硅酸盐学报

CaO-MgO-Al₂O₃复合氧化物材料结构、性能与应用前景

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古晨伟 ¹^,² , 王战民 ¹^,² , 陈卢 ²

硅酸盐学报 | 综合评述 2026,54(9): 3264-3273

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硅酸盐学报 |综合评述 2026 , 54 (9) : 3264 -3273

CaO-MgO-Al₂O₃复合氧化物材料结构、性能与应用前景

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古晨伟¹^,², 王战民¹^,², 陈卢²

作者信息

^1．河南科技大学材料科学与工程学院，河南洛阳 471000

^2．中钢集团洛阳耐火材料研究院有限公司，先进耐火材料全国重点实验室，河南洛阳 471000

通讯作者:

王战民（1966—），男，博士，教授级高级工程师。

作者简介:

古晨伟（1997—），男，博士研究生。

Structure, Properties, and Application Prospects of CaO-MgO-Al₂O₃ Composite Oxide Materials

Chenwei GU¹^,², Zhanmin WANG¹^,², Lu CHEN²

Affiliations

^1.School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471000, Henan, Chain

^2.State Key Laboratory of Advanced Refractories, Sinosteel Luoyang Institute of Refractories Research Co., Ltd. Luoyang 471039, Henan, China

Corresponding Author:

{WANG} Zhanmin (1966-), male, Ph.D. Professor-level Senior Engineer. E-mail: wangzm@lirrc.com

GU Chenwei (1997-), male, Doctoral candidate. E-mail: 1739899376@qq.com

出版时间: 2026-08-18 doi: 10.14062/j.issn.0454-5648.20250773

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摘要

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CaO-MgO-Al₂O₃（以下称CMA材料）系列材料主要包括CaMg₂Al₁₆O₂₇（以下称CM₂A₈）和Ca₂Mg₂Al₂₈O₄₆ （以下称C₂M₂A₁₄） 2种化合物相。在Al₂O₃-CaO-MgO三元相图中，CMA材料位于CaAl₁₂O₁₉和MgAl₂O₄连线上，其结构由磁铅石（CaAl₁₂O₁₉以下称CA₆）层与镁铝尖晶石（MgAl₂O₄，以下称MA）层交替堆叠而成，该结构有效的融合了前者优异的高温稳定性和后者良好的热机械性能，被视为极具潜力的新一代高性能耐火材料。然而，其巨大的应用潜力正被一个固有矛盾所严重制约：赋予其优异性能的层状晶体结构，同样导致了严重的烧结各向异性生长，使得常规方法难以获得高致密体。本文系统梳理了CMA材料的研究进展，首先厘清其结构-性能关联，继而将论述核心聚焦于这一根本矛盾，比较了改善此困境的多种技术路径（热压工艺、电熔工艺、添加剂改性），分析其机理、成效与代价。更进一步，提出CMA材料的应用需从一味追求致密化转向性能适配与缺点转化，即在其难以致密的定型制品中优化制备，同时在其不定型材料中主动利用板片状晶粒的增强效应，乃至将其分解行为转化为设计多孔结构的工具。最后，基于当前研究现状，本文指明了结合多尺度模拟、开发新型烧结工艺及构建CMA基元功能材料等具体未来方向。

关键词

氧化钙-氧化镁-氧化铝 / 各向异性生长 / 致密化 / 合成机制 / 耐火材料

Abstract

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The development of high-temperature industrial technologies, such as steelmaking and cement production, relies critically on refractory materials. Conventional systems like magnesia, alumina-silica, and magnesia-alumina spinel, despite their maturity, exhibit inherent limitations, i.e., poor thermal shock resistance, insufficient stability under reducing atmospheres, or high costs. Furthermore, environmental concerns regarding toxic Cr⁶⁺ from magnesia-chromium bricks have an urgent demand for eco-friendly, high-performance alternatives.

In this context, the CaO-MgO-Al₂O₃(CMA) ternary system, specifically the compounds CaMg₂Al₁₆O₂₇ (CM₂A₈) and Ca₂Mg₂Al₂₈O₄₆ (C₂M₂A₁₄), has attracted considerable attention. These materials possess a unique hybrid crystal structure composed of alternating magnetoplumbite (CaAl₁₂O₁₉, CA₆) and spinel (MgAl₂O₄, MA) layers stacked along the c-axis. This structure ingeniously combines the high melting point and chemical stability of CA₆ with the favorable thermomechanical properties of MA, having CMA as a promising candidate for next-generation refractories.

However, the same layered structure that confers these advantages also causes an intense anisotropic grain growth during conventional solid-phase sintering. Grains develop plate-like or rhombohedral morphologies and prematurely interlock, forming a rigid porous skeleton that entraps pores and severely impedes densification. Consequently, CMA materials typically exhibit a high apparent porosity (i.e., >20%) when processed by conventional methods, creating a fundamental contradiction between performance potential and processability.

To overcome this densification challenge, researchers have explored three main technological pathways, i.e., 1) Hot Pressing Sintering: Application of uniaxial pressure during sintering effectively inhibits an anisotropic grain growth, yielding near-fully dense (>97% purity) CMA ceramics with apparent porosity of <0.2%. The properties reported include bulk density (i.e., 3.66-3.71 g/cm³), flexural strength (i.e., 248-262 MPa), and fracture toughness (i.e., 2.17-2.23 MPa·m^1/2). However, high costs and low productivity limit this method to fundamental research; 2) Additive Engineering: Introduction of trace additives modifies grain boundary energy or diffusion kinetics, promoting a morphological transformation from plate-like to equiaxed grains. For instance, 3% MnO addition reduces apparent porosity from 32.5% to 8.4% at 1700 ℃, while 1% Fe₂O₃ achieves 12.5% porosity at 1780 ℃. However, foreign ions may compromise a long-term high-temperature performance, requiring careful optimization; and 3) Electric Melting Composite Method: Melting raw materials at > 2000 ℃ followed by rapid cooling produces CMA-based multiphase materials with a bulk density up to 3.50 g·cm^-3. Despite relatively dense structures, this approach suffers from high energy consumption and compositional homogeneity challenges.

Based on the cost and complexity of achieving full densification, a paradigm shift is proposed, rather than solely pursuing densification. The inherent characteristics of CMA should be used for specific applications.

For high-end dense products (e.g., metallurgical crucibles), optimized additive engineering combined with advanced forming techniques remain the most viable approach for achieving low porosity and high strength.

For monolithic refractories (i.e., castables, gunning mixes), the plate-like morphology that hinders densification becomes advantageous. Some studies demonstrate that introducing CMA aggregates enables plate-like grains to form interlocking structures within the matrix, significantly enhancing toughness and thermal shock resistance through crack deflection and bridging mechanisms. Crucially, plate-like CMA crystals can grow into adjacent corundum aggregates, creating mechanical interlocking that substantially strengthens aggregate-matrix bonding.

For lightweight and functional applications, the decomposition behavior of CMA can be exploited. Introducing C₂M₂A₁₄ into magnesia or spinel-based systems generates uniform micropores via the Kirkendall effect during firing, achieving lightweighting, while improving thermal shock resistance through pore-induced crack blunting and thermal stress buffering.

Regarding corrosion resistance, CMA exhibits a highly selective performance governed by specific interface reaction mechanisms. Against high-basicity LF refining slag, CM₂A₈ forms a continuous dense CaAl₂O₄ protective layer through Ca²⁺exchange, while dissolved Al³⁺ and Mg²⁺ increase a slag viscosity for creating a dual barrier. Against low-basicity RH slag, such protective layers fail to form, leading to an accelerated penetration. This underscores that CMA applications must precisely match service environments.

Summary and Prospects

This review systematically analyzes the structure-property-processability relationships of CMA materials, highlighting the fundamental contradiction between their excellent performance and challenging densification. A strategic shift toward "performance adaptation and defect transformation" is proposed rather than pursuing densification at all costs, i.e., utilizing plate-like CMA grains as reinforcing phases in monolithic refractories, and exploiting decomposition behavior for lightweight structure design.

Future research directions include, 1) multi-scale mechanistic studies combining first-principles calculations, phase-field simulations, and in-situ characterization; 2) systematic investigation of structure-property relationships in CMA-based monolithic systems; and 3) exploration of novel composites and applications in emerging high-temperature processes. Through such integrated approaches, CMA materials are positioned to contribute significantly to the green transformation of high-temperature industries as environmentally friendly, high-performance refractories.

Key words

calcium oxide-magnesium oxide-aluminum oxide / anisotropic growth / densification / synthetic mechanism / refractories

引用本文

古晨伟, 王战民, 陈卢. CaO-MgO-Al₂O₃复合氧化物材料结构、性能与应用前景. 硅酸盐学报, 2026 , 54 (9) : 3264 -3273 . DOI: 10.14062/j.issn.0454-5648.20250773

Chenwei GU, Zhanmin WANG, Lu CHEN. Structure, Properties, and Application Prospects of CaO-MgO-Al₂O₃ Composite Oxide Materials[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (9) : 3264 -3273 . DOI: 10.14062/j.issn.0454-5648.20250773

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2026年第54卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250773

接收时间：2025-10-24
首发时间：2026-10-22
出版时间：2026-08-18

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收稿日期：2025-10-24
修回日期：2025-11-17

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作者信息

^1．河南科技大学材料科学与工程学院，河南洛阳 471000

^2．中钢集团洛阳耐火材料研究院有限公司，先进耐火材料全国重点实验室，河南洛阳 471000

通讯作者:

王战民（1966—），男，博士，教授级高级工程师。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 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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