助熔剂法中碳酸钠与氯化钠对二氧化铈微纳米形貌的调控机制

杨志鹏; 甘雪萍; 刘荣辉

doi:10.19976/j.cnki.43-1448/TF.2025046

粉末冶金材料科学与工程 >

2025 , Vol. 30 >Issue 5: 456 - 470

DOI: https://doi.org/10.19976/j.cnki.43-1448/TF.2025046

工艺技术

助熔剂法中碳酸钠与氯化钠对二氧化铈微纳米形貌的调控机制

杨志鹏 ,
甘雪萍 ,
刘荣辉

展开

中南大学粉末冶金全国重点实验室,长沙 410083

收稿日期: 2025-05-16

修回日期: 2025-10-03

网络出版日期: 2025-11-27

收起

Regulatory mechanisms of Na₂CO₃ and NaCl on the micro-nano morphology of CeO₂ in the flux method

YANG Zhipeng ,
GAN Xueping ,
LIU Ronghui

Expand

State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China

Received date: 2025-05-16

Revised date: 2025-10-03

Online published: 2025-11-27

Fold

摘要

CeO₂成本低廉、应用广泛,对其进行形貌调控是一直以来的重要课题。本文采用助熔剂法对块状CeO₂进行球化,系统探究Na₂CO₃、NaCl及其复合助熔剂对CeO₂形貌调控的作用机制。结果表明：助熔剂种类与浓度会显著影响CeO₂的球形化过程,Na₂CO₃在900 ℃以上通过化学活性作用促进微米级(约5 μm)近球形颗粒形成,其机理涉及Na⁺晶格掺杂与氧空位协同效应,在1 000 ℃、Na₂CO₃和原料的质量比为1.8∶10时可获得圆度为0.80的高品质球形CeO₂;而NaCl主要通过物理熔盐效应诱导纳米级(500~800 nm)颗粒生成,但存在严重团聚问题。复合助熔剂体系中两种组分呈现作用机制冲突,导致球形度劣于单一体系。研究证实工艺调控可突破传统固相法形貌控制瓶颈,其中Na₂CO₃体系兼具工艺简单、成本低廉与产物分散性高的特点,为工业化生产中在1~10 μm范围内制备粒径可调的球形CeO₂提供了新的参考思路。

关键词： 氧化铈; 固相法; 烧结; 助熔剂; 形貌调控

本文引用格式

杨志鹏 , 甘雪萍 , 刘荣辉 . 助熔剂法中碳酸钠与氯化钠对二氧化铈微纳米形貌的调控机制[J]. 粉末冶金材料科学与工程, 2025 , 30(5) : 456 -470 . DOI: 10.19976/j.cnki.43-1448/TF.2025046

Abstract

As an economically viable material with extensive applications, morphology regulation of CeO₂ has remained a critical challenge. This study developed a flux method for spheroidizing blocky CeO₂, with systematic investigation into the regulatory mechanisms of Na₂CO₃, NaCl, and their composite fluxes on CeO₂ morphology. The results reveal flux type and concentration can significantly affect the spheroidization process of CeO₂. Na₂CO₃ facilitates micro-scale (~5 μm) quasi-spherical particle evolution above 900 ℃ through chemically activated mechanisms combining Na⁺ lattice intercalation and oxygen vacancy compensation. Optimized spherical CeO₂ with sphericity index 0.80 is achieved at 1 000 ℃ when mass ratio of Na₂CO₃ and raw materials is 1.8∶10. Comparatively, NaCl-dominated systems generate nano-sized particles (500-800 nm) via physical fluxing effects but exhibit pronounced agglomeration. The composite flux system demonstrate antagonistic interactions between components, leading to degraded sphericity relative to single-component counterparts. This work confirms that process regulation can overcome intrinsic limitations of conventional solid-phase method morphology control. The Na₂CO₃-dominated system features operational simplicity, cost-effectiveness, and superior particle dispersibility, offering a scalable pathway for industrial synthesis of spherical CeO₂ with precisely tunable diameters (1-10 μm).

Key words： CeO₂; solid-phase method; sintering; flux; morphology control

参考文献

[1] DUDNIK O V, LAKIZA S M, GRECHANYUK I M, et al.Composite ceramics for thermal barrier coatings produced from ZrO₂ doped with yttrium-subgroup rare-earth metal oxides[J]. Powder Metallurgy and Metal Ceramics, 2021, 59(11): 672-680.
[2] ZHENG W P, HAO L F, ZHOU Y, et al.Strengthen corrosion resistance of epoxy coating by synergy of oxygen vacancies of CeO₂ nanoparticles as charge capture centers and BTA/TEOS[J]. Progress in Organic Coatings, 2024, 192: 108481.
[3] SUKUMARAN J, VENKATESAN R, PRIYA M, et al.Eco-friendly synthesis of CeO₂ nanoparticles using Morinda citrifolia L. leaf extracts: evaluation of structural, antibacterial, and anti-inflammatory activity[J]. Inorganic Chemistry Communications, 2024, 170: 113411.
[4] RAY S K, DAHAL R, ASHIE M D, et al.Recent progress on cerium oxide-based nanostructures for energy and environmental applications[J]. Advanced Energy and Sustainability Research, 2025, 6(10): 2500022.
[5] 高天佐, 于晓丽, 张玉玺, 等. 不同形貌二氧化铈的制备及其紫外屏蔽性能研究[J]. 湿法冶金, 2018, 37(6): 497-500.
GAO Tianzuo, YU Xiaoli, ZHANG Yuxi, et al.Preparation and UV-shielding properties of ceria with different morphologies[J]. Hydrometallurgy of China, 2018, 37(6): 497-500.
[6] DUDNIK O V, LAKIZA S M, GRECHANYUK M I, et al.Composite ceramics for thermal-barrier coatings produced from zirconia doped with rare earth oxides[J]. Powder Metallurgy and Metal Ceramics, 2022, 61(7): 441-450.
[7] WANG J S, SUN J B, JING Q S, et al.Phase stability and thermo-physical properties of ZrO₂-CeO₂-TiO₂ ceramics for thermal barrier coatings[J]. Journal of the European Ceramic Society, 2018, 38(7): 2841-2850.
[8] ZHU Y Z, WANG W X, CHEN G J X, et al. Influence of Ni doping on oxygen vacancy-induced changes in structural and chemical properties of CeO₂ nanorods[J]. Crystals, 2024, 14(8): 746-755.
[9] MISHRA A K, WILLOUGHBY J, ESTES S L, et al.Impact of morphology and oxygen vacancy content in Ni, Fe co-doped ceria for efficient electrocatalyst based water splitting[J]. Nanoscale Advances, 2024, 6(18): 4672-4682.
[10] 文素芬, 邹金住, 周学凡, 等. 微米级二氧化硅空心微球的制备及表征[J]. 粉末冶金材料科学与工程, 2022, 27(3): 336-344.
WEN Sufen, ZOU Jinzhu, ZHOU Xuefan, et al.Preparation and characterization of micron hollow silica microspheres[J]. Materials Science and Engineering of Powder Metallurgy, 2022, 27(3): 336-344.
[11] 吕凤程, 王丁, 李中林, 等. 水热法制备γ-AlOOH对酸性大红GR的吸附性能[J]. 粉末冶金材料科学与工程, 2022, 27(5): 550-558.
LÜ Fengcheng, WANG Ding, LI Zhonglin, et al.Adsorption performance of acid scarlet GR by γ-Al OOH prepared with hydrothermal method[J]. Materials Science and Engineering of Powder Metallurgy, 2022, 27(5): 550-558.
[12] 吴浩, 甘雪萍. 喷雾干燥法制备Cu-Al₂O₃复合粉末及其复合材料的组织与性能[J]. 粉末冶金材料科学与工程, 2023, 28(1): 74-82.
WU Hao, GAN Xueping.Fabrication of Cu-Al₂O₃ composite powder by spray drying and its microstructure and properties[J]. Materials Science and Engineering of Powder Metallurgy, 2023, 28(1): 74-82.
[13] CHIBISOV A N, PUGACHEVSKII M A, KUZMENKO A P, et al.Effect of morphology and size on the thermodynamic stability of cerium oxide nanoparticles: experiment and molecular dynamics calculation[J]. Nanotechnology Reviews, 2022, 11(1): 620-624.
[14] ZHANG C Y, JIA J C, CHANG Y, et al.The corrosion resistant Pt₅Ce-CeO₂ structure provides significant oxygen reduction catalysis[J]. International Journal of Hydrogen Energy, 2024, 51: 1169-1175.
[15] 陈欢欢. 改性二氧化铈复合材料[M]. 北京: 化学工业出版社, 2024.
CHEN Huanhuan.Modified Cerium Dioxide Composite Material[M]. Beijing: Chemical Industry Press, 2024.
[16] FADZIL N A M, RAHIM M H A B, MANIAM G P. Brief review of ceria and modified ceria: synthesis and application[J]. Materials Research Express, 2018, 5(8): 085019.
[17] 丁林敏. 铈基氧化物材料及前驱体的合成及抛光性能研究[D]. 南昌: 南昌大学, 2022.
DING Linmin.Synthesis and polishing properties of cerium-based oxide materials and precursors[D]. Nanchang: Nanchang University, 2022.
[18] 徐筱李, 韦宝禧, 侯金丽, 等. 典型纳米多孔隔热材料文献综述[C]// 中国航天第三专业信息网, 中国科协航空发动机产学联合体. 中国航天第三专业信息网第四十届技术交流会暨第四届空天动力联合会议论文集, 2019: 129-141.
XU Xiaoli, WEI Baoxi, HOU Jinli, et al.Literature review of typical nanoporous thermal insulation materials[C]// China Aerospace Third Professional Information Network, CAST Alliance for Aero-Engine Industry and Academy. Conference Proceedings of 40th Technical Exchange Conference of China Aerospace Third Professional Information Network and 4th Aerospace Power Joint Conference, 2019: 129-141.
[19] LU X X, ZHAO X, ZHANG J Y, et al.Spherical CeO₂ synthesized by molten-salt with unique fast variable valence properties for lithium-ion battery anode[J]. Materials Letters, 2023, 349: 134780.
[20] SONG S P, LI Y J, BAI S B, et al.Production of spherical polymeric composite powder for selective laser sintering via plasma assisted solid state shear milling: from theory to piezoelectric application[J]. Chemical Engineering Journal, 2021, 415: 129035.
[21] YANG B, WANG A Q, LIU K D, et al.Effects of CeO₂ on the Si precipitation mechanism of SiC_p/Al-Si composite prepared by powder metallurgy[J]. Materials, 2020, 13(19): 4365-4374.
[22] BJØRK R. The sintering behavior of ellipsoidal particles[J]. Journal of the American Ceramic Society, 2022, 105(10): 6427-6436.
[23] TACHIBANA M.Beginner’s Guide to Flux Crystal Growth[M]. Berlin: Springer, 2017.
[24] SANTIAGO R T, FABIÁN M, ŠEPELÁK V, et al. Local structure analysis of Bi₂(Ga₁-_xFe_x)₄O₉ mullite-type solid solutions synthesized via combination of ball milling and thermal treatment[J]. Solid State Sciences, 2018, 82(1): 106-110.
[25] GRADY Z, NDAYISHIMIYE A, ZAENGLE T, et al. Progress and opportunities in the application of cold sintering to solid-state, electrochemical,ceramic devices[J]. ECS Meeting Abstracts, 2021, MA2021-02: 1382.
[26] ALAM M A, YA H B, AZEEM M, et al.Advancements in aluminum matrix composites reinforced with carbides and graphene: a comprehensive review[J]. Nanotechnology Reviews, 2023, 12: 20230111.
[27] BONDIOLI F, MANFREDINI T, KOMARNENI S.Synthesis and characterisation of nanosize CeO₂ powders by flux method[C]// VINCENZINI P. Advances in Science and Technology. Faenza, Italy: Techna, 1999: B293-B300.
[28] LIANG Y J, YU D Y, HUANG W Z, et al.Molten salt synthesis and luminescent properties of nearly spherical YAG:Ce phosphor[J]. Materials Science in Semiconductor Processing, 2015, 30: 92-97.
[29] DAN X, WANG C, XU X, et al.Improving the sinterability of CeO₂ by using plane-selective nanocubes[J]. Journal of the European Ceramic Society, 2019, 39(14): 4429-4434.
[30] LAN X, LI Z B, ZHANG H, et al.Effect of rare earth oxide doping on microstructure and mechanical property of Mo-30 W solid solution alloy[J]. International Journal of Refractory Metals and Hard Materials, 2023, 110: 106014.
[31] MANIVANNAN V, PARHI P, KRAMER J W.Metathesis synthesis and characterization of complex metal fluoride, KMF₃ (M=Mg, Zn, Mn, Ni, Cu and Co) using mechanochemical activation[J]. Bulletin of Materials Science, 2008, 31(7): 987-993.
[32] KIM G H, SOHN I.Effects of alkali metal cations and fluoride anions on viscosity and structure of CaO-SiO₂-Al₂O₃ system[J]. Journal of Materials Research and Technology, 2022, 20: 2335-2347.
[33] BAO S S, YU D M, TANG Z, et al.Conformationally regulated “nanozyme-like” cerium oxide with multiple free radical scavenging activities for osteoimmunology modulation and vascularized osseointegration[J]. Bioactive Materials, 2024, 34: 64-79.
[34] WU X X, WEI J X, ZHANG T, et al.Novel synthesis of in situ CeO_x nanoparticles decorated on CoP nanosheets for highly efficient electrocatalytic oxygen evolution[J]. Inorganic Chemistry Frontiers, 2021, 8(20): 4440-4447.
[35] 段淑贞. 熔盐化学:原理和应用[M]. 北京: 冶金工业出版社, 1990.
DUAN Shuzhen.Molten Salt Chemistry: Principles and Applications[M]. Beijing: Metallurgical Industry Press, 1990.
[36] 曾燕伟. 无机材料科学基础: 第2版[M]. 武汉: 武汉理工大学出版社, 2015.
ZENG Yanwei.Scientific Fundamentals of Inorganic Materials: 2nd Edition[M]. Wuhan: Wuhan University of Technology Press, 2015.

Options

文章导航

模态框（Modal）标题

摘要

本文引用格式

Abstract

参考文献