氮化硅粉体制备技术及粉体质量研究进展

doi:10.11949/0438-1157.20210866

摘要/Abstract

摘要：

氮化硅(Si₃N₄)具有优异的物化性能，在国防、电子信息等关键领域都占据重要的地位。高质量粉体是制备高性能Si₃N₄陶瓷的首要前提。通常高质量Si₃N₄粉体需要满足粒径细、分布窄、α相含量高、杂质含量低等条件。基于合成反应体系综述了当前国内外制备Si₃N₄粉体的方法，着重从强化传热与传质角度介绍了改善粉体质量的研究进展，并介绍了当前工业生产现状，展望了高质量Si₃N₄粉体制备技术的发展趋势和方向。

关键词: 氮化硅, 粉体技术, 碳热氮化法, 硅粉直接氮化法, 化学气相沉积法, 硅胺前体转化法, 合成机理

Abstract:

Silicon nitride (Si₃N₄) has excellent physical and chemical properties and occupies an important position in key fields such as national defense and electronic information. High quality Si₃N₄ powders are the primary prerequisite for the preparation of high performance Si₃N₄ ceramics. The high-quality powder requisites the conditions of fine particle size with narrow distribution, high α phase, low impurity and so on. The research advances in preparation technology of silicon nitride powder are summarized from the point of the synthesis reaction system, with the emphasis on summarizing the progress of the improvement of powder quality by enhancing heat and mass transfer. In addition, the present situations of industrial manufacture are introduced, and the development trend and direction of the preparation technology of high quality Si₃N₄ powder are also prospected.

Key words: silicon nitride, powder technology, carbo-thermal nitriding method, silicon directly nitriding method, chemical vapor deposition method, silamine precursor conversion method, synthesis mechanism

中图分类号:

TQ 174

向茂乔, 耿玉琦, 朱庆山. 氮化硅粉体制备技术及粉体质量研究进展[J]. 化工学报, 2022, 73(1): 73-84.

Maoqiao XIANG, Yuqi GENG, Qingshan ZHU. Research advances in preparation technology and quality of silicon nitride powder[J]. CIESC Journal, 2022, 73(1): 73-84.

图/表 9

图1 SiO2-C-N2体系在不同温度和分压下的优势区域图(采用HSC 6.0 热力学分析软件计算)

Fig.1 Predominance area diagram of the SiO2-C-N2 system under different temperature and partial pressure (calculated by HSC 6.0 thermodynamic analysis software)

图2 SiO2-C-N2体系生成产物图

Fig.2 Product of the SiO2-C-N2 system

表1 国内外采用碳热氮化SiO2生产Si3N4粉体质量

Table 1 The quality of Si3N4 powders synthesized by carbothermal nitriding of SiO2 in the domestic and overseas

企业	α相/%(质量)	C/%(质量)	O/%(质量)	Fe/%(质量)	Al/%(质量)	Mg/%(质量)	Ca/%(质量)
日本东芝	约96	0.09~0.8	0.9~3.5	约0.0044	约0.0006	约0.0002	0.0018~0.0052
日本住友	约99	0.6~1.3	1.0~4.1	约0.003	约0.0022	约0.0009	约0.002
臻璟新材	约95.3	约0.9	约1.5	<0.01	<0.01	<0.01	<0.01
凯新特材	约90	0.2~3.8	约1.3	<0.01	<0.01	<0.01	<0.01

图3 氮化反应过程示意图[24]

Fig.3 Schematic diagram of the process of nitridation reaction[24]

表2 Si和α-Si3N4不同取向时产生的应变［35］

Table 2 Misfit strain between Si and α-Si3N4 with different orientation［35］

取向关系	失配应变/%
α-Si₃N₄ Si	失配应变/%
(2 $1 ˉ$ $1 ˉ$ 0) // (1 1 0)	1.8
(0 3 $3 ˉ$ 0) // (1 1 2)	1.8
(2 $1 ˉ$ $1 ˉ$ 1) // (1 1 1)	2.2
(3 $1 ˉ$ $2 ˉ$ 1) // (2 1 0)	-4.1
(0 0 0 2) // (1 1 1)	10.8

表2 Si和α-Si3N4不同取向时产生的应变［35］

Table 2 Misfit strain between Si and α-Si3N4 with different orientation［35］

取向关系	失配应变/%
α-Si₃N₄ Si	失配应变/%
(2 $1 ˉ$ $1 ˉ$ 0) // (1 1 0)	1.8
(0 3 $3 ˉ$ 0) // (1 1 2)	1.8
(2 $1 ˉ$ $1 ˉ$ 1) // (1 1 1)	2.2
(3 $1 ˉ$ $2 ˉ$ 1) // (2 1 0)	-4.1
(0 0 0 2) // (1 1 1)	10.8

图4 硅粉直接氮化产品TEM图

Fig.4 TEM image of product by the direct nitridation of Si powder

图5 自蔓延燃烧反应合成氮化硅反应示意图及产品形貌图

Fig.5 Schematic diagram and micrograph of Si3N4 production through self -propagating combustion method

表3 国内外采用自蔓延燃烧技术生产Si3N4粉体质量

Table 3 The quality of Si3N4 powders synthesized by self-propagating combustion technology in the domestic and overseas

企业	α相/%(质量)	Si/%(质量)	O/%(质量)	Fe/%(质量)	Al/%(质量)	Ca/%(质量)
H?gan?s(H.C.Starck)	90	≤0.9	1.3	0.0005	0.001	0.0005
ALZChem	93	≤0.2	≤1.0	0.0015	0.0001	0.0008
烟台同立高科	90	≤0.1	≤1.6	0.0002	0.0004	0.0003
埃克诺新材料	92	0.1	1.3	0.0005	0.0005	0.0005
河北高富	80	0.1	1.0	0.01	0.01	0.01
淄博恒世科技	90	0.1	≤0.6	0.0003	0.0003	0.0003
青岛瓷兴	>90	0.2	≤1.5	≤0.0005	≤0.0005	≤0.0005
中材高新	93	0.2	≤1.5	≤0.00002	<0.01	<0.01
德盛特种陶瓷	90	0.025	1.2	0.002	—	0.001
北京中联阳光	90	0.15	≤1.0	0.001	0.0005	0.0005
泰晟新材料	92	1.2	1.5	<0.01	0.003	0.001
安赛美精细陶瓷	93.5	0.5	1.5	0.06	0.01	0.008

图6 日本宇部液氨法制备氮化硅产品流程及产品图

Fig.6 Flow chart and microscopic image for preparing high quality Si3N4 powder by UBE industry

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