 2021， 16（2）： 13-17.
	ZHANG J W， BI J. Analysis of the thermal distortion characteristics of the reflectors irradiated by laser［J］. Journal of Changchun University of Science and Technology （Natural Science Edition）， 2021， 16（2）： 13-17 （in Chinese）.
[4]	吴泽华，李刚，邓淞文，等. 近红外波段99.999%超高反射率激光反射镜［J/OL］. 中国激光， 2025： 1-3 （2025-05-20）［2025-08-12］. https://link.cnki.net/urlid/31.1339.TN.20250519.1437.014.
	WU Z H， LI G， DENG S W， et al. Near-infrared band 99.999 % ultra-high reflectivity laser mirror［J］. Chinese Journal of Lasers， 2025： 1-3 （2025-05-20）［2025-08-12］. https://link.cnki.net/urlid/31.1339.TN.20250519.1437.014 （in Chinese）.
[5]	王艳萍，田远. 低膨胀材料及其复合陶瓷材料的应用进展及发展前景［J］. 中国建材科技， 2021， 30（5）： 42-44.
	WANG Y P， TIAN Y. Application progress and development prospect of low expansion materials and their composite ceramics［J］. China Building Materials Science & Technology， 2021， 30（5）： 42-44 （in Chinese）.
[6]	邓建明，凌宁. 高功率激光反射镜的几个关键技术［J］. 强激光与粒子束， 1998， 10（4）： 518-522.
	DENG J M， LING N. Several key manufacture technologies of mirror in high power laser system［J］. High Power Laser and Particle Beams， 1998， 10（4）： 518-522 （in Chinese）.
[7]	YU C Y， LIN K， JIANG S H， et al. Plastic and low-cost axial zero thermal expansion alloy by a natural dual-phase composite［J］. Nature Communications， 2021， 12： 4701. DOI PMID
[8]	LIU J N， MAYNARD-CASELY H E， BRAND H E A， et al. Sc_1.5Al_0.5W₃O₁₂ exhibits zero thermal expansion between 4 and 1 400 K［J］. Chemistry of Materials， 2021， 33（10）： 3823-3831. DOI URL
[9]	KAMIYA T， MIZUTANI T. Comparison of material properties between ultra low thermal expansion ceramics and conventional low thermal expansion glass［C］// Material Technologies and Applications to Optics， Structures， Components， and Sub-Systems III. August 6-10， 2017. San Diego， United States： SPIE Optical Engineering+Applications， 2017： 7.
[10]	王峰，贺智勇，王晓波，等. 近零膨胀堇青石陶瓷的制备［J］. 陶瓷学报， 2024， 45（3）： 463-467.
	WANG F， HE Z Y， WANG X B， et al. Cordierite ceramics with near-zero expansion［J］. Journal of Ceramics， 2024， 45（3）： 463-467 （in Chinese）.
[11]	张丛，尹飞，郭建斌，等. 堇青石材料在光刻机领域的应用进展［J］. 材料导报， 2022， 36（增刊2）： 71-73.
	ZHANG C， YIN F， GUO J B， et al. Application advances of cordierite materials in lithography［J］. Materials Reports， 2022， 36（supplement 2）： 71-73 （in Chinese）.
[12]	黄硕，熊芬，刘丹丹，等. 低热膨胀系数堇青石蜂窝陶瓷载体制备及性能研究［J］. 陶瓷学报， 2024， 45（6）： 1185-1192.
	HUANG S， XIONG F， LIU D D， et al. Preparation and properties of low thermal expansion coefficient cordierite honeycomb ceramic carriers［J］. Journal of Ceramics， 2024， 45（6）： 1185-1192 （in Chinese）.
[13]	王子健，左桂鸿，郑友进，等. 堇青石合成与改性研究进展［J］. 中国陶瓷， 2023， 59（11）： 11-19.
	WANG Z J， ZUO G H， ZHENG Y J， et al. Research on synthesis and modification of cordierite［J］. China Ceramics， 2023， 59（11）： 11-19 （in Chinese）.
[14]	VEPA S S V S S， UMARJI A M. Effect of substitution of Ca on thermal expansion of cordierite （Mg₂Al₄Si₅O₁₈）［J］. Journal of the American Ceramic Society， 1993， 76（7）： 1873-1876. DOI URL
[15]	UNNO H， TOH S， SUGAWARA J， et al. Microstructures of La-doped low thermal expansion cordierite ceramics［C］// Mechanical Properties and Performance of Engineering Ceramics and Composites VII， The American Ceramic Society， New Jersey， 2012： 153-162.
[16]	AGRAWAL D K， STUBICAN V S， MEHROTRA Y. Germanium-modified cordierite ceramics with low thermal expansion［J］. Journal of the American Ceramic Society， 1986， 69（12）： 847-851. DOI URL
[17]	KAMIYA T， MIZUTANI T. Development of ultra-lightweight and thermally-stable cordierite ceramic mirrors［C］// Advances in Optical and Mechanical Technologies for Telescopes and Instrumentation III. June 10-15， 2018. Austin， United States： SPIE Optical Engineering+Applications， 2018： 23.
[18]	APPIAH M， YANG Y X， ULLAH B， et al. Phase structural characteristics and microwave dielectric properties of Ge-doped cordierite-based ceramics［J］. Materials Research Bulletin， 2024， 179： 112939. DOI URL
[19]	ZHANG W Q， LI S P， BAO H， et al. Study on the reaction process and mechanism of the system of cordierite with zirconia［J］. Ceramics International， 2019， 45（4）： 5066-5071. DOI URL
[20]	KUMAR M S， PERUMAL A E， VIJAYARAM T R， et al. Processing and characterization of pure cordierite and zirconia-doped cordierite ceramic composite by precipitation technique［J］. Bulletin of Materials Science， 2015， 38（3）： 679-688. DOI URL
[21]	GOEL A， SHAABAN E R， RIBEIRO M J， et al. Influence of NiO on the crystallization kinetics of near stoichiometric cordierite glasses nucleated with TiO₂ ［J］. Journal of Physics： Condensed Matter， 2007， 19（38）： 386231.
[22]	王不赖，王峰，白志民，等. 低热膨胀系数的堇青石陶瓷研究进展［J］. 耐火材料， 2024， 58（6）： 536-542. DOI
	WANG B L， WANG F， BAI Z M， et al. Research process on cordierite ceramics with low thermal expansion coefficient［J］. Refractories， 2024， 58（6）： 536-542 （in Chinese）. DOI
[23]	WU S， SONG K X， LIU P， et al. Effect of TiO₂ doping on the structure and microwave dielectric properties of cordierite ceramics［J］. Journal of the American Ceramic Society， 2015， 98（6）： 1842-1847. DOI URL
[24]	LI Z F， JIANG H B， CUI J P， et al. Dense and high flexural strength cordierite ceramics doped with Li₂O［J］. Ceramics International， 2024， 50（13）： 24119-24125. DOI URL
[25]	湛玲丽，贾涵，张晓峰，等. 不同Al₂O₃/SiO₂比的MgO-Al₂O₃-SiO₂微晶玻璃制备及性能研究［J］. 硅酸盐通报， 2023， 42（12）： 4490-4500.
	ZHAN L L， JIA H， ZHANG X F， et al. Preparation and properties of MgO-Al₂O₃-SiO₂ glass-ceramics with different Al₂O₃/SiO₂ ratios［J］. Bulletin of the Chinese Ceramic Society， 2023， 42（12）： 4490-4500 （in Chinese）.
[26]	于永生，郝小非，彭琪，等. 珍珠岩制备单一α-堇青石微晶玻璃及其性能［J］. 硅酸盐通报， 2017， 36（3）： 770-777.
	YU Y S， HAO X F， PENG Q， et al. Preparation and characterization of single α-cordierite glass-ceramics from perlite［J］. Bulletin of the Chinese Ceramic Society， 2017， 36（3）： 770-777 （in Chinese）.
[27]	赖岳飞，王辉军，曾强，等. 工业废渣制备堇青石基陶瓷材料研究现状［J］. 硅酸盐通报， 2024， 43（12）： 4521-4531.
	LAI Y F， WANG H J， ZENG Q， et al. Progress on cordierite based ceramic materials prepared from industrial wastes［J］. Bulletin of the Chinese Ceramic Society， 2024， 43（12）： 4521-4531 （in Chinese）.
[28]	徐培杰，杜贝贝. 管状埃洛石结构优化及其应用［M］. 北京：冶金工业出版社， 2024： 1-2.
	XU P J， DU B B. Optimization of tubular halloysite structure and its application［M］. Beijing： Metallurgical Industry Press， 2024： 1-2 （in Chinese）.
[29]	YUAN P， TAN D Y， ANNABI-BERGAYA F， et al. Changes in structure， morphology， porosity， and surface activity of mesoporous halloysite nanotubes under heating［J］. Clays and Clay Minerals， 2012， 60（6）： 561-573. DOI URL
[30]	夏熠，石凯. 堇青石合成过程中的物相及结构演变［J］. 硅酸盐通报， 2018， 37（9）： 2802-2805.
	XIA Y， SHI K. Phase and micro structure evolution of cordierite during preparation［J］. Bulletin of the Chinese Ceramic Society， 2018， 37（9）： 2802-2805 （in Chinese）.
[31]	GOUBY I， THOMAS P， MERCURIO D， et al. Powder X-ray diffraction and infrared study of the structural evolution in highly K-doped cordierites［J］. Materials Research Bulletin， 1995， 30（5）： 593-599. DOI URL
[32]	李月丽，刘建，胡华，等. 钾钠含量对堇青石蜂窝陶瓷性能的影响［J］. 人工晶体学报， 2012， 41（1）： 183-187.
	LI Y L， LIU J， HU H， et al. Effects of potassium and sodium content on properties of cordierite honeycomb ceramic［J］. Journal of Synthetic Crystals， 2012， 41（1）： 183-187 （in Chinese）.
[33]	CHINTAPALLI R K. Influence of sandblasting on zirconia in restorative dentistry［D］. Barcelona： Polytechnic University of Catalonia， 2012.
[34]	田莳，王敬民，王瑶，等. 材料物理性能［M］. 2版北京：北京航空航天大学出版社， 2022： 314-315.
	TIAN S， WANG J M， WANG Y， et al. Physical properties of materials［M］. 2nd ed. Beijing： Beihang University Press， 2022： 314-315 （in Chinese）.
[35]	王建江，刘宏伟，张龙，等. 反应火焰喷涂工艺对复相陶瓷涂层孔隙率和硬度的影响［J］. 金属热处理， 2008， 33（3）： 59-62.
	WANG J J， LIU H W， ZHANG L， et al. Influence of reactive flame spraying process on properties of multi-phased ceramic coating［J］. Heat Treatment of Metals， 2008， 33（3）： 59-62 （in Chinese）.
[36]	李俊，石旭海，肖卓豪，等. 氧化镁含量及原料煅烧对堇青石陶瓷热膨胀性能的影响［J］. 中国陶瓷工业， 2016， 23（4）： 6-10.
	LI J， SHI X H， XIAO Z H， et al. Effect of MgO addition and raw material calcination on CET of synthetic cordierite ceramics［J］. China Ceramic Industry， 2016， 23（4）： 6-10 （in Chinese）.
[37]	周健儿，张小珍，李家科，等. 透气过滤用堇青石蜂窝陶瓷材料的研究［J］. 中国陶瓷， 2006， 42（2）： 3-7.
	ZHOU J E， ZHANG X Z， LI J K， et al. Study on the cordierite honeycomb ceramics matrix with gas filtration［J］. China Ceramics， 2006， 42（2）： 3-7 （in Chinese）.
[38]	TOKIZONO T， TSURU Y， ATSUMI T， et al. Theoretical approaches for studying anisotropic negative thermal expansion： a case of cordierite［J］. Journal of the Ceramic Society of Japan， 2016， 124（6）： 744-749. DOI URL
[39]	MIYAKE A. Effects of ionic size in the tetrahedral and octahedral sites on the thermal expansion of low-temperature cordierite［J］. Journal of the American Ceramic Society， 2005， 88（2）： 362-366. DOI URL
[40]	IKAWA H， OTAGIRI T， IMAI O， et al. Crystal structures and mechanism of thermal expansion of high cordierite and its solid solutions［J］. Journal of the American Ceramic Society， 1986， 69（6）： 492-498. DOI URL
[41]	HAZEN R， PREWITT C. Effects of temperature and pressure on interatomic distances in oxygen‐based minerals［J］. American Mineralogist， 1977， 62（3-4）： 309-315.
[42]	EVANS D L， FISCHER G R， GEIGER J E， et al. Thermal expansions and chemical modifications of cordierite［J］. Journal of the American Ceramic Society， 1980， 63（11/12）： 629-634. DOI URL
[43]	何峰，刘纳，谢峻林，等. 脱硝催化剂用堇青石多孔陶瓷的制备与性能研究［J］. 硅酸盐通报， 2017， 36（5）： 1464-1469+1479.
	HE F， LIU N， XIE J L， et al. Preparation and properties of the porous cordierite ceramic for catalystic denitration［J］. Bulletin of the Chinese Ceramic Society， 2017， 36（5）： 1464-1469+1479 （in Chinese）.