Li_2O-ZnO-SiO_2系封接玻璃结构和性能的研究
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摘要
本文简要地论述了微晶玻璃的发展特点以及封接玻璃。用高温熔融法制备了Li_2O-ZnO-SiO_2系统玻璃及其结晶型玻璃焊料，探讨了各种因素(包括玻璃组成、热处理制度等)对微晶玻璃的结构和性能的影响；利用X射线衍射分析、DTA、红外光谱分析以及扫描电镜等现代测试手段，对玻璃的结构与性能进行研究，测定了玻璃及微晶玻璃的线膨胀系数、转变温度和软化温度，同时对影响微晶玻璃的强度的因素进行了探讨，并对该体系玻璃的流散性进行了测定，对它的析晶过程和析晶机理进行探讨，为实际生产和与玻璃、陶瓷及金属封接提供了一定的理论参考价值。
实验结果表明：在Li_2O-ZnO-SiO_2系统中，以P_2O_5为晶核剂，研制出的微晶玻璃中的主晶相有方石英，此外还有Li_2O．ZnO．SiO_2和硅酸锂锌(Li_3Zn_(0.5)SiO_4)，其膨胀系数从室温至500℃高达161×10~(-7)／℃，玻璃的软化点低于500℃，适合与金属不锈钢、铜封接；而无晶核剂，玻璃析出的微晶玻璃中的主晶相除Li_2O．SiO_2，还有Li_2O．ZnO．SiO_2和硅酸锂锌(Li_3Zn_(0.5)SiO_4)，其膨胀系数从室温至500℃高达106℃10~(-7)/℃，玻璃的软化点也低于500℃，适合与金属合金和平板玻璃封接；
B_2O_3在该体系中存在反常现象：当B_2O_3＞3％时，B_2O_3在玻璃中以层状结构的[BO_3]存在；当B_2O_3=3％时，B_2O_3在玻璃中虽以架状结构的[BO_4]存在；玻璃组成对封接玻璃析晶程度及析出主晶相的种类、微晶玻璃的性能有着重要的影响；随着热处理制度的变化，晶体的类型、膨胀系数相应发生变化；金属预处理的温度和时间以及封接工艺参数对封接质量有着重要影响，该体系玻璃焊料有着良好的流散性能，在630～680℃能与玻璃、陶瓷以及金属等封接。
In this paper, the development and properties of glass-ceramic and sealing glass were briefly reviewed. The glass and crystalline glass-solders of Li2O-ZnO-SiO2 system were prepared by conventional melt technology. The various factors effecting on glass ceramics and glass were investigated,which include glass chemical composition and heat-treatment and so on. And then by means of XRD, DTA, IR and SEM, the structure and properties of the glass and glass-ceramic were studied. The coefficient of linear expansion , transform temperature and soft temperature wer measured. And then the factors that effect the mechanical strength of glass-ceramic were discussed and the fluxion property was determined and the crystallization course and mechanism were discussed, which can provide certain therial reference value for practice producing and glass seals to glass, ceramics and metal.
The results of the experiments indicate that the examiners of glass-ceramic which manufactured with P2O5 as nuclear of crystallization in the Li2O-ZnO-SiO2 system included cristobalite, Li2O.ZnO.SiO2 and Li3Zn0.5SiO4 which have high expansion coefficient and low sotting temperature.This glass solders compatibly seal stainless steel and cuprum. There are Li2O.SiO2,Li2O.ZnO.SiO2 and Li3Zn0.5SiO4.in the same system without P2O5.Its expansion coefficient is around 106 10-7/ C and glass soft temperature is lower than 500 C,whicn can compatibly seal to alloy and flat glass.
In this system,Boron shows the deregulation And then deregulation phenomenon,whicn can be found by IR..The glass compositions have important influence on the crystalline type and crystalline degree and the properties of the glass-ceramics. The type major phase and expansion coefficient were changed with transformation of heat-treatments. And the time and temperature of pretreatment-metal and technics parameter of seals play a important role to seals quality. And then glass solders have favorouble fluxion property and can seal
with glass, ceramic and metal at 630 C ~680 C.
实验结果表明：在Li_2O-ZnO-SiO_2系统中，以P_2O_5为晶核剂，研制出的微晶玻璃中的主晶相有方石英，此外还有Li_2O．ZnO．SiO_2和硅酸锂锌(Li_3Zn_(0.5)SiO_4)，其膨胀系数从室温至500℃高达161×10~(-7)／℃，玻璃的软化点低于500℃，适合与金属不锈钢、铜封接；而无晶核剂，玻璃析出的微晶玻璃中的主晶相除Li_2O．SiO_2，还有Li_2O．ZnO．SiO_2和硅酸锂锌(Li_3Zn_(0.5)SiO_4)，其膨胀系数从室温至500℃高达106℃10~(-7)/℃，玻璃的软化点也低于500℃，适合与金属合金和平板玻璃封接；
B_2O_3在该体系中存在反常现象：当B_2O_3＞3％时，B_2O_3在玻璃中以层状结构的[BO_3]存在；当B_2O_3=3％时，B_2O_3在玻璃中虽以架状结构的[BO_4]存在；玻璃组成对封接玻璃析晶程度及析出主晶相的种类、微晶玻璃的性能有着重要的影响；随着热处理制度的变化，晶体的类型、膨胀系数相应发生变化；金属预处理的温度和时间以及封接工艺参数对封接质量有着重要影响，该体系玻璃焊料有着良好的流散性能，在630～680℃能与玻璃、陶瓷以及金属等封接。
In this paper, the development and properties of glass-ceramic and sealing glass were briefly reviewed. The glass and crystalline glass-solders of Li2O-ZnO-SiO2 system were prepared by conventional melt technology. The various factors effecting on glass ceramics and glass were investigated,which include glass chemical composition and heat-treatment and so on. And then by means of XRD, DTA, IR and SEM, the structure and properties of the glass and glass-ceramic were studied. The coefficient of linear expansion , transform temperature and soft temperature wer measured. And then the factors that effect the mechanical strength of glass-ceramic were discussed and the fluxion property was determined and the crystallization course and mechanism were discussed, which can provide certain therial reference value for practice producing and glass seals to glass, ceramics and metal.
The results of the experiments indicate that the examiners of glass-ceramic which manufactured with P2O5 as nuclear of crystallization in the Li2O-ZnO-SiO2 system included cristobalite, Li2O.ZnO.SiO2 and Li3Zn0.5SiO4 which have high expansion coefficient and low sotting temperature.This glass solders compatibly seal stainless steel and cuprum. There are Li2O.SiO2,Li2O.ZnO.SiO2 and Li3Zn0.5SiO4.in the same system without P2O5.Its expansion coefficient is around 106 10-7/ C and glass soft temperature is lower than 500 C,whicn can compatibly seal to alloy and flat glass.
In this system,Boron shows the deregulation And then deregulation phenomenon,whicn can be found by IR..The glass compositions have important influence on the crystalline type and crystalline degree and the properties of the glass-ceramics. The type major phase and expansion coefficient were changed with transformation of heat-treatments. And the time and temperature of pretreatment-metal and technics parameter of seals play a important role to seals quality. And then glass solders have favorouble fluxion property and can seal
with glass, ceramic and metal at 630 C ~680 C.
引文
[1] P. W. McMillan. Glass-ceramics 2nd Edition, Academic Press, London, 1979
[2] Bull .Am. Coming Develops New Ceramic Material,Ceram Soc., 1957, 36(4): 279
[3] 肖汉宁，彭文琴，邓春明．微晶陶瓷的制备技术、性能及用途，中国陶瓷，2000，(5)
[4] S. D. Stookey, Glastochn Ber, K32, 1959
[5] Li Rounan, Zhu Peinan. Phlogopite-based glass ceramics, Non-Cry Solids, 1986, 80(6): 600
[6] 干福熹．新技术领域中的硅酸盐材料，硅酸盐学报，1991，19(1)：52
[7] Toshihiro Kasuga et al. Am Ceram Soc., 1993, 76(7): 1885
[8] 干福熹．《现代玻璃科学技术》，上海：上海科学出版社，1990
[9] [英]P.W.麦克米伦．《微晶玻璃》，北京：中国建筑出版社，1988
[10] Selcuk A, Atkinson A, Senerveratne D. Mechanical strength of glass to metal joints, Metal Abstract, 1999, 32(Ⅱ): 202～206
[11] Hermetic Glass to Metal Seal Manufacture [DB/OL] http://www.wesley-coe.com/seals/manufacture.html
[12] 马英仁．封接玻璃(一)，玻璃与搪瓷，1992，20(4)：58
[13] DAI Chang-ding, XIE Qi-yuan. Handbook of Electronic Industry Productive Technology(4), Benjing: National Defense Industry Press, 1990:534
[14] 沈健，李启甲．SnO-PbO-B_2O_3三元系统封接玻璃的研究，陕西科技大学学报，1993，6：30～33
[15] 马英仁．封接玻璃(二)，玻璃与搪瓷，1992，20(5)：59
[16] 胡忠武，王警卫．玻璃-金属封接技术，电源技术，2000，24(5)：251～252
[17] 马英仁．封接玻璃(四)，玻璃与搪瓷，1992，21(1)：58～62
[18] T. J. Clark, J.S. Reed.Am Ceram Soc., 1986, 69(11): 837
[19] P artridge J H. Glass-to-metal seals, London: The Society of Glass Technology, 1989:200～205
[20] 游翔，严增濯．封接玻璃的应用，光电技术，1993，23(3)：52～53
[21] 梁忠友．Li_2O-ZnO-SiO_2-PbO系高膨胀封接微晶玻璃的研究，玻璃与搪瓷，1998，
27(6)：28
[22] 卢安贤，黄继武，卢仁伟．SiO_2-PbO-ZnO系统微晶玻璃的制备和性能，中国陶瓷，1998，34(6)：21
[23] Kucharski J. Of 17th international congress on glass, Beijing:International Academic Publishers, 1995, 5:435
[24] Partridge. G., McMillan. p. w. Glass Technol, 1963, 4:173
[25] Partddge.G., McMillan. p. w., Philips.S.V.Joumal Mater sci, 1966, 1:269
[26] Partridge. G., Riley. J. N., Philips. S. V. Trans Journal Brit Ceram Soc, 1973, 72: 253
[27] Fairweather. M. J.,Topping. J. A & Murthy. M. K. Jour Am Cera Soc,1963,58 (5～6)
[28] Erdem Demirkesen, Z. Erkmen & Nil Yildiz. JourAm Cera Soc, 1999, 82(12): 48
[29] West. A. R. and Glasser. F. P. Material Science, 1970, 5(7): 435
[30] 马英仁．封接玻璃(十)，玻璃与搪瓷，1994，22(2)：49
[31] 吕楠，朱玉梅，刘铁山．ZnO-B_2O_3-SiO_2系统焊料玻璃析晶过程的研究，陶瓷学报，1997，18(4)：49
[32] 王德利．彩色显象管封接用焊料玻璃，玻璃与搪瓷，1988，19(4)：38
[33] 韦林．焊料玻璃封接，译自美国陶瓷协会志，1971，39(3)：109～112
[34 韦林．电子封装封接玻璃的热分析与X射线分析，译自美国陶瓷协会通报，1971，50(8)：109～112
[35] 凯旋．低熔点微晶玻璃封接玻璃的应用研究，应用光学，1995，16(3)：37
[36] 蔡春平．低熔点微晶玻璃封接玻璃的研究，应用光学，1995，165(5)：33
[37] 胡忠武，包杰．氧化膜对玻璃-Kovar合金封接的影响，稀有金属材料与工程，2000，29(6)：427～429
[38] Zhongwu. Hu, Jingwei. Wang. Technique of glass-to-metal seals, Chinese Journal of Power Source, 2000, 24(4): 251～252
[39] Zanchetta. A., Lefort. P. Thermal Expansion and Adhesion of Ceramic to Metal Sealing: Case of Porcelain-Kovar Junctions, Journal of European Ceramic Society, 1995, 15:233～238
[40] Zanchetta. A., Labbe. J. C .& Lefort. P. Role du monoxide de fer sur la mouilabilit de kovarpar leverre, Chemistry Physics., 1994, 91:563
[41] 马英仁．封接玻璃(三)，玻璃与搪瓷，1992，20(6)：52
[42] 马英仁．封接玻璃(七)，玻璃与搪瓷，1993，21(4)：50
[43] 马英仁．封接玻璃(八)，玻璃与搪瓷，1993，21(5)：46
[44] 马英仁．封接玻璃(续八)，玻璃与搪瓷，1993，21(6)：53
[45] McMillan. P. W. Glass Ceramics Academic Press, New York, London,1964
[46] 西北轻工学院，《玻璃工艺学》，轻工业出版社，1982：43
[47] 西北轻工学院，《玻璃工艺学》，北京：轻工业出版社，1982：222
[48] 南京玻璃纤维研究设计院，《玻璃测试技术》，北京：中国建设工业出版社，1987
[49] 杨南如．《无机非金属材料测试技术》，武汉：武汉工业大学出版社，1990
[50] 南京大学．《粉晶X射线衍射物相分析》，北京：地质出版社，1980
[51] 杨淑珍．《无机非金属材料测试试验》，武汉：武汉工业大学出版社，1990
[52] 陈建华，孙方明．玻璃与搪瓷，1995，16(1)：43
[53] 干福熹．《玻璃的光学和光谱性质》，上海：上海科学技术出版社，1992
[54] 干福熹．《现代玻璃科学技术》(下册)，上海：上海科学技术出版社，1990
[55] 程继健．硅酸盐学报，1978，7(3)：244
[56] Zu Xiong Chert and P. W. Mcmillan. Phy Chem Glass, 1984, 25(5): 142
[2] Bull .Am. Coming Develops New Ceramic Material,Ceram Soc., 1957, 36(4): 279
[3] 肖汉宁，彭文琴，邓春明．微晶陶瓷的制备技术、性能及用途，中国陶瓷，2000，(5)
[4] S. D. Stookey, Glastochn Ber, K32, 1959
[5] Li Rounan, Zhu Peinan. Phlogopite-based glass ceramics, Non-Cry Solids, 1986, 80(6): 600
[6] 干福熹．新技术领域中的硅酸盐材料，硅酸盐学报，1991，19(1)：52
[7] Toshihiro Kasuga et al. Am Ceram Soc., 1993, 76(7): 1885
[8] 干福熹．《现代玻璃科学技术》，上海：上海科学出版社，1990
[9] [英]P.W.麦克米伦．《微晶玻璃》，北京：中国建筑出版社，1988
[10] Selcuk A, Atkinson A, Senerveratne D. Mechanical strength of glass to metal joints, Metal Abstract, 1999, 32(Ⅱ): 202～206
[11] Hermetic Glass to Metal Seal Manufacture [DB/OL] http://www.wesley-coe.com/seals/manufacture.html
[12] 马英仁．封接玻璃(一)，玻璃与搪瓷，1992，20(4)：58
[13] DAI Chang-ding, XIE Qi-yuan. Handbook of Electronic Industry Productive Technology(4), Benjing: National Defense Industry Press, 1990:534
[14] 沈健，李启甲．SnO-PbO-B_2O_3三元系统封接玻璃的研究，陕西科技大学学报，1993，6：30～33
[15] 马英仁．封接玻璃(二)，玻璃与搪瓷，1992，20(5)：59
[16] 胡忠武，王警卫．玻璃-金属封接技术，电源技术，2000，24(5)：251～252
[17] 马英仁．封接玻璃(四)，玻璃与搪瓷，1992，21(1)：58～62
[18] T. J. Clark, J.S. Reed.Am Ceram Soc., 1986, 69(11): 837
[19] P artridge J H. Glass-to-metal seals, London: The Society of Glass Technology, 1989:200～205
[20] 游翔，严增濯．封接玻璃的应用，光电技术，1993，23(3)：52～53
[21] 梁忠友．Li_2O-ZnO-SiO_2-PbO系高膨胀封接微晶玻璃的研究，玻璃与搪瓷，1998，
27(6)：28
[22] 卢安贤，黄继武，卢仁伟．SiO_2-PbO-ZnO系统微晶玻璃的制备和性能，中国陶瓷，1998，34(6)：21
[23] Kucharski J. Of 17th international congress on glass, Beijing:International Academic Publishers, 1995, 5:435
[24] Partridge. G., McMillan. p. w. Glass Technol, 1963, 4:173
[25] Partddge.G., McMillan. p. w., Philips.S.V.Joumal Mater sci, 1966, 1:269
[26] Partridge. G., Riley. J. N., Philips. S. V. Trans Journal Brit Ceram Soc, 1973, 72: 253
[27] Fairweather. M. J.,Topping. J. A & Murthy. M. K. Jour Am Cera Soc,1963,58 (5～6)
[28] Erdem Demirkesen, Z. Erkmen & Nil Yildiz. JourAm Cera Soc, 1999, 82(12): 48
[29] West. A. R. and Glasser. F. P. Material Science, 1970, 5(7): 435
[30] 马英仁．封接玻璃(十)，玻璃与搪瓷，1994，22(2)：49
[31] 吕楠，朱玉梅，刘铁山．ZnO-B_2O_3-SiO_2系统焊料玻璃析晶过程的研究，陶瓷学报，1997，18(4)：49
[32] 王德利．彩色显象管封接用焊料玻璃，玻璃与搪瓷，1988，19(4)：38
[33] 韦林．焊料玻璃封接，译自美国陶瓷协会志，1971，39(3)：109～112
[34 韦林．电子封装封接玻璃的热分析与X射线分析，译自美国陶瓷协会通报，1971，50(8)：109～112
[35] 凯旋．低熔点微晶玻璃封接玻璃的应用研究，应用光学，1995，16(3)：37
[36] 蔡春平．低熔点微晶玻璃封接玻璃的研究，应用光学，1995，165(5)：33
[37] 胡忠武，包杰．氧化膜对玻璃-Kovar合金封接的影响，稀有金属材料与工程，2000，29(6)：427～429
[38] Zhongwu. Hu, Jingwei. Wang. Technique of glass-to-metal seals, Chinese Journal of Power Source, 2000, 24(4): 251～252
[39] Zanchetta. A., Lefort. P. Thermal Expansion and Adhesion of Ceramic to Metal Sealing: Case of Porcelain-Kovar Junctions, Journal of European Ceramic Society, 1995, 15:233～238
[40] Zanchetta. A., Labbe. J. C .& Lefort. P. Role du monoxide de fer sur la mouilabilit de kovarpar leverre, Chemistry Physics., 1994, 91:563
[41] 马英仁．封接玻璃(三)，玻璃与搪瓷，1992，20(6)：52
[42] 马英仁．封接玻璃(七)，玻璃与搪瓷，1993，21(4)：50
[43] 马英仁．封接玻璃(八)，玻璃与搪瓷，1993，21(5)：46
[44] 马英仁．封接玻璃(续八)，玻璃与搪瓷，1993，21(6)：53
[45] McMillan. P. W. Glass Ceramics Academic Press, New York, London,1964
[46] 西北轻工学院，《玻璃工艺学》，轻工业出版社，1982：43
[47] 西北轻工学院，《玻璃工艺学》，北京：轻工业出版社，1982：222
[48] 南京玻璃纤维研究设计院，《玻璃测试技术》，北京：中国建设工业出版社，1987
[49] 杨南如．《无机非金属材料测试技术》，武汉：武汉工业大学出版社，1990
[50] 南京大学．《粉晶X射线衍射物相分析》，北京：地质出版社，1980
[51] 杨淑珍．《无机非金属材料测试试验》，武汉：武汉工业大学出版社，1990
[52] 陈建华，孙方明．玻璃与搪瓷，1995，16(1)：43
[53] 干福熹．《玻璃的光学和光谱性质》，上海：上海科学技术出版社，1992
[54] 干福熹．《现代玻璃科学技术》(下册)，上海：上海科学技术出版社，1990
[55] 程继健．硅酸盐学报，1978，7(3)：244
[56] Zu Xiong Chert and P. W. Mcmillan. Phy Chem Glass, 1984, 25(5): 142