汪雪峰， 刘鹏飞， 韩召， 李杰
安徽工业大学 冶金工程学院， 安徽 马鞍山 243000
引用格式：
汪雪峰， 刘鹏飞， 韩召， 等. 硅亚胺球磨制备等轴状氮化硅颗粒［J］. 中国粉体技术， 2026， 32（6）： 1-11.
WANG Xuefeng， LIU Pengfei， HAN Zhao， et al. Preparation of equiaxed silicon nitride powders by silicon imine ball milling［J］. China Powder Science and Technology， 2026， 32（6）： 1-11.
收稿日期：2025-01-22， 修回日期： 2025-02-20，上线日期：2026-05-16。
基金项目：国家自然科学基金项目，编号：52074003。
第一作者： 汪雪峰（2000—），男，硕士生，研究方向为高能球磨法制备氮化硅颗粒。E-mail：1954811856@qq.com。
通信作者： 韩召（1977—），男，副教授，博士，博士生导师，研究方向为氮化硅颗粒制备及应用技术。E-mail：authan@163.com。
摘要： 【目的】 制备用于氮化硅（Si3N4）陶瓷的高品质等轴状氮化硅颗粒，解决氮化硅颗粒形貌及粒径难以控制的问题。 【方法】 以硅亚胺（Si（NH）2）为原料，利用高能球磨处理，通过高温热解制备具有规则形貌的Si3N4颗粒； 探讨不同球磨工艺参数对Si3N4颗粒形貌和粒径的影响规律。 【结果】 高能球磨处理后，Si3N4粉末由不规则形貌的小颗粒转变为表面光滑、形貌规则的六棱柱状大颗粒；随着球磨的进行，Si3N4颗粒粒径呈先减小后增大的趋势，在转速为200 r/min时，球料比（介质与物料的质量比，下同）为20，球磨时间2 h的条件下，得到表面光滑、形貌规则且平均粒径约为823 nm的α相Si3N4颗粒； Si3N4颗粒的生长过程分为成核和生长2个阶段，Si（NH）2经过球磨处理后，非晶化程度增强，且球磨时的机械力作用下，Si（NH）2中形成微量结晶的核心； 球磨阶段产生的结晶核心为热解过程中非晶Si3N4分解产生的气相产物提供足够的形核位点，诱导Si3N4沿结晶的核心生长，最终形成等轴状形貌规则的Si3N4颗粒。 【结论】 高能球磨Si（NH）2可以加速非晶Si3N4形核速率并提供形核位点，是调节Si3N4粉末颗粒形貌与粒度的关键。
关键词： 硅亚胺； 高能球磨； 氮化硅； 机械力
Abstract
Objective As applications of silicon nitride ceramics expand， the demand for high-quality silicon nitride powders grows. This paper focuses on controlling the morphology and particle size of silicon nitride powder to successfully prepare high-quality equiaxed silicon nitride powder for ceramics.
Methods Silicon nitride （Si3N4） powders with regular morphology were prepared using silicon imine （Si（NH）2） as the raw material through high-energy ball milling and high-temperature pyrolysis. The effects of different ball milling parameters on the morphology and particle size of Si3N4 powders were investigated. First， the Si（NH）2 powder was dry-milled in a horizontal planetary ball mill under different ball-to-powder weight ratios， milling times， and milling velocities. The ball milling process was conducted in an Ar atmosphere， using Si3N4 ceramic balls as the ball milling medium. After ball milling， the powder was sieved and encapsulated in a graphite crucible under Ar protection. Finally， the crucible was placed in a tube furnace and heated to a certain temperature at a heating rate of 5 °C/min under a flowing nitrogen atmosphere. The holding time was 2 h， and the Si3N4 powder was obtained after cooling to room temperature within the furnace.
Results and Discussion High-energy ball milling treatment significantly impacted the morphology and particle size of Si3N4 powder. After ball milling， the powder changed from small particles with irregular morphology to large hexagonal prism particles with smooth surfaces and regular morphology. As ball milling progressed， the particle size of Si3N4 powder initially decreased and then increased. When the rotation speed was 200 r/min， the ball-to-powder weight ratio （mass ratio） was 20， and the ball milling time was 2 h， α-phase Si3N4 powder with smooth surfaces， regular morphology， and an average particle size of about 823 nm was obtained. The growth process of Si3N4 powder particles was divided into two stages： nucleation and growth. After ball milling， the degree of amorphization of Si（NH）2 increased， and the mechanical force during ball milling formed trace crystalline cores in Si（NH）2. These crystalline cores， generated during the ball milling stage， provided sufficient nucleation sites for the gas phase products produced by the decomposition of amorphous Si3N4 during the pyrolysis process. This induced Si3N4 to grow along the crystalline cores， ultimately forming Si3N4 powder with equiaxed regular morphology.
Conclusion High-energy ball milling Si（NH）2 accelerates the nucleation rate of amorphous Si3N4 and provides nucleation sites， which is key to adjusting the morphology and particle size of Si3N4 powder particles. The study provides a new reference for high-end Si3N4 powder preparation and supports China’s raw material capabilities in key areas.
Keywords： silicon imide； high-energy ball milling； silicon nitride； mechanical force
参考文献（References）
［1］WANG W X， LI D H， LIU Z C， et al. Strong piezoelectricity in nanosized silicon nitride prepared by laser-induced chemical vapor deposition ［J］. Applied Physics Letters， 1993， 62（3）： 321-322.
［2］XIE T， WU G S， GENG B Y， et al. A simple route to large scale synthesis of crystalline α-Si3N4 nanowires ［J］. Applied Physics A， 2005， 80（5）： 1057-1059.
［3］DAI Q J， HE D H， MENG F C， et al. Dielectric constant， dielectric loss and thermal conductivity of Si3N4 ceramics by hot pressing with CeO2-MgO as sintering aid ［J］. Materials Science in Semiconductor Processing， 2021， 121： 105409.
［4］LIU W， TONG W X， HE R X， et al. Effect of the Y2O3 additive concentration on the properties of a silicon nitride ceramic substrate ［J］. Ceramics International， 2016， 42（16）： 18641-18647.
［5］LEE S M， KIM H N， KO J W， et al. Experimental study on ELID grinding of silicon nitride ceramics for G5 class bearing balls ［J］. Applied Sciences-Basel， 2023， 13（19）：10584.
［6］LV X A， HUANG J W， DONG X F， et al. Influence of α-Si3N4 coarse powder on densification， microstructure， mechanical properties， and thermal behavior of silicon nitride ceramics ［J］. Ceramics International， 2023， 49（13）： 21815-21824.
［7］ZHANG X Y， HUO W L， QI F， et al. Ultralight silicon nitride ceramic foams from foams stabilized by partially hydrophobic particles ［J］. Journal of the American Ceramic Society， 2016， 99（9）： 2920-2926.
［8］HIROSAKI N， OGATA S， KOCER C， et al. Molecular dynamics calculation of the ideal thermal conductivity of single-crystal α-and β- Si3N4［J］. Physical Review B， 2002， 65（13）： 134110.
［9］FUKASAWA T， DENG Z Y， ANDO M， et al. Synthesis of porous silicon nitride with unidirectionally aligned channels using freeze-drying process ［J］. Journal of the American Ceramic Society， 2002， 85（9）： 2151-2155.
［10］JIANG G P，YANG J F，GAO J Q，et al. Porous silicon nitride ceramics prepared by extrusion using starch as binder ［J］. Journal of the American Ceramic Society， 2008， 91（11）： 3510-3516.
［11］YAMAO T， HONDA M， JIDA S， et al. Silicon nitride powder， silicon nitride sintered body and circuit substrate， and production method for said silicon nitride powder： US Patent 10，399，854［P］. 2019-09-03.
［12］SHIBATA K， OHMARU T， YAMAO T， et al. Silicon nitride powder production method， silicon nitride powder， silicon nitride sintered body and circuit substrate using same： US Patent 9，085，462［P］. 2015-07-21.
［13］LANGE H， WÖTTING G， WINTER G. Silicon nitride：from powder synthesis to ceramic materials ［J］. Angewandte Chemie： International Edition in English， 1991， 30（12）： 1579-1597.
［14］YAO G S， LI Y， JIANG P， et al. Formation mechanisms of Si3N4 and Si2N2O in silicon powder nitridation ［J］. Solid State Sciences， 2017， 66： 50-56.
［15］CUI W， LI F， TIAN Z B， et al. Coarse-grained β-Si3N4 powders prepared by combustion synthesis ［J］. Journal of the American Ceramic Society， 2021， 104（7）： 2919-2923.
［16］GE Y Y， WANG Q， CUI W， et al. Crystal growth in the combustion synthesis of α-Si3N4 using Si with different particle sizes ［J］. Journal of the American Ceramic Society， 2015， 98（10）： 3398-3403.
［17］ZHAO S， DU S M， SUN S Y， et al. Synthesis of spherical Si3N4 powders by liquid-phase modified carbothermal reduction and nitridation ［J］. Journal of the American Ceramic Society， 2024， 107（1）： 16-23.
［18］郗威， 周杨杨， 刘鹏飞， 等. 球磨介质对氮化硅粉体的微观形貌和表面氧化硅层的影响［J］. 中国粉体技术， 2023， 29（6）： 82-90.
XI W， ZHOU Y Y， LIU P F， et al. Effect of ball milling medium on morphology and surface silicon oxide layer of silicon nitride powder［J］. China Powder Science and Technology， 2023， 29（6）： 82-90.
［19］HU Z L， ZHU T B， WU W W， et al. Growth mechanism of α-Si3N4 submicron rods prepared from amorphous Si3N4 powders ［J］. Ceramics International， 2018， 44（17）： 22003-22007.
［20］YAMADA T， KAWAHITO T， IWAI T. Crystallization of amorphous Si3N4 prepared by the thermal decomposition of Si （NH）2［J］. Journal of Materials Science Letters， 1983， 2： 275-278.
［21］DORN F W， KRQUSE W， SCHRÖDER F. Particle size control during production of ceramic nitride powders［J］. Advanced Materials， 1992， 4（3）： 221-224.
［22］HU Z L， LIU J， XIE Z P. Synthesis of α-Si3N4 whiskers or equiaxed particles from amorphous Si3N4 powders ［J］. Ceramics International， 2020， 46（15）： 23734-23741.
［23］LIU P F， XI W， LI Y， et al. Synthesis of equiaxed Si3N4 from Si（NH）2 by adding seeds formed by in situ nitridation of silicon［J］.Ceramics International， 2024， 50（16）： 28411-28418.
［24］CHEN Y， WILLIAMS J S， CAMPBELL S J， et al. Increased dissolution of ilmenite induced by high-energy ball milling ［J］. Materials Science and Engineering： A， 1999， 271（1/2）： 485-490.
［25］HUANG Y J， LAI C H， WU P W， et al. Fabrication of large-area colloidal crystals by electrophoretic deposition in vertical arrangement［J］. Electrochemical and Solid-state Letters， 2008， 11（12）： 20-22.
［26］Liao C-H， Hung P-S， Cheng Y， et al. Combination of microspheres and sol-gel electrophoresis for the formation of large-area ordered macroporous SiO2 ［J］. Electrochemistry Communications， 2017， 85： 6-10
