Kovar合金的可控氧化及其与硼硅玻璃润湿性研究

硅酸盐通报 ›› 2024, Vol. 43 ›› Issue (11): 4215-4223.

Kovar合金的可控氧化及其与硼硅玻璃润湿性研究

郭宏伟¹, 聂栋¹, 王毅¹, 刘密¹, 朱南沺¹, 郭首一¹, 高依博¹, 赵志龙²

1.陕西科技大学材料科学与工程学院,西安 710021;
2.东旭集团有限公司,北京 100036

收稿日期:2024-04-28 修订日期:2024-07-28 出版日期:2024-11-15 发布日期:2024-11-21
作者简介:郭宏伟(1979—),男,博士,副教授。主要从事电子玻璃与封装的研究。E-mail:03guohongwei@163.com
基金资助:
国家重点研发计划(2017YFB0310201)

Controllable Oxidation of Kovar Alloy and Wetting Performance with Borosilicate Glass

GUO Hongwei¹, NIE Dong¹, WANG Yi¹, LIU Mi¹, ZHU Nantian¹, GUO Shouyi¹, GAO Yibo¹, ZHAO Zhilong²

1. School of Materials Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China;
2. Dongxu Group Co., Ltd., Beijing 100036, China

Received:2024-04-28 Revised:2024-07-28 Published:2024-11-15 Online:2024-11-21

摘要/Abstract

摘要： 本文在不同氧化气氛条件下对Kovar合金进行高温氧化处理,优化得到Kovar合金最佳氧化工艺,并与硼硅玻璃进行润湿试验和封接试验,同时运用XRD、XPS、SEM、EDS等分析手段对氧化成分和封接界面进行机理分析。结果表明,高温下Fe、Co、Ni元素均参与了氧化反应,Kovar合金氧化动力学遵循抛物线规律,Kovar合金的最佳氧化工艺为:氧化温度850 ℃、氧化时间11.7 min、N₂流量1 L/min、露点30 ℃。不同气氛氧化处理后,Kovar合金与玻璃封接的气密性变化较小,玻璃与表面氧化物为Fe₃O₄的Kovar合金封接后抗拉强度最大。

关键词: Kovar合金, 硼硅玻璃, 玻璃封接, 可控氧化, 润湿性, 气密性

Abstract: In this paper, the high temperature oxidation treatment of Kovar alloy was carried out under different oxidation atmosphere conditions, and the optimum oxidation process of Kovar alloy was optimized. The wetting test and sealing test were carried out with borosilicate glass. At the same time, the oxidation composition and sealing interface were analyzed by XRD, XPS, SEM, EDS and other analytical methods. The results show that Fe, Co and Ni elements all participate in oxidation reaction at high temperature, and the oxidation dynamics of Kovar alloy follow the parabolic rule. The optimal oxidation process of Kovar alloy is: oxidation temperature 850 ℃, oxidation time 11.7 min, N₂ flow 1 L/min, and dew point 30 ℃.After oxidation treatment in different atmospheres, the hermeticity of Kovar alloy and glass sealing changes little. The tensile strength of glass and Kovar alloy with surface oxide of Fe₃O₄ is the highest after sealing.

Key words: Kovar alloy, borosilicate glass, glass sealing, controllable oxidation, wetting performance, hermeticity

中图分类号:

TQ171

郭宏伟, 聂栋, 王毅, 刘密, 朱南沺, 郭首一, 高依博, 赵志龙. Kovar合金的可控氧化及其与硼硅玻璃润湿性研究[J]. 硅酸盐通报, 2024, 43(11): 4215-4223.

GUO Hongwei, NIE Dong, WANG Yi, LIU Mi, ZHU Nantian, GUO Shouyi, GAO Yibo, ZHAO Zhilong. Controllable Oxidation of Kovar Alloy and Wetting Performance with Borosilicate Glass[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(11): 4215-4223.

参考文献

[1] 杨国庆. 玻璃与可伐合金的表面润湿性及其钎焊连接[D]. 兰州: 兰州理工大学, 2021.
YANG G Q. Surface wettability of glass and Kovar alloy and its brazing connection[D]. Lanzhou: Lanzhou University of Technology, 2021 (in Chinese).
[2] DE PABLOS-MARTÍN A, RODRÍGUEZ-LÓPEZ S, PASCUAL M J. Processing technologies for sealing glasses and glass-ceramics[J]. International Journal of Applied Glass Science, 2020, 11(3): 552-568.
[3] GUO H W, DANG M Y, LIU L, et al. Alkali barium glasses for hermetic compression seals: compositional effect, processing, and sealing performance[J]. Ceramics International, 2019, 45(17): 22589-22595.
[4] 刘星, 陈长军, 王晓南, 等. 玻璃与金属封接研究进展[J]. 焊接技术, 2014, 43(5): 1-6.
LIU X, CHEN C J, WANG X N, et al. Research progress of sealing between glass and metal[J]. Welding Technology, 2014, 43(5): 1-6 (in Chinese).
[5] NASCIMENTO J U, ZAMBUZI G C, FERREIRA J O, et al. A simple process to tune wettability of pectin-modified silanized glass[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019, 577: 67-74.
[6] TETERIN Y A, MASLAKOV K I, MURAV'EV E N, et al. X-ray photoelectron spectroscopy study of indium tin mixed oxides on the surface of silicate glass[J]. Inorganic Materials, 2020, 56(5): 482-493.
[7] HUANG Q X, LIU J L, HE X, et al. Analysis of structure evolution and performance in alkali-free glass substrates via XPS and infrared: boron-aluminum anomaly[J]. Journal of Non-Crystalline Solids, 2021, 555: 120531.
[8] 冷文波, 沈卓身. 可伐合金气密封接的预氧化[J]. 电子与封装, 2004, 4(3): 33-41.
LENG W B, SHEN Z S. Preoxidation of Kovar alloy for hermetic sealing[J]. Electronics & Packaging, 2004, 4(3): 33-41 (in Chinese).
[9] KALENDOVÁ A. Effects of particle sizes and shapes of zinc metal on the properties of anticorrosive coatings[J]. Progress in Organic Coatings, 2003, 46(4): 324-332.
[10] 郭宏伟, 王毅, 白赟, 等. 基于响应面法优化航天电连接器的封接工艺研究[J]. 硅酸盐通报, 2023, 42(5): 1886-1895.
GUO H W, WANG Y, BAI Y, et al. Study on optimization of sealing process of aerospace electrical connector based on response surface methodology[J]. Bulletin of the Chinese Ceramic Society, 2023, 42(5): 1886-1895 (in Chinese).
[11] SHEN X H, ZHENG Y G, CHANG L, et al. Microstructural characterization of glass-to-metal brazed joint[J]. Advanced Materials Research, 2012, 616/617/618: 1732-1735.
[12] 郭宏伟, 党梦阳, CHI Longxing, 等. 电连接器用玻璃的封接工艺优化与连接机理[J]. 硅酸盐通报, 2019, 38(11): 3506-3511+3523.
GUO H W, DANG M Y, CHI L X, et al. Optimization of sealing process and connection mechanism of glass in electrical connector[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(11): 3506-3511+3523 (in Chinese).
[13] 罗大为, 李雪, 赵治亚, 等. 可伐合金与玻璃一步封接工艺的研究[J]. 电子元件与材料, 2013, 32(5): 52-55.
LUO D W, LI X, ZHAO Z Y, et al. Research of one-step sealing process for glass to Kovar alloy[J]. Electronic Components and Materials, 2013, 32(5): 52-55 (in Chinese).
[14] CHERN T S, TSAI H L. Wetting and sealing of interface between 7056 glass and Kovar alloy[J]. Materials Chemistry and Physics, 2007, 104(2/3): 472-478.
[15] CHANMUANG C, NAKSATA M, CHAIRUANGSRI T, et al. Microscopy and strength of borosilicate glass-to-Kovar alloy joints[J]. Materials Science and Engineering: A, 2008, 474(1/2): 218-224.
[16] LUO D, SHEN Z. Oxidation behavior of Kovar alloy in controlled atmosphere[J]. Acta Metallurgica Sinica (English Letters), 2008, 21(6): 409-418.
[17] WANG Z J, GAO Z, CHU J L, et al. Low temperature sealing process and properties of Kovar alloy to DM305 electronic glass[J]. Metals, 2020, 10(7): 941.
[18] 陶星空, 高增, 牛济泰. 低温封接玻璃的研究现状及发展趋势[J]. 硅酸盐通报, 2017, 36(10): 3325-3329.
TAO X K, GAO Z, NIU J T. Research status and development trend of glass with low sealing temperature[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(10): 3325-3329 (in Chinese).
[19] AKBARI N, NANDY S, CHAE K H, et al. Unraveling the dynamic behavior of iron-doped oxidized cobalt-nickel alloy in the oxygen-evolution reaction[J]. ACS Applied Energy Materials, 2023, 6(22): 11613-11625.
[20] KHAYAT ARDESTANI S S, DASHTIZAD V, KAFLOU A. Experimental investigations on time, temperature and atmosphere influence on microstructure and mechanical properties of borosilicate glass to Kovar-alloy seals[J]. Materials Characterization, 2021, 171: 110805.
[21] PASK J A, FULRATH R M. Fundamentals of glass-to-metal bonding: viii, nature of wetting and adherence[J]. Journal of the American Ceramic Society, 1962, 45(12): 592-596.
[22] FAN Z C, HU K J, HUANG Z Y, et al. Optimized sealing process and real-time monitoring of glass-to-metal seal structures[J]. Journal of Visualized Experiments, 2019(151): 1-11.