低温封接玻璃的研究进展

doi:10.16552/j.cnki.issn1001-1625.2024.1231

摘要/Abstract

摘要： 与有机封接相比,无机玻璃封接具有电绝缘性高、气密性好和寿命长等特点,广泛应用于航空、航天、电子及新能源汽车等领域。低温封接玻璃是封接温度低于600 ℃的玻璃。目前,低温封接玻璃体系主要包括铅酸盐玻璃、磷酸盐玻璃、钒酸盐玻璃和铋酸盐玻璃等,相关研究主要涉及探究低温封接玻璃的“组成-结构-性能”本构关系,为设计优化新型低温封接玻璃体系提供理论指导;评价考核低温封接玻璃的热膨胀系数、转变温度和化学稳定性等关键性能,实现匹配封接和长寿命服役;建立低温封接玻璃材料性能测试标准规范,拓展低温封接玻璃应用场景。本文综述了低温封接玻璃的典型体系,介绍了低温封接玻璃的应用场景,最后展望了低温封接玻璃的发展趋势。

关键词: 低温封接玻璃, 环境友好型玻璃, 转变温度, 热膨胀系数, 应用场景

Abstract: Compared with organic sealing, inorganic glass sealing has the characteristics of high electrical insulation, good air tightness and long life, and is widely used in aviation, aerospace, electronics and new energy vehicles. Low-temperature sealing glass is glass with a sealing temperature below 600 ℃. Currently, low-temperature sealing glass systems mainly include plumbate glass, phosphate glass, vanadate glass, and bismuth glass. The related research mainly involves exploring the ‘composition-structure-performance’ constitutive relationship of low temperature sealing glass, which provides theoretical guidance for the design and optimization of new low-temperature sealing glass system. The key properties such as coefficient of thermal expansion, transition temperature and chemical stability of low-temperature sealing glass are evaluated to achieve matching sealing and long life service. To establish a standard specification for the performance test of low-temperature sealing glass materials and expand the application scenarios of low-temperature sealing glass. This paper reviews the typical systems of low-temperature sealing glass, introduces the application scenarios of low-temperature sealing glass, and finally looks forward to the development trend of low-temperature sealing glass.

Key words: low-temperature sealing glass, environment-friendly glass, transition temperature, coefficient of thermal expansion, application scenario

中图分类号:

TQ171

兰杨, 殷先印, 王衍行, 高锡平, 黄翱翔, 韩滨. 低温封接玻璃的研究进展[J]. 硅酸盐通报, 2025, 44(5): 1850-1858.

LAN Yang, YIN Xianyin, WANG Yanhang, GAO Xiping, HUANG Aoxiang, HAN Bin. Research Progress on Low-Temperature Sealing Glass[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(5): 1850-1858.

参考文献

[1] 唐会毅, 李伟, 王华, 等. 一种耐高温高压密封材料的封装工艺研究[J]. 功能材料, 2011, 42(增刊2): 377-378.
TANG H Y, LI W, WANG H, et al. The research of the sealing technology on a high-temperature and high-pressure resistance sealing material[J]. Journal of Functional Materials, 2011, 42(supplement 2): 377-378 (in Chinese).
[2] 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.
[3] WEI M J, HE F, CAO X H, et al. Structure and sintering behavior of BaO-SrO-B₂O₃-SiO₂ sealing glass for Al₂O₃ ceramic substrates[J]. Ceramics International, 2022, 48(19): 27718-27730.
[4] CAI Y Y, LIU Z, GONG K Q, et al. The effect of reinforcement particle size on the mechanical and fracture properties of glass matrix composites[J]. Heliyon, 2023, 9(11): e21895.
[5] JIA H, BAI J L, AO C, et al. Experimental investigations on B₂O₃-Al₂O₃-SiO₂ glass-ceramics with different K₂O/Na₂O ratios for sealing to Kovar alloy[J]. Materials Today Communications, 2024, 40: 109911.
[6] 赵偶. 低温封接玻璃的研究[D]. 长沙: 湖南大学, 2007.
ZHAO O. Study on the glasses with low sealing temperature[D]. Changsha: Hunan University, 2007 (in Chinese).
[7] 牛济泰, 董文伟, 高增, 等. 铋酸盐封接玻璃的研究及其连接应用现状[J]. 机械工程材料, 2024, 48(1): 1-9.
NIU J T, DONG W W, GAO Z, et al. Progress on bismuthate sealing glass research and its joining application[J]. Materials for Mechanical Engineering, 2024, 48(1): 1-9 (in Chinese).
[8] CHENG Y, XIAO H N, GUO W M. Influence of compositions on sealing temperature and properties of lead borate non-crystallizing sealing glasses[J]. Materials Science and Engineering: A, 2007, 464(1/2): 210-215.
[9] SEN S, LANCELOTTI R F, HUNG I, et al. Characterization of the Pb coordination environment and its connectivity in lead silicate glasses: results from 2D ²⁰⁷Pb NMR spectroscopy[J]. The Journal of Physical Chemistry B, 2024, 128(11): 2811-2820.
[10] RADA S, UNGURESAN M, ZAGRAI M, et al. Structural, optical, and magnetic studies of the metallic lead effect on MnO₂-Pb-PbO₂ vitroceramics[J]. Materials, 2022, 15(22): 8061.
[11] KALRA G, UPADHYAY M, ABHAYA S, et al. Thermal, structural, and defect studies on Pb modified GeSe glasses[J]. Journal of Non-Crystalline Solids, 2017, 460: 146-152.
[12] SHI J P, WANG L L, XIE H, et al. Effect of PbO on the chemical durability of low-temperature PbO-B₂O₃-ZnO glass for cesium immobilization[J]. Ceramics International, 2024, 50(12): 20851-20859.
[13] HRUŠKA B, CHROMČÍKOVÁ M, OSIPOV A A, et al. Structural investigation and thermal properties of Al₂O₃-PbO-B₂O₃ glasses[J]. Journal of Non-Crystalline Solids, 2024, 626: 122813.
[14] BARADARAN A, TAVOOSI M, GHASEMI A. Structural, optical and thermal characteristics of GeO₂-PbO-SrO-AlF₃-MgF₂ glasses[J]. Journal of Asian Ceramic Societies, 2018, 6(2): 162-168.
[15] CHENG Y, XIAO H N, GUO W M, et al. Thermal behavior of GeO₂ doped PbO-B₂O₃-ZnO-Bi₂O₃ glasses[J]. Materials Science and Engineering: A, 2006, 423(1/2): 184-188.
[16] TSAUR G, TSAUR F, WANG T H. Capsule sealing composition and its sealing method thereof: US10729619[P]. 2020-08-04.
[17] XU J H, GAO D, WANG X X, et al. Joining ZnS ceramics by using PbTiO₃-doped PbO-B₂O₃-ZnO[J]. Journal of Materials Science, 2020, 55(21): 8814-8828.
[18] PUGLIESE D, VEBER A, LEMIÈRE A, et al. Effect of post-heat-treatment on the structural, spectroscopic and dissolution properties of a highly stable Er³⁺-doped multi-component phosphate glass[J]. Journal of Alloys and Compounds, 2021, 883: 160878.
[19] ZHANG Y, CAO W J, LI M M, et al. Influences of La₂O₃ on the structure and properties of 50P₂O₅-30Sb₂O₃-10CaO-5Al₂O₃-5TeO₂ low-melting glasses[J]. Applied Physics A, 2018, 124(9): 658.
[20] ZHANG D W, XU X, YU T L, et al. Investigation on structure and properties of nitride-tin-boron-fluorophosphate glass for low-temperature sealing[J]. Journal of Non-Crystalline Solids, 2021, 557: 120504.
[21] DIAO J L, XU X, LI Z Y, et al. Effect of NH₄H₂PO₄ content on properties of P-Sn-W-B glass system with ultra-low melting sealing temperature[J]. Journal of Non-Crystalline Solids, 2019, 507: 38-45.
[22] MAHDY E A, IBRAHIM S, ABO-MOSALLAM H A. The influence of Bi₂O₃ on structural and enhancing physical properties of Li₂O-Fe₂O₃-In₂O₃-P₂O₅ glasses[J]. Materials Chemistry and Physics, 2023, 309: 128406.
[23] MOHAN BABU M, SYAM PRASAD P, HIMA BINDU S, et al. Investigations on physico-mechanical and spectral studies of Zn²⁺ doped P₂O₅-based bioglass system[J]. Journal of Composites Science, 2020, 4(3): 129.
[24] ELKHOSHKHANY N, REDA A, EMBABY A M. Preparation and study of optical, thermal, and antibacterial properties of vanadate-tellurite glass[J]. Ceramics International, 2017, 43(17): 15635-15644.
[25] 王方. V₂O₅-TeO₂-X体系低温封接玻璃的性能研究[D]. 青岛: 中国海洋大学, 2012.
WANG F. Properties of low temperature sealing glasses in V₂O₅-TeO₂-X system[D]. Qingdao: Ocean University of China, 2012 (in Chinese).
[26] SHEARER A, LANAGAN M, FEINEMAN M, et al. Dielectric and electrical transport properties of alkaline earth vanadate glasses[J]. Journal of the American Ceramic Society, 2024: 107(12): 8178-8190.
[27] EFTIMIE M, FILIP A V, DANESCU C B, et al. Obtaining and conductive properties of a vanadate-borate-phosphate glass[J]. Scientific Reports, 2023, 13(1): 16054.
[28] SALEHIZADEH S A, MELO B M G, FREIRE F N A, et al. Structural and electrical properties of TeO₂-V₂O₅-K₂O glassy systems[J]. Journal of Non-Crystalline Solids, 2016, 443: 65-74.
[29] LI H, YU H T, CHEN P, et al. Glass forming region and bonding mechanism of low-melting V₂O₅-TeO₂-Bi₂O₃ glass applied in vacuum glazing sealing[J]. Journal of the American Ceramic Society, 2021, 104(10): 5050-5066.
[30] JEONG D G, CHA J M, SHIN J Y, et al. Water resistances of Ag₂O-, BaO-, and CuO-doped V₂O₅-P₂O₅-TeO₂ glass sealants[J]. Journal of Nanoscience and Nanotechnology, 2019, 19(3): 1388-1392.
[31] GE W J, REN H S, ZHANG Y, et al. Investigation of the glass forming regularity and thermal behavior of lead-free V₂O₅-TeO₂-RO (R = Ca, Sr, Ba) low temperature sealing glass for electronics packaging[J]. Journal of Alloys and Compounds, 2024, 971: 172561.
[32] ALMUQRIN A H, KUMAR A, ALASALI H J, et al. Impact of high concentration of the Bi₂O₃ on the physical, mechanical and gamma ray shielding capability of the Bi₂O₃-TeO₂-CdO glass system[J]. Journal of Materials Science: Materials in Electronics, 2023, 34(13): 1112.
[33] SAYYED M I, ALRASHEDI M F, ALMUQRIN A H, et al. Recycling and optimizing waste lab glass with Bi₂O₃ nanoparticles to use as a transparent shield for photons[J]. Journal of Materials Research and Technology, 2022, 17: 2073-2083.
[34] JIMÉNEZ J A. Spectroscopic and dilatometric analysis of low-melting bismuth borate glasses in the Bi₂O₃-BaO-Li₂O-B₂O₃ quaternary[J]. Materials Chemistry and Physics, 2020, 255: 123635.
[35] LAN S H, WANG W X, CHEN C C, et al. The study on the decolorization and properties of bismuth glass[J]. Advances in Condensed Matter Physics, 2023, 2023: 7366612.
[36] LIANG Y H, ZHOU X, FU Y, et al. Crystallization resistance behavior of Al₂O₃-doped calcium bismuth borate glasses[J]. Journal of Non-Crystalline Solids, 2022, 578: 121339.
[37] LIU J Y, XU X, ZHENG T, et al. Effect of Bi₂O₃ content on the structure and properties of Bi₂O₃-B₂O₃-BaO-ZnO glass[J]. Journal of Non-Crystalline Solids, 2022, 575: 121211.
[38] WANG B, QU S G, LI X Q. Effect of the different high volume fraction of SiC particles on the junction of bismuthate glass-SiC_p/Al composite[J]. Scanning, 2018, 2018: 7394040.
[39] SINGH S P, KARMAKAR B. Synthesis and characterization of low softening point high Bi₂O₃ glasses in the K₂O-B₂O₃-Bi₂O₃ system[J]. Materials Characterization, 2011, 62(6): 626-634.
[40] CUI C T, YANG C Q, MA S H, et al. Effect of different carbon materials on the structure and glass crystallization temperature, wettability, and expansion coefficient properties of glass[J]. Ceramics International, 2023, 49(17): 28415-28433.
[41] SUN Q, YANG W C, LIU Y H, et al. Microstructure and mechanical properties of tempered glass joint bonded with Bi-B-Zn low melting glass[J]. Journal of Materials Processing Technology, 2019, 271: 404-412.
[42] POLAT E O, CETIN M M, TABAK A F, et al. Transducer technologies for biosensors and their wearable applications[J]. Biosensors, 2022, 12(6): 385.
[43] GOONERATNE C P, LI B D, MOELLENDICK T E. Downhole applications of magnetic sensors[J]. Sensors, 2017, 17(10): 2384.
[44] AGORASTOU Z, NOULIS T, SISKOS S. Analog sensor interface for field mill sensors in atmospheric applications[J]. Sensors, 2022, 22(21): 8405.
[45] FAN Z C, DIAO X Z, LIU M L, et al. On-line monitoring of sealing glass in electrical penetration assembly based on femto-laser inscribed fiber Bragg grating sensors[J]. Optics Express, 2019, 27(2): 608-620.
[46] WANG Z Y, YANG C Q, LI S S, et al. Study on structure and performance of Bi-B-Zn sealing glass encapsulated fiber Bragg grating[J]. Ceramics International, 2023, 49(9): 14432-14444.
[47] ROSOLEM J B, PENZE R S, FLORIDIA C, et al. Techniques and materials for optical fiber sensors sealing in dynamic environments with high pressure and high temperature[J]. Sensors, 2021, 21(19): 6531.
[48] DEMIRHAN AYDIN G, AKAR O S, AKIN T. Wafer level vacuum packaging of MEMS-based uncooled infrared sensors[J]. Micromachines, 2024, 15(8): 935.
[49] SHRIKHANDE V K. Preparation and characterization of special glasses for sealing and other applications[J]. IOP Conference Series: Materials Science and Engineering, 2009, 2: 012016.
[50] SHIKAMA K, KOIKE Y. Reflowable optical connector with glass-ceramic ferrule for advanced pluggable transceiver packaging[J]. Optical Fiber Technology, 2020, 54: 102074.
[51] PEERZADA A R, JOBSON C M, KASSA E, et al. Versatile optical fiber feedthroughs for ultra-high vacuum applications[J]. Vacuum, 2020, 180: 109542.
[52] ZHOU Y T, YANG Y X, HUANG F H, et al. Characterization of new tellurite glasses and crystalline phases in the TeO₂-PbO-Bi₂O₃-B₂O₃ system[J]. Journal of Non-Crystalline Solids, 2014, 386: 90-94.
[53] IQBAL F, KIM S, KIM H. Degradation of phosphor-in-glass encapsulants with various phosphor types for high power LEDs[J]. Optical Materials, 2017, 72: 323-329.
[54] CHIBA H, SUZUKI Y, YASUDA Y, et al. DUV-LED packaging using high density TSV in silicon cavity and laser-glass-frit-bonded UV transmitting glass cap[J]. Sensors and Actuators A: Physical, 2022, 344: 113700.