高熵多孔磷酸盐陶瓷的制备、结构及其隔热机理研究

张佩雄; 王恩会; 刘静静; 杨涛; 王海龙; 侯新梅

doi:10.1007/s12613-023-2788-1

Volume 31 Issue 7

Jul. 2024

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文章导航 > 矿物冶金与材料学报（英文） > 2024 > 31(7): 1651-1658

Peixiong Zhang, Enhui Wang, Jingjing Liu, Tao Yang, Hailong Wang, and Xinmei Hou, Porous high-entropy rare-earth phosphate (REPO₄, RE = La, Sm, Eu, Ce, Pr and Gd) ceramics with excellent thermal insulation performance via pore structure tailoring, Int. J. Miner. Metall. Mater., 31(2024), No. 7, pp. 1651-1658. https://doi.org/10.1007/s12613-023-2788-1

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Peixiong Zhang, Enhui Wang, Jingjing Liu, Tao Yang, Hailong Wang, and Xinmei Hou, Porous high-entropy rare-earth phosphate (REPO4, RE = La, Sm, Eu, Ce, Pr and Gd) ceramics with excellent thermal insulation performance via pore structure tailoring, Int. J. Miner. Metall. Mater., 31(2024), No. 7, pp. 1651-1658. https://doi.org/10.1007/s12613-023-2788-1

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研究论文

高熵多孔磷酸盐陶瓷的制备、结构及其隔热机理研究

1)
北京科技大学碳中和研究院, 北京 100083, 中国
2)
辽宁材料实验室, 沈阳 110000, 中国
3)
北京科技大学金属冶炼重大事故防控技术支撑基地, 北京 100083, 中国
4)
郑州大学材料科学与工程学院, 郑州, 450001, 中国

通讯作者:
王恩会 E-mail: wangenhui@ustb.edu.cn

侯新梅 E-mail: houxinmeiustb@ustb.edu.cn

文章亮点

(1) 制备了单相元素分布均匀的高熵(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄粉体，晶体结构为单斜独居石结构，属于P2_1/n (Z = 4)空间群。

(2) 研究了淀粉含量对高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷的物相组成、微观结构、孔径分布及尺寸、力学性能和热学性能的影响。

(3) 探索了高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷的隔热机理，遴选出适用于淀粉造孔法制备的高熵多孔(La1/6Ce1/6Pr1/6Sm1/6Eu1/6Gd1/6)PO4陶瓷的室温热导率预测模型。

中文摘要

多孔陶瓷由于具有孔隙率高、低密度和低热导率等优点广泛应用于隔热材料。目前，氧化物陶瓷例如YSZ、钙长石和Y₂SiO₅由于具有良好的抗氧化性和耐腐蚀性被广泛用作隔热材料。尽管这些多孔材料具有明显的优势，但它们仍然有一些缺点，这些陶瓷材料由于存在较高的热导率和高温相稳定性较差的问题而被有所限制。近年来，由于航空航天的热防护材料提出了更高的要求，迫切需要寻找新型的高性能轻质高强度隔热材料。稀土磷酸盐（REPO₄, RE = La–Gd）由于具有高熔点、良好的高温相稳定性等一系列优异的性能，被认为是隔热材料的有力候选者。然而，对稀土磷酸盐陶瓷的研究主要集中在致密陶瓷块体和热/环境障涂层上，目前关于多孔磷酸盐隔热材料研究的报道很少。高熵策略通过增加构型熵可以提高材料的力学性能和相稳定性、降低热导率、晶粒生长速率，是调控材料性能的热门和可行手段。本工作以稀土硝酸盐（RE(NO₃)₃·6H₂O, RE = La, Ce, Pr, Sm, Eu, Gd）和H₃PO₄为原料，采用化学共沉淀法制备了高熵(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄粉体。在此基础上，以淀粉为造孔剂，制备了不同淀粉含量的高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷，研究了淀粉含量对高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷的物相组成、微观结构、孔径分布及尺寸、热导率和耐压强度的影响。研究结果表明，利用淀粉造孔法制备的高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷具有分级孔隙结构，分别为孔径尺寸10 μm的球形大孔和0.5–1.5 μm的小孔。随着淀粉含量的增加，高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷的孔隙率增加，热导率和耐压强度呈现降低的变化趋势。当淀粉添加量为60wt%时，高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷具有较低的热导率（0.061 W/(m·K)）、耐压强度（0.23 MPa）和良好的高温孔结构稳定性（收缩率为1.67%），这些优异的性能表明高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷具有优异的高温隔热性能，有望作为新型的隔热材料使用。此外，由于淀粉造孔法制备的孔结构的特性，高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷的室温热导率与ME2模型预测的热导率结果变化趋势基本符合。

关键词:

高熵多孔(La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄陶瓷;
高熵策略;
造孔法;
隔热材料;
热导率

Research Article

Porous high-entropy rare-earth phosphate (REPO₄, RE = La, Sm, Eu, Ce, Pr and Gd) ceramics with excellent thermal insulation performance via pore structure tailoring

+ Author Affiliations

1)
Institute for Carbon Neutrality, University of Science and Technology Beijing, Beijing 100083, China
2)
Liaoning Academy of Materials, Shenyang 110000, China
3)
Technical Support Center for Prevention and Control of Disastrous Accidents in Metal Smelting, University of Science and Technology Beijing, Beijing 100083, China
4)
School of Materials Science Engineering, Zhengzhou University, Zhengzhou 450001, China

Xinmei Hou is an editorial board member for this journal and was not involved in the editorial review or the decision to publish this article. The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Corresponding authors:
Enhui Wang E-mail: wangenhui@ustb.edu.cn

Xinmei Hou E-mail: houxinmeiustb@ustb.edu.cn
Received: 31 July 2023; Revised: 30 October 2023; Accepted: 17 November 2023; Available online: 21 November 2023

Abstract

Abstract

Thermal insulation materials play an increasingly important role in protecting mechanical parts functioning at high temperatures. In this study, a new porous high-entropy (La_1/6Ce_1/6Pr_1/6Sm_1/6Eu_1/6Gd_1/6)PO₄ (HE (6RE_1/6)PO₄) ceramics was prepared by combining the high-entropy method with the pore-forming agent method and the effect of different starch contents (0–60vol%) on this ceramic properties was systematically investigated. The results show that the porous HE (6RE_1/6)PO₄ ceramics with 60vol% starch exhibit the lowest thermal conductivity of 0.061 W·m⁻¹·K⁻¹ at room temperature and good pore structure stability with a linear shrinkage of approximately 1.67%. Moreover, the effect of large regular spherical pores (>10 μm) on its thermal insulation performance was discussed, and an optimal thermal conductivity prediction model was screened. The superior properties of the prepared porous HE (6RE_1/6)PO₄ ceramics allow them to be promising insulation materials in the future.

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