熔融Sn-xSc合金在氮化硅陶瓷表面的反应润湿

doi:10.11949/0438-1157.20250563

摘要/Abstract

摘要：

针对氮化硅（Si₃N₄）陶瓷与金属钎焊中润湿性差，活性组元界面活性不足的问题，提出以Sc替代传统Ti活性组元，采用改良座滴法，系统地研究了Sn-xSc［x=1%，2%，2.5%，3%（原子分数）］合金在700~800℃范围内对Si₃N₄陶瓷的润湿行为。实验结果表明，随着活性元素Sc的引入，Sn-xSc/Si₃N₄体系的接触角显著降低，并且表现出对温度和Sc浓度的强烈依赖性。在800℃时，Sn-3%Sc/Si₃N₄体系的接触角降至0°，实现了完全润湿。通过界面微观结构分析发现，在800℃下Sn-3%Sc/Si₃N₄体系界面处形成了约1.3 μm厚的反应层，主要由ScN和ScSi化合物组成。此外，还发现前驱膜的形成机制符合快速吸附-薄层漫流机制。热力学和动力学分析表明，体系润湿性是由生成的ScN和ScSi决定的。这一发现为优化Sn-Sc合金在Si₃N₄陶瓷上的润湿性和界面结合提供了理论依据。

关键词: 界面, 反应润湿, 稀土元素, 动力学, 热力学

Abstract:

To address the poor wettability and insufficient interfacial activity of active components in brazing silicon nitride (Si₃N₄) ceramics to metals, we proposed replacing the traditional Ti active component with Sc. Using a modified sessile drop method, we systematically investigated the wetting behavior of Sn-xSc [x=1%, 2%, 2.5% and 3%(atomic fraction)] alloys on Si₃N₄ ceramics over the temperature range of 700—800℃. The experimental findings demonstrated that the incorporation of the active element Sc substantially decreased the contact angle of the Sn-xSc/Si₃N₄ system. The wetting performance exhibited a pronounced dependence on both temperature and Sc concentration. At 800℃, the contact angle of the Sn-3% Sc/Si₃N₄ system reduced to 0°, achieving complete wetting. Interfacial microstructural analysis revealed that a reaction layer approximately 1.3 μm thick formed at the Sn-3% Sc/Si₃N₄ interface at 800℃, primarily composed of ScN and ScSi compounds. Furthermore, the formation mechanism of the precursor film was identified as conforming to the rapid adsorption-thin layer diffusion mechanism. Thermodynamic and kinetic analyses indicated that the wetting behavior of the system was governed by the formation of ScN and ScSi. This investigation provides a theoretical foundation for enhancing the wetting and interfacial bonding of Sn-Sc alloys on Si₃N₄ ceramics.

Key words: interface, reactive wetting, rare earth element, kinetics, thermodynamics

中图分类号:

O 647.5

王淼, 林巧力. 熔融Sn-xSc合金在氮化硅陶瓷表面的反应润湿[J]. 化工学报, 2025, 76(11): 5998-6007.

Miao WANG, Qiaoli LIN. Reactive wetting of molten Sn-xSc alloy with silicon nitride ceramic surfaces[J]. CIESC Journal, 2025, 76(11): 5998-6007.

图/表 10

图1 Si3N4陶瓷基板表面的三维形貌和局部粗糙度示意图

Fig.1 Three-dimensional morphology and local roughness of the Si3N4 ceramic substrate surface

图2 实验装置照片和t=0时刻的图像

Fig.2 Photos of the experimental setup and the image at t=0

图3 接触角和铺展直径随时间变化

Fig.3 Contact angle and spreading diameter vary with time

图4 润湿实验后Sn-Sc熔滴的宏观形貌

Fig.4 The macroscopic morphology of Sn-Sc molten droplets after the wetting experiment

图5 润湿实验后的典型纵截面微观结构

Fig.5 The typical cross-sectional microstructure after the wetting experiment

图6 熔滴腐蚀去除后裸露界面的微观结构

Fig.6 The microstructure of the exposed interface after the droplet corrosion removal

图7 800℃ Sn-3%Sc/Si3N4体系的三相线前沿结构及元素分布谱图

Fig.7 Phase diagram and elemental distribution map of the triple line front of the 800℃ Sn-3%Sc/Si3N4 system

图8 熔滴腐蚀去除后所裸露的固/液界面的XRD谱图

Fig.8 XRD patterns of the solid/liquid interface exposed after the droplet corrosion removal

图9 不同温度下Sn-3%Sc/Si3N4体系的ln (cos θe-cos θd)/(cos θe-cos θ0)与时间t的函数关系

Fig.9 The functional relationship between ln cos(θe-cos θd)/(cos θe-cos θ0) and time t of the Sn-3%Sc/Si3N4 system at different temperatures

图10 动力学常数k与温度的Arrhenius曲线

Fig.10 The Arrhenius curve of kinetic constant k with respect to temperature

参考文献 31

[1]	Herrmann M, Klemm H, Schubert C. Silicon nitride based hard materials[M]//Handbook of Ceramic Hard Materials. Weinheim: Wiley-VCH Verlay GmbH, 2000: 749-801.
[2]	Vu C H, Seo D W, Kim H J, et al. Surface wetting properties of Si₃N₄/SiC ceramics by Cu alloys[J]. Key Engineering Materials, 2006, 306/307/308: 423-428.
[3]	Katz R N. Applications of silicon nitride based ceramics in the U.S[J]. MRS Online Proceedings Library, 1992, 287(1): 197-208.
[4]	Yuan Y, Li Z T, Cao L, et al. Modification of Si₃N₄ ceramic powders and fabrication of Si₃N₄/PTFE composite substrate with high thermal conductivity[J]. Ceramics International, 2019, 45(13): 16569-16576.
[5]	Zhang H, Yao D X, Zhu M, et al. Porous Si₃N₄ ceramics with uniform microstructure fabricated by in situ pre-gel casting combined with non-directional freeze-drying[J]. Journal of the European Ceramic Society, 2025, 45(10): 117369.
[6]	Chen J, Wei P, Mei Q, et al. The wettability of Y-Al-Si-O-N oxynitride glasses and its application in silicon nitride joining[J]. Journal of the European Ceramic Society, 2000, 20(14/15): 2685-2689.
[7]	Ghosh S, Chakraborty R, Dandapat N, et al. Characterization of alumina-alumina/graphite/monel superalloy brazed joints[J]. Ceramics International, 2012, 38(1): 663-670.
[8]	Zhao Z L, Li Y F, Zheng Q L, et al. Revealing the mechanism of abruptly dropping of the wetting angle for the cast iron and zirconia ceramic system[J]. Materials & Design, 2024, 244: 113232.
[9]	Wang H J, Fu W, Xue Y D, et al. Wettability and spreading behavior of Sn-Ti alloys on Si₃N₄ [J]. Crystals, 2022, 12(7): 921.
[10]	Kim D H, Hwang S H, Chun S S. The wetting, reaction and bonding of silicon nitride by Cu-Ti alloys[J]. Journal of Materials Science, 1991, 26(12): 3223-3234.
[11]	Shao N, Dai J W, Li G Y, et al. Effect of La on the wettability of Al₂O₃ by molten aluminum[J]. Materials Letters, 2004, 58(14): 2041-2044.
[12]	Yang L L, Shen P, Cong X S, et al. Wetting and reaction of molten La with poly- and mono-crystalline MgO at 1323K[J]. Journal of Materials Science, 2013, 48(2): 960-966.
[13]	潘复生, 张静, 陈晖, 等. 稀土对Al-Zn-Mg-Cu/Al₂O₃陶瓷界面润湿性的影响[J]. 复合材料学报, 1998, 15(1): 46-51.
	Pan F S, Zhang J, Chen H, et al. Effect of rare earth additions on the wettability of an Al-Zn-Mg-Cu/Al₂O₃ system[J]. Acta Materiae Compositae Sinica, 1998, 15(1): 46-51.
[14]	Naidich Y V. Advance in the theory of ceramics/liquid metal systems wettability. Peculiarity of contact processes for transition and non-transition metals [J]. Адгезия расплавов и пайка материалов, 2013(46): 3-62.
[15]	Xie K B, Lin Q L, Wang M, et al. Study on wetting mechanism of Sn₃Sc alloy on silica and sapphire surfaces[J]. Surfaces and Interfaces, 2024, 51: 104671.
[16]	赵东亮, 高岭. 功率模块用陶瓷覆铜基板研究进展[J]. 真空电子技术, 2014(5): 17-20, 24.
	Zhao D L, Gao L. Development of research on bonding copper to ceramic substrates for power module[J]. Vacuum Electronics, 2014(5): 17-20, 24.
[17]	Ciprian L, Mihalic S, Lüttich C, et al. Thermal expansion coefficient of ScN(111) thin films grown on Si(111) determined by X-ray diffraction[J]. Applied Physics Letters, 2024, 124(5): 052203.
[18]	Luz A P, Ribeiro S. Wetting behaviour of silicon nitride ceramics by Ti-Cu alloys[J]. Ceramics International, 2008, 34(2): 305-309.
[19]	Song X G, Passerone A, Fu W, et al. Wetting and spreading behavior of Sn-Ti alloys on SiC[J]. Materialia, 2018, 3: 57-63.
[20]	Iddaoudi A, Selhaoui N, Ait Amar M, et al. Thermodynamic assessment of the Sc-Sn system[J]. Calphad, 2013, 41: 71-75.
[21]	Safarian J, Kolbeinsen L, Tangstad M. Thermodynamic activities in silicon binary melts[J]. Journal of Materials Science, 2012, 47(14): 5561-5580.
[22]	Qin A N, Liu D D, Chen C, et al. Heat contents of Sc₅Si₃ and ScSi intermetallics and thermodynamic modeling of the Sc-Si system[J]. Journal of Thermal Analysis and Calorimetry, 2015, 119(2): 1315-1321.
[23]	Bascom W, Cottington R, Singleterry C. Dynamic Surface Phenomena in the Spontaneous Spreading of Oils on Solids[M]. Columbus, Ohio: ACS Publications, 1964: 355-379.
[24]	Hardy W B. Ⅲ. The spreading of fluids on glass[J]. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, 1919, 38(223): 49-55.
[25]	庄鸿寿,罗格夏特. 高温钎焊[M]. 北京: 国防工业出版社, 1989: 166-168.
	Zhuang H S, Lugscheider E. High Temperature Brazing[M]. Beijing: National Defense Industry Press, 1989: 166-168.
[26]	Xian A P. Precursor film of tin-based active solder wetting on ceramics[J]. Journal of Materials Science, 1993, 28(4): 1019-1030.
[27]	Eustathopoulos N, Nicholas M G, Drevet B. Wettability at High Temperatures[M]. UK: Elsevier, 1999: 239-242.
[28]	Niessen A K, de Boer F R, Boom R, et al. Model predictions for the enthalpy of formation of transition metal alloys Ⅱ[J]. Calphad, 1983, 7(1): 51-70.
[29]	Dezellus O, Hodaj F, Eustathopoulos N. Progress in modelling of chemical-reaction limited wetting[J]. Journal of the European Ceramic Society, 2003, 23(15): 2797-2803.
[30]	Dezellus O, Eustathopoulos N. Fundamental issues of reactive wetting by liquid metals[J]. Journal of Materials Science, 2010, 45(16): 4256-4264.
[31]	Lide D R, Haynes W M. Handbook of Chemistry and Physics, Internet Version[M]. Boca Raton: CRC Press, 2005: 1291-1295.

相关文章 15

[1]	段浩磊, 陈浩远, 梁坤峰, 王林, 陈彬, 曹勇, 张晨光, 李硕鹏, 朱登宇, 何亚茹, 杨大鹏. 纯电动车热管理系统低GWP工质替代方案性能分析与综合评价[J]. 化工学报, 2025, 76(S1): 54-61.
[2]	郭松源, 周晓庆, 缪五兵, 汪彬, 耑锐, 曹庆泰, 陈成成, 杨光, 吴静怡. 火箭上升段含多孔板液氧贮箱增压输运数值研究[J]. 化工学报, 2025, 76(S1): 62-74.
[3]	臧子晴, 李修真, 谈莹莹, 刘晓庆. 分凝器对两级分离自复叠制冷循环特性影响研究[J]. 化工学报, 2025, 76(S1): 17-25.
[4]	曹庆泰, 郭松源, 李建强, 蒋赞, 汪彬, 耑锐, 吴静怡, 杨光. 负过载下多孔隔板对液氧贮箱蓄液性能的影响研究[J]. 化工学报, 2025, 76(S1): 217-229.
[5]	李银龙, 刘国强, 晏刚. 分馏与闪蒸分离耦合自复叠制冷循环性能分析[J]. 化工学报, 2025, 76(S1): 26-35.
[6]	朱腾飞, 刘晔. 低GWP制冷剂在新能源汽车空调应用性能分析[J]. 化工学报, 2025, 76(S1): 343-350.
[7]	吴迪, 胡斌, 姜佳彤. R1233zd（E）高温热泵实验研究与应用分析[J]. 化工学报, 2025, 76(S1): 377-383.
[8]	吴馨, 龚建英, 李祥宇, 王宇涛, 杨小龙, 蒋震. 超声波激励疏水表面液滴运动的实验研究[J]. 化工学报, 2025, 76(S1): 133-139.
[9]	苏伟, 赵大海, 金旭, 刘忠彦, 李静, 张小松. 吸湿液滴与混合润湿性表面协同抑霜特性研究[J]. 化工学报, 2025, 76(S1): 140-151.
[10]	赵维, 邢文乐, 韩朝旭, 袁兴中, 蒋龙波. g-C₃N₄基非金属异质结光催化降解水中有机污染物的研究进展[J]. 化工学报, 2025, 76(9): 4752-4769.
[11]	刘卓龙, 甘云华, 屈可扬, 陈宁光, 潘铭晖. 均匀电场对生物柴油小尺度射流扩散燃烧特性影响研究[J]. 化工学报, 2025, 76(9): 4800-4808.
[12]	王偲凡, 栗一帆, 陈江波, 周桓. 碳酸盐型卤水Li⁺， Na⁺， K⁺， CO $32$ ^--H₂O体系热力学与相图模型化[J]. 化工学报, 2025, 76(9): 4770-4785.
[13]	李相海, 赖德林, 孔纲, 周健. 双仿生表面水下疏油协同机制的分子动力学模拟研究[J]. 化工学报, 2025, 76(9): 4551-4562.
[14]	曾宁, 郭振江, 陈建华, 张子轩, 曾玉娇, 肖炘, 刘松林, 薛绍秀, 周智武, 卢振明, 王利民. 二水湿法磷酸工艺中非水溶磷的分子动力学模拟[J]. 化工学报, 2025, 76(9): 4539-4550.
[15]	徐佳琪, 张文君, 余燕萍, 苏宝根, 任其龙, 杨启炜. 热等离子体重整炼厂气制合成气过程数值模拟与实验研究[J]. 化工学报, 2025, 76(9): 4462-4473.