预氧化温度控制可伐合金-玻璃封接的界面结构与气密性

doi:10.16552/j.cnki.issn1001-1625.2025.0694

摘要/Abstract

摘要：

本研究系统探讨了预氧化温度对4J29可伐合金-硼硅玻璃封接界面微观结构及力学性能的影响机制。在湿氮气氛下，采用连续网带式氧化炉对4J29可伐合金样品进行了550、700、850和1 000 ℃的预氧化处理。研究了不同预氧化温度下4J29可伐合金表面氧化膜的形成机制、相组成演变规律及其对电子元器件封接底座插针耐弯曲性能和封接气密性的影响。结果表明，预氧化温度是调控界面结合机制的关键因素：在550~700 ℃的较低温度范围内，生成的氧化物数量较少且主要分布于晶界处，主要物相为Fe₃O₄；而在850和1 000 ℃高温下，合金表面生成致密氧化膜，主要物相为FeO和Fe₃O₄，并促使封接界面形成具有明显铁元素扩散带的化学键合结构。力学性能测试表明，850 ℃预氧化处理后的样品在经受10 N弯曲力反复作用（3次循环）后，封接界面仍保持良好的气密性，表现出优异的界面结合强度。然而，1 000 ℃高温处理导致封接界面产生大量气泡，出现了玻璃爬杆现象，削弱了界面完整性和长期可靠性。

关键词: 可伐合金, 预氧化温度, 玻璃-金属封接, 界面微观结构, 气密性

Abstract:

This study systematically investigated the influence mechanism of pre-oxidation temperature on the interfacial microstructure and mechanical properties of 4J29 Kovar alloy-borosilicate glass seals. 4J29 Kovar alloy samples were pre-oxidized at 550， 700， 850， and 1 000 ℃ in a wet nitrogen atmosphere using a continuous mesh belt oxidation furnace. The research investigated the formation mechanism of the oxide film on the surface of 4J29 Kovar alloy at different pre-oxidation temperatures， the evolution of phase composition， and the impact on the bending resistance and sealing heameticity of electronic component sealing base pins. The results show that the pre-oxidation temperature is a key factor in regulating the interface bonding mechanism： at the lower temperature range of 550~700 ℃， fewer oxides are formed， which are mainly distributed at grain boundaries， with the primary component being Fe₃O₄. In contrast， at higher temperatures of 850 and 1 000 ℃， a dense oxide film forms on the alloy surface， primarily composed of FeO and Fe₃O₄ phases， promoting the formation of a chemical bonding structure with a distinct iron diffusion zone at the sealing interface. Mechanical performance tests testing indicates that samples pre-oxidized at 850 ℃ retain good hermeticity after enduring 10 N bending force for 3 cycles， demonstrating excellent interface bonding strength. However， high-temperature treatment at 1 000 ℃ causes the formation of numerous bubbles at the sealing interface， along with glass climbing phenomenon， which compromises interface integrity and long-term reliability.

Key words: Kovar alloy, pre-oxidation temperature, glass-to-metal sealing, interface microstructure, hermeticity

中图分类号:

TQ171

聂志坚, 王强, 杨秀富, 马兴, 石磊, 李世欣. 预氧化温度控制可伐合金-玻璃封接的界面结构与气密性[J]. 硅酸盐通报, 2026, 45(1): 299-308.

NIE Zhijian, WANG Qiang, YANG Xiufu, MA Xing, SHI Lei, LI Shixin. Interfacial Structure and Hermeticity of Kovar Alloy-Glass Seals via Pre-Oxidation Temperature Control[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(1): 299-308.

图/表 9

图1 继电器的底座部分示意图

Fig.1 Schematic diagram of base part of relay

图2 不同氧化温度的4J29合金表面氧化膜SEM照片与O元素分布

Fig.2 SEM images and O element distribution of oxide layer on 4J29 alloy surface at different pre-oxidation temperatures

图3 不同预氧化温度的4J29合金单位增重

Fig.3 Unit weight gain of 4J29 alloy at different

图4 不同预氧化温度的4J29合金的XRD谱

Fig.4 XRD patterns of 4J29 alloy at different pre-oxidation temperatures pre-oxidation temperatures

图5 不同预氧化温度的4J29合金与玻璃封接后的金相界面

Fig.5 Metallographic interface of 4J29 alloy sealed with glass at different pre-oxidation temperatures

图6 不同预氧化温度的4J29合金与玻璃封接后的界面元素线性扫描

Fig.6 Linear scanning of interface elements in 4J29 alloy sealed with glass at different pre-oxidation temperatures

图7 不同预氧化温度的4J29合金与玻璃封接后外观形貌

Fig.7 Appearance and morphology of 4J29 alloy sealed with glass at different pre-oxidation temperatures

图8 不同预氧化温度的4J29合金与玻璃封接后的泄漏率

Fig.8 Leakage rate of 4J29 alloy sealed with glass at different pre-oxidation temperatures

图9 玻璃与金属封接界面示意图

Fig.9 Schematic diagram of glass-to-metal sealing interface

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