硅酸盐学报

Al-Si-Al₂O₃复合材料中多型体硅铝氧氮致密层的合成

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马晨红 ¹ , 李勇 ¹ , 罗华明 ² , 职佳爽 ¹ , 高原 ¹ , 高长贺 ²

硅酸盐学报 | 碳中和与耐火材料专题—研究论文 2025,53(9): 2550-2558

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硅酸盐学报 |碳中和与耐火材料专题—研究论文 2025 , 53 (9) : 2550 -2558

Al-Si-Al₂O₃复合材料中多型体硅铝氧氮致密层的合成

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马晨红¹, 李勇¹, 罗华明², 职佳爽¹, 高原¹, 高长贺²

作者信息

^1．北京科技大学材料科学与工程学院，北京 100083

^2．北京金隅集团股份有限公司，北京 100013

通讯作者:

高长贺（1977—），男，博士，教授。

作者简介:

马晨红（1993—），女，博士，讲师。

Synthesis of Dense Layer of 21R-SiAlON in Al-Si-Al₂O₃ Composite Refractory

Chenhong MA¹, Yong LI¹, Huaming LUO², Jiashuang ZHI¹, Yuan GAO¹, Changhe GAO²

Affiliations

^1.School of Material Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China

^2.BBMG Corporation, Beijing, 100013, China

Corresponding Author:

GAO Changhe (1977-), male, Ph.D., Professor. E-mail: gaochanghe@bbmg.com.cn

MA Chenhong (1993-), female, Ph.D., Lecturer. E-mail: machenhong1993@163.com

出版时间: 2025-09-20 doi: 10.14062/j.issn.0454-5648.20240703

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摘要

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基于高温下金属Al、Si对氧分压敏感特性，将Al-Si-Al₂O₃复合材料在1550 ℃氮气气氛下保温3 h烧成，制备了“多型体硅铝氧氮（21R-SiAlON）致密层AlN-SiC固溶体增强刚玉多孔结构层”梯度功能材料。结合反应热力学计算，研究了其合成机理。结果表明：试样表面的氧分压较高，金属铝、硅的“活性氧化-间接氮化”为主导反应机制。表面层金属铝、硅优先发生活性氧化反应，生成Al₂O、SiO等气态亚氧化物，使氧分压降低。高温低氧分压氮气气氛下，体系中金属铝、硅和活性氧化铝微粉进一步与氮气发生反应，生成21R-SiAlON。在浓度梯度作用下，Al₂O、SiO气相扩散至试样外层氮化沉积，促进了片状21R-SiAlON的交错生长发育，形成致密功能层（气孔率<4%）；随着外层铝、硅的活性氧化对O₂的逐层消耗，试样内部的氧分压降至极低值，金属铝、硅的“直接氮化/碳化”反应机制成为主导。试样内部的铝、硅直接与氮气和酚醛树脂残碳反应，原位生成粒状AlN-SiC固溶体增强相，形成高强度多孔结构（气孔率约为15%），缓解温度梯度导致的应力集中。

关键词

功能梯度耐火材料 / 铝-硅-刚玉复合材料 / 硅铝氧氮致密层 / 反应机理

Abstract

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Introduction

Refractories are important supporting materials for high-temperature industries. During high-temperature service, refractories are subjected to severe thermal shock, complex chemical corrosion, and mechanical wear, and must balance superior properties like thermal shock resistance, corrosion resistance, and high strength. However, the key service properties of refractories are often interdependent, such as superior corrosion resistance requiring a dense structure, which sacrifices the thermal shock resistance of the material. The superior thermal shock resistance requires a certain amount of pores to relieve thermal stress, but this reduces the strength and corrosion resistance of the material. Developing novel refractories with gradient composition and structure based on the different service micro-environments of refractory products in different regions, such as cold and hot surfaces, to enhance key service performance in different zones is an important research direction. In this paper, a gradient functional material with "21R-SiAlON dense layer AlN-SiC solid solution reinforced corundum porous structure" was developed based on the sensitivity of metal Al and Si to oxygen partial pressure at high temperatures.

Methods

Tabular alumina (3-1 mm, 1-0 mm; w(Al₂O₃) > 99.31%; Anmai Aluminum Co., China), α-Al₂O₃ powder (≤5 μm; w(Al₂O₃) > 99.28%), active α-Al₂O₃ powder (≤ 5 μm; w(Al₂O₃)>99.28%; Anmai Aluminum Co., China), metal aluminum powder (≤ 45 μm; w(Al)>99.77%, Henan Yuayang Co., China) and silicon powder (≤ 45 μm; w(Si)>99.52%; Yingkou Xianren Island Taihe Silicon Co., China) were used as raw materials, with phenolic resin (residual carbon of about 56%, Shengquan Group, China) as a binder. In the preparation, the weighted raw materials were mixed in a planetary mixer for 40 min to obtain uniform mixed slip. Afterwards, Al-Si-Al₂O₃ composite green brick samples (with the sizes of 230 mm × 113 mm × 65 mm) were obtained by compacting the mixed slip under 200 MPa by a model 630 t friction press. After natural dehydration for 24 h, the sample bricks were dried in a tunnel kiln at 200 ℃ for 12 h. The dried samples were nitriding sintered in a high-temperature nitriding furnace at 1550 ℃ for 3 h.

The phase composition of the sintered samples was analyzed by X-ray diffraction (XRD; Ultima IV, Rigaku Co., Japan). The microstructures of the samples were analyzed by scanning electron microscopy (SEM) in a model NOVA NANOSEM 450 electron microscope (FEI Co., USA). The pore structure of the samples was determined by a model FF35 CT microfocus industrial computered tomography (CT, YXLON International GmbH, Germany).

Results and discussion

Based on the sensitivity of metal Al and Si to oxygen partial pressure at high temperatures, Al-Si-Al₂O₃ composites are sintered in a nitrogen atmosphere at 1550 ℃ for 3 h to prepare a gradient functional material, which is composed of "21R-SiAlON dense layer-AlN-SiC solid solution reinforced corundum with a porous structure". The synthesis mechanism is analyzed by CT, SEM, and XRD combined with thermodynamic analysis. The results indicate that P(O₂) on the surface of the sample is higher, where the"active oxidation to indirect nitridation"mechanism of Al and Si is predominated. Al and Si on the surface layer preferentially undergo active oxidation, generating gaseous sub oxides such as Al₂O and SiO, and reducing the local P(O₂). 21R-SiAlON is formed via a reaction of metal Al, Si, active α-Al₂O₃ powder and N₂. Under the action of concentration gradient, the preformed gaseous sub-oxides diffuse into the surface layer and react with nitrogen to form 21R-SiAlON, thus promoting the staggered growth of sheet-like 21R-SiAlON and ultimately forming a dense layer (with porosity<4%), which is constructive to the corrosion resistance of the material. As the active oxidation of outer Al and Si consumes O₂ layer by layer, P(O₂) inside the brick becomes extremely low, and the "direct nitriding/carbonization" reaction mechanism of Al and Si becomes dominant. Al and Si inside the brick react directly with nitrogen and residual carbon of phenolic resin, generating granular AlN-SiC solid solution reinforcement phase in-situ, forming a high-strength porous structure (with a porosity of 15%), which can alleviate a stress concentration caused by temperature gradient and improve thermal shock resistance.

Conclusions

A gradient functional material with a "21R-SiAlON reinforced denselayer—AlN-SiC solid solution reinforced porous structure" was prepared via nitriding Al-Si-Al₂O₃ composite in a nitrogen atmosphere at 1550 ℃ for 3 h. During sintering, there were two reaction mechanisms for metal Al and Si in different regions of the outer and inner layers of the sample, i.e., the "active oxidation to indirect nitridation" mechanism and the "direct nitridation/carbonization" mechanism in the outer and inner layers resulting in a gradient change in the composition and structure of the material. In the outer layer of the sample, the oxygen partial pressure was higher, and metal Al and Si preferentially underwent an active oxidation, generating gaseous sub oxides (i.e., Al₂O, AlO, SiO, etc.), which reduced the oxygen partial pressure. As the oxygen partial pressure decreased, Al powder, Si powder, and α-Al₂O₃ micro powder reacted with nitrogen to form 21R-SiAlON. Gaseous metastable phases such as Al₂O and SiO diffused to the outer layer of the sample to deposition, further promoting the staggered growth and development of sheet-like 21R-SiAlON, forming a dense layer. The porosity of this dense layer was less than 4%, and it was mainly composed of closed micropores. With the consumption of O₂ by the outer metal Al and Si of the sample, the oxygen partial pressure inside the sample was reduced to an extremely low level. Metal Al and Si directly reacted with N₂ and residual carbon of phenolic resin, generating AlN-SiC solid solution reinforcement phase in-situ. The porosity inside the sample was approximately 15%.

Key words

functional gradient refractory / aluminum-silicon-corundum composite / sialon dense layer / reaction mechanism

引用本文

马晨红, 李勇, 罗华明, 职佳爽, 高原, 高长贺. Al-Si-Al₂O₃复合材料中多型体硅铝氧氮致密层的合成. 硅酸盐学报, 2025 , 53 (9) : 2550 -2558 . DOI: 10.14062/j.issn.0454-5648.20240703

Chenhong MA, Yong LI, Huaming LUO, Jiashuang ZHI, Yuan GAO, Changhe GAO. Synthesis of Dense Layer of 21R-SiAlON in Al-Si-Al₂O₃ Composite Refractory[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (9) : 2550 -2558 . DOI: 10.14062/j.issn.0454-5648.20240703

基金

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国家自然科学基金(52402019)

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2025年第53卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240703

接收时间：2024-11-04
首发时间：2026-10-21
出版时间：2025-09-20

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出版历史

收稿日期：2024-11-04
修回日期：2024-11-12

基金

国家自然科学基金(52402019)

作者信息

^1．北京科技大学材料科学与工程学院，北京 100083

^2．北京金隅集团股份有限公司，北京 100013

通讯作者:

高长贺（1977—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240703

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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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