二氧化钛对铝酸锌耐火陶瓷性能的影响

doi:10.16552/j.cnki.issn1001-1625.2025.0053

摘要/Abstract

摘要： 为了发展低热导率、高力学性能的铝酸锌(ZnAl₂O₄)耐火陶瓷,添加二氧化钛(TiO₂)对其性能进行改性。以氧化铝和氧化锌为铝源和锌源,氧化镁为烧结助剂,通过固相反应烧结制备ZnAl₂O₄耐火陶瓷,研究TiO₂添加量对ZnAl₂O₄耐火陶瓷性能的影响,并从物相、微观形貌的变化揭示其改性机理。结果表明,随着TiO₂添加量增加,ZnAl₂O₄陶瓷的性能均有提升。当TiO₂添加量为11%(质量分数)、烧结温度为1 500 ℃时,烧结得到的ZnAl₂O₄陶瓷各项性能最为优异,其显气孔率为3.5%,体积密度为4.21 g/cm³,线性收缩率为28.53%,抗折强度达到最大值202.3 MPa,热导率为10.003 W/(m·K)。TiO₂的添加会促进铝酸锌晶粒生长,并与其生成固溶体Zn_1.5Ti_0.25Al₄O₈,使铝酸锌晶粒更完善,结构更致密。同时,TiO₂的添加也可降低铝酸锌陶瓷的烧结温度,符合节能环保要求。

关键词: 耐火陶瓷, 铝酸锌, 致密度, 抗折强度, 热导率

Abstract: In order to develop zinc aluminate (ZnAl₂O₄) refractory ceramics with low thermal conductivity and high mechanical properties, titanium dioxide (TiO₂) was added to modify its properties. ZnAl₂O₄ refractory ceramics was prepared by solid-phase reaction sintering method using alumina and zinc oxide as aluminum and zinc sources, and magnesium oxide as sintering aid. The effect of TiO₂ content on the properties of ZnAl₂O₄ refractory ceramics was investigated, and the modification mechanism was revealed from the changes of phase and micromorphology. The results indicate that the properties of ZnAl₂O₄ ceramics are improved with the increase of TiO₂ content. When the TiO₂ content is 11% (mass fraction), the ZnAl₂O₄ ceramics obtained by sintering at 1 500 ℃ have the best performance. Their apparent porosity is 3.5%, bulk density is 4.21 g/cm³, linear shrinkage rate is 28.53%, the maximum flexural strength is 202.3 MPa, and the thermal conductivity is 10.003 W/(m·K). The addition of TiO₂ can promote the growth of zinc aluminate grain and generate solid solution Zn_1.5Ti_0.25Al₄O₈, which makes the zinc aluminate grain more perfect and the structure more dense. At the same time, the addition of TiO₂ can also reduce the sintering temperature of zinc aluminate ceramics, which meets the requirements of energy saving and environmental protection.

Key words: refractory ceramics, zinc aluminate, density, flexural strength, thermal conductivity

中图分类号:

TQ175.7

刘琦, 黄世谋, 郝建英, 崔步哲, 朱振国, 白朔. 二氧化钛对铝酸锌耐火陶瓷性能的影响[J]. 硅酸盐通报, 2025, 44(8): 3042-3048.

LIU Qi, HUANG Shimou, HAO Jianying, CUI Buzhe, ZHU Zhenguo, BAI Shuo. Influence of Titanium Dioxide on Properties of Zinc Aluminate Refractory Ceramics[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(8): 3042-3048.

参考文献

[1] 王长安, 邓丽娜, 王雅兰. 水泥窑用耐火材料质量现状及发展趋势[J]. 中国水泥, 2024(增刊2): 15-19.
WANG C A, DENG L N, WANG Y L. Quality status and development trend of refractories for cement kiln[J]. China Cement, 2024(supplement 2): 15-19 (in Chinese).
[2] LOTFIAN N, NOURBAKHSH A, MIRSATTARI S N, et al. Functionalization of nano-MgCr₂O₄ additives by silanol groups: a new approach to the development of magnesia-chrome refractories[J]. Ceramics International, 2021, 47(22): 31724-31731.
[3] XUAN S T, TIAN Y M, KONG X C, et al. Effect of different MgO/Al₂O₃ ratios on microstructural densification, sintering process and mechanical property of MgAl₂O₄ materials[J]. Journal of Materials Research and Technology, 2023, 25: 2518-2526.
[4] 朱伯铨, 李享成. 刚玉-莫来石-锌铝尖晶石复相材料合成的热力学研究[J]. 耐火材料, 2004, 38(2): 63-65+69.
ZHU B Q, LI X C. Thermodynamics study on synthesizing corundum-mullite-gahnite multiphase materials[J]. Refractories, 2004, 38(2): 63-65+69 (in Chinese).
[5] 李享成, 朱伯铨, 龚荣洲. 刚玉-莫来石-锌铝尖晶石复相材料的合成与烧结[J]. 硅酸盐学报, 2005, 33(1): 7-11.
LI X C, ZHU B Q, GONG R Z. Synthesis and sinterability of corundum-mullite-ZnO·Al₂O₃ multiphase materials[J]. Journal of the Chinese Ceramic Society, 2005, 33(1): 7-11 (in Chinese).
[6] SHEN Q K, HAO J Y, ZHU Z G, et al. Preparation and performance optimization of zinc aluminate ceramic by solid-state reaction sintering[J]. Ceramics International, 2024, 50(20): 39574-39580.
[7] SHEN Q K, HAO J Y, ZHU Z G, et al. Optimization of compactness and mechanical properties of zinc aluminate ceramics under the synergistic control of pyrolusite doping and sintering temperature[J]. Ceramics International, 2025, 51(6): 8107-8115.
[8] 谢永涣. 水泥窑用方镁石-锌铝尖晶石耐火材料研究[D]. 鞍山: 辽宁科技大学, 2023: 35-58.
XIE Y H. Study on periclase-zinc alumina spinel refractory for cement kiln[D]. Anshan: University of Science and Technology Liaoning, 2023: 35-58 (in Chinese).
[9] 杨帅. 锌铝尖晶石的合成及应用[D]. 鞍山: 辽宁科技大学, 2021: 22-31.
YANG S. Synthesis and application of zinc-aluminum spinel[D]. Anshan: University of Science and Technology Liaoning, 2021: 22-31 (in Chinese).
[10] PAVLOV A, SAGDOLDINA Z, ZHILKASHINOVA A, et al. Synthesis and investigation of properties of beryllium ceramics modified with titanium dioxide nanoparticles[J]. Materials, 2023, 16(19): 6507.
[11] VELAPPAN S, NIVEDHITA P, VIMALA R, et al. Role of nano titania on the thermomechanical properties of silicon carbide refractories[J]. Ceramics International, 2020, 46(16): 25921-25926.
[12] 路跃. CaZrO₃材料结构、性能研究及其与高温合金界面反应探索[D]. 洛阳: 中钢集团洛阳耐火材料研究院有限公司, 2024: 32-45.
LU Y. The microstructure and properties of CaZrO₃ materials andthe exploration of its interface reaction with superalloys[D]. Luoyang: Sinosteel Luoyang Refractory Research Institute Co., Ltd., 2024: 32-45 (in Chinese).
[13] 周立忠, 汪长安, 刘伟渊, 等. TiO₂对堇青石多孔陶瓷微观结构和性能的影响[J]. 稀有金属材料与工程, 2009, 38(增刊2): 366-368.
ZHOU L Z, WANG C A, LIU W Y, et al. Influence of titanium dioxide on the microstructure and properties of porous cordierite ceramics[J]. Rare Metal Materials and Engineering, 2009, 38(supplement 2): 366-368 (in Chinese).
[14] 刘继富, 沈仰云. 颗粒弥散强化复相陶瓷临界颗粒尺寸的优化设计[J]. 材料科学与工艺, 1995, 3(3): 52-56.
LIU J F, SHEN Y Y. Optimization of the critical particle size in particle dispersion strengthened multiphase ceramics[J]. Materials Science and Technology, 1995, 3(3): 52-56 (in Chinese).
[15] RICE R W. Comparison of stress concentration versus minimum solid area based mechanical property-porosity relations[J]. Journal of Materials Science, 1993, 28(8): 2187-2190.
[16] 马逸飞, 李其松, 黄权, 等. 碳化硅陶瓷热导率影响因素研究[J]. 中原工学院学报, 2024, 35(1): 23-34+64.
MA Y F, LI Q S, HUANG Q, et al. Research on influencing factors of the SiC ceramic thermal conductivity[J]. Journal of Zhongyuan University of Technology, 2024, 35(1): 23-34+64 (in Chinese).
[17] 邵凤翔, 陈晓鸽, 张红松. (Sm_0.5Nd_0.5-xLa_x)₂Ce₂O₇陶瓷材料热物理性能[J]. 陶瓷学报, 2017, 38(4): 559-563.
SHAO F X, CHEN X G, ZHANG H S. Thermophysical properties of (Sm_0.5Nd_0.5-xLa_x)₂Ce₂O₇ ceramics[J]. Journal of Ceramics, 2017, 38(4): 559-563 (in Chinese).
[18] SURENDRAN K P, BIJUMON P V, MOHANAN P, et al. (1-x)MgAl₂O₄-xTiO₂ dielectrics for microwave and millimeter wave applications[J]. Applied Physics A, 2005, 81(4): 823-826.
[19] 高鸣阳, 李元勋, 陈旻澍, 等. Zn_0.9Mg_0.1Al₂O₄微波导热陶瓷材料的改性研究[J]. 压电与声光, 2021, 43(2): 260-264.
GAO M Y, LI Y X, CHEN M S, et al. Study on modification of Zn_0.9Mg_0.1Al₂O₄ microwave thermal conductive ceramic material[J]. Piezoelectrics & Acoustooptics, 2021, 43(2): 260-264 (in Chinese).
[20] CAO X Q, VASSEN R, STOEVER D. Ceramic materials for thermal barrier coatings[J]. Journal of the European Ceramic Society, 2004, 24(1): 1-10.
[21] VAN DER LAAG N J, SNEL M D, MAGUSIN P C M M, et al. Structural, elastic, thermophysical and dielectric properties of zinc aluminate (ZnAl₂O₄)[J]. Journal of the European Ceramic Society, 2004, 24(8): 2417-2424.
[22] 石凯, 夏熠. 直接复合制备水泥窑用轻重复合硅莫砖研究[J]. 耐火材料, 2019, 53(2): 86-90.
SHI K, XIA Y. Preparation of light-heavy-weight composite SiC-mullite bricks for cement kilns by direct compounding[J]. Refractories, 2019, 53(2): 86-90 (in Chinese).
[23] ZHOU Y, YE D C, WU Y Q, et al. Low-cost preparation and characterization of MgAl₂O₄ ceramics[J]. Ceramics International, 2022, 48(5): 7316-7319.
[24] 张菡欣. 轻量化方镁石-镁铝尖晶石耐火材料的制备及性能研究[D]. 淮南: 安徽理工大学, 2024.
ZHANG H X. Preparation and performance study of lightweight periclase-magnesium aluminate spinel refractories[D]. Huainan: Anhui University of Science & Technology, 2024 (in Chinese).
[25] FENG M, WU Y Q, JI G R, et al. Sintering mechanism and properties of corundum-mullite duplex ceramic with MnO₂ addition[J]. Ceramics International, 2022, 48(10): 14237-14245.
[26] HUANG C L, YANG T J, HUANG C C. Low dielectric loss ceramics in the ZnAl₂O₄-TiO₂ system as a τ_f compensator[J]. Journal of the American Ceramic Society, 2009, 92(1): 119-124.
[27] WATANABE M, SEKI T. Initial sintering kinetics of non-stoichiometricCeO_2-x[J]. Materials Science and Engineering: B, 2021, 272: 115369.