BaO-TiO_2-SiO_2体系玻璃陶瓷结构及性能研究
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摘要
本文系统研究了BaO-TiO_2-SiO_2体系中BaTiSi_2O_7相，分别制备了BaTiSi_2O_7陶瓷和Ba_2TiSi_2O_8极性玻璃陶瓷，并分析了BaTiSi_2O_7的结构与性能以及掺杂不同氧化物对Ba_2TiSi_2O_8极性玻璃陶瓷性能的影响。
采用传统氧化物混合法制备了BaTiSi_2O_7陶瓷，通过调节烧结温度，组成，利用DSC、IR、XRD、Raman、SEM等测试手段，确定了BaTiSi_2O_7陶瓷的烧结工艺制度。实验结果表明，制备BaTiSi_2O_7陶瓷需要在900℃和1000℃两次预烧， 首先生成中间相－Ba2TiSi_2O_8相，然后在1145℃烧结生产高纯BaTiSi_2O_7相。此外，BaTiSi_2O_7陶瓷对组成变化极为敏感，BaTiO_3和SiO_2比值低于1:2时，主晶相为Ba_2TiSi_2O_8相，还含有BaTiSi_2O_7相；高于1:2时，则主晶相转变为BaTiSi_2O_7相。因此，BaTiO_3和SiO_2的比例应当严格控制在1:2。通过对DSC曲线积分处理，计算出BaTiO_3和SiO2生成BaTiSi_2O_7相的活化能约为366KJ/mol。
通过IR、XRD、Raman等测试手段分析了BaTiSi_2O_7陶瓷结构，实验表明样品中含有TiO_5四方单锥结构和独立的硅氧环状结构。BaTiSi_2O_7陶瓷的介电常数在0.1K～1GHz频率范围内为10～8，介电损耗在10－4左右。
通过XRD、SEM、压电常数d33等分析了掺杂氧化物CaO和ZrO_2对Ba2TiSi_2O_8极性玻璃陶瓷性能的影响，并得出以下结论：加入氧化钙和氧化锆不会改变主晶相，但加入氧化锆将使玻璃陶瓷中出现BaZrSi_3O_9第二相；此外，加入氧化钙有利于BTS晶体的定向析出，使d33增加，相反，加入氧化锆则不利于BTS晶体的定向析出，使d33减小。
The paper studies the phase of BaTiSi_2O_7 in the system of BaO-TiO_2-SiO_2, and prepares BaTiSi_2O_7 ceramic and polar Ba2TiSi2O8 glass ceramic，analyses the structure and properties of BaTiSi_2O_7，investigates the crystalline of the polar Ba_2TiSi_2O_8 glass ceramic with additive oxide.
The paper prepares ceramic of BaTiSi_2O_7 by the method of traditional oxide mixture, gives the sintering technology of BaTiSi2O7 ceramic with the method of DSC, IR, XRD, Raman, SEM by controlling tempt rue and composition. It is concluded that it is necessary calcining at 900℃ and 1000℃ to prepare BaTiSi_2O_7 ceramic. BaTiSi_2O_7 ceramic is sensitive to variety of composition, when the proportion of BaTiO3 and SiO2 is under 1:2, the main phase is Ba2TiSi2O8, and there id BaTiSi2O7 also；When it is above1:2, the main phase is BaTiSi2O7; so the proportion of BaTiO3 and SiO2 must be strictly controlled at 1:2. Additionally, we calculate the activation energy of BaTiSi2O7 phase synthesized by BaTiO3 and SiO2 by integrating the curve of DSC, and the activation energy is about 366KJ/mol. We analyze the structure of BaTiSi2O7 ceramic by methods of IR、XRD、Raman etc, the results indicate that there is structure of TiO5 pyramids and independent ring of silica oxide. The dielectric constant of BaTiSi_2O_7 is 10～8 in the frequency of 0.1K～1GHz, and the dielectric loss is about 10－4.
We analyze the properties of polar Ba_2TiSi_2O_8 glass ceramic with additive CaO and ZrO_2 by XRD, SEM, d33 etc. And we conclude that: Additive CaO and ZrO2 can not influence the main phase, but the phase of BaZrSi_3O_9 occur; moreover, it is advantage to oriental crystallize BTS with CaO and disadvantage to crystallize BST
with ZrO2.
采用传统氧化物混合法制备了BaTiSi_2O_7陶瓷，通过调节烧结温度，组成，利用DSC、IR、XRD、Raman、SEM等测试手段，确定了BaTiSi_2O_7陶瓷的烧结工艺制度。实验结果表明，制备BaTiSi_2O_7陶瓷需要在900℃和1000℃两次预烧， 首先生成中间相－Ba2TiSi_2O_8相，然后在1145℃烧结生产高纯BaTiSi_2O_7相。此外，BaTiSi_2O_7陶瓷对组成变化极为敏感，BaTiO_3和SiO_2比值低于1:2时，主晶相为Ba_2TiSi_2O_8相，还含有BaTiSi_2O_7相；高于1:2时，则主晶相转变为BaTiSi_2O_7相。因此，BaTiO_3和SiO_2的比例应当严格控制在1:2。通过对DSC曲线积分处理，计算出BaTiO_3和SiO2生成BaTiSi_2O_7相的活化能约为366KJ/mol。
通过IR、XRD、Raman等测试手段分析了BaTiSi_2O_7陶瓷结构，实验表明样品中含有TiO_5四方单锥结构和独立的硅氧环状结构。BaTiSi_2O_7陶瓷的介电常数在0.1K～1GHz频率范围内为10～8，介电损耗在10－4左右。
通过XRD、SEM、压电常数d33等分析了掺杂氧化物CaO和ZrO_2对Ba2TiSi_2O_8极性玻璃陶瓷性能的影响，并得出以下结论：加入氧化钙和氧化锆不会改变主晶相，但加入氧化锆将使玻璃陶瓷中出现BaZrSi_3O_9第二相；此外，加入氧化钙有利于BTS晶体的定向析出，使d33增加，相反，加入氧化锆则不利于BTS晶体的定向析出，使d33减小。
The paper studies the phase of BaTiSi_2O_7 in the system of BaO-TiO_2-SiO_2, and prepares BaTiSi_2O_7 ceramic and polar Ba2TiSi2O8 glass ceramic，analyses the structure and properties of BaTiSi_2O_7，investigates the crystalline of the polar Ba_2TiSi_2O_8 glass ceramic with additive oxide.
The paper prepares ceramic of BaTiSi_2O_7 by the method of traditional oxide mixture, gives the sintering technology of BaTiSi2O7 ceramic with the method of DSC, IR, XRD, Raman, SEM by controlling tempt rue and composition. It is concluded that it is necessary calcining at 900℃ and 1000℃ to prepare BaTiSi_2O_7 ceramic. BaTiSi_2O_7 ceramic is sensitive to variety of composition, when the proportion of BaTiO3 and SiO2 is under 1:2, the main phase is Ba2TiSi2O8, and there id BaTiSi2O7 also；When it is above1:2, the main phase is BaTiSi2O7; so the proportion of BaTiO3 and SiO2 must be strictly controlled at 1:2. Additionally, we calculate the activation energy of BaTiSi2O7 phase synthesized by BaTiO3 and SiO2 by integrating the curve of DSC, and the activation energy is about 366KJ/mol. We analyze the structure of BaTiSi2O7 ceramic by methods of IR、XRD、Raman etc, the results indicate that there is structure of TiO5 pyramids and independent ring of silica oxide. The dielectric constant of BaTiSi_2O_7 is 10～8 in the frequency of 0.1K～1GHz, and the dielectric loss is about 10－4.
We analyze the properties of polar Ba_2TiSi_2O_8 glass ceramic with additive CaO and ZrO_2 by XRD, SEM, d33 etc. And we conclude that: Additive CaO and ZrO2 can not influence the main phase, but the phase of BaZrSi_3O_9 occur; moreover, it is advantage to oriental crystallize BTS with CaO and disadvantage to crystallize BST
with ZrO2.
引文
1 钟代英. 电子陶瓷材料. 西安邮电学院学报. Mar.1996 NO.1
2 卢安贤, 卢仁伟, 严长舒. 电子陶瓷材料研究的一些新进展.中国陶瓷. Vol.31 No.3 June 1995
3 小西良弘. 电子陶瓷基础和应用. 1983年：12～59
4 Sheppard L M. Recent. Development and the outlook for electronic ceramics. Silicates Industrials. 1993: 5~6, 83~98
5 殷声编著. 现代陶瓷及应用. 北京科学技术出版社. 1990：88
6 Hank, Safari N A, Riman R. Colloidal processing for improved piezoelectric properties of flexible 0－3 ceramic polymer composites. J Am ceram soc. 1991: 74(7): 1699~1702.
7 （日）工业调查会编辑部编. 陈俊严译. 最新精细陶瓷技术. 北京：中国建筑工业出版社. 1988：54
8 Zhou L, Jiang Z, Zhang S. Electrical properties of Sr0.7Ba0.3TiO3 Ceramics doped with Nb2O5, 3Li2O·2SiO2, and Bi2O3.J Am ceram soc, 1991: 74（11）2825~2927
9 Li C, Chiu C, Desu S. Formation of lead in molten salt system J Am ceram soc. 1991: 74（1）42~47.
10 Ravindranathan P. Synthesis and dielectric properties of solution sol-gel-derived 0.9Pb(Mg1/3 Nb2/3)O3-0.1PbTiO3 Ceramics. J am ceram soc. 1991: 74（12）: 2996~2999.
11 Boufrou B. Degardin G. Raveau B. Tetragonal Tungsten Bronze Niodate, K0.2Sr0.4NbO3-a new material for capacitors with flat dielectric curves. J Am Ceram. 1991: 74(11) 2809~2814.
Ogama T. Highly functional and high-performance piezoelectric ceramics.
12 Ceramic Bulletin. 1991: 70(6) 1042~1048.
13 范福康. 几种电子陶瓷材料的研究与思考. 江苏省硅酸盐学会特种陶瓷专业委员会第17届学术年会论文集. 2000: 65~67.
14 宋英，王福平，周玉. 微波介质陶瓷材料的研究进展. 材料科学与工艺. 1998年，第六卷，第二期. 60～61.
15 高春华，黄新友. 微波介质陶瓷及其展望. 陶瓷. 2002，第1期：42～43.
16 何进，杨传仁. 微波介质陶瓷材料综述. 电子元件与材料. 1995: Vol.14 No.2 10.
17 苏建华，徐永利，陈汴琨. 高品质高稳定性压电陶瓷的发展与展望. 压电与声光. 1995: Vol. 17，No.3: 35～36.
18 Christian R?ssel. Oriented crystallization of glass. A review Journal of Non-Crystalline Solids 219(1997) 212~28.
19 乔冠军，金志浩. 微晶玻璃的发展—组成、性能及应用. 硅酸盐通报. 1994年第4期: 52~56.
20 张剑平，丁振亚；Ba2O-SrO-TiO2-SiO2系统压电微晶玻璃的研究 硅酸盐学报，Vol.19,No.5, October 1991: 431~436.
21 谢为民, 方承平. 极性微晶玻璃的恒温定向析晶. 硅酸盐学报. Vol.25, No.1, February 1997: 395~398.
22 段非, 方承平, 丁振亚. Ba2O-SrO-TiO2-SiO2透明极性微晶玻璃的研究. 硅酸盐学报. Vol.26.No.3, June 1998
23 Halliyal et al, New Glass Ceramics for Piezoelectric Devices. Journal of the American Ceramic Society. Vol 67, No.5.
24 朱满康, 王如志等. 极性微晶玻璃恒温场晶粒定向机理研究. 硅酸盐学报，5(2002).
25 G.Partridge. A review of surface crystallization in vitreous systems Glass Technology. Vol.28.No.1 February 1987.
V. N. Sigaev, P. D. Sarkia et al. Ferroelectric-Pyroelectric Texture Based on
26 Glass-Ceramic Stollwellite like Phase. Vol. 22, No. 2, 1996. p. 117-124.
27 朱满康, 邵明明, 孙诗兵等. BTS极性微晶玻璃显微结构及SAW特性研究.硅酸盐通报. No.2, 2002.
28 Halliyal et al; Grain-Oriented Glass-Ceramics for Piezoelectric Devices Journal of the American Ceramic Society. Vol. 67, No.5.
29 Chandra S.RAY, Delbert E.DAY. CRYTALLIZATION OF BRARIA-TITANIA-SILICA GLASSES Journal of Non-crystalline Solids. 81 (1986) 173~183.
30 Francois Farges. Coordination of Ti in crystalline and glassy frenoites: A high-resolution XANES spectroscopy study at the Ti K-edge. Journal of Non-Crystalline Solids 204 (1996) 53-64.
31 M.A. Roberts, G. Sankar, J.M. Thomas, et al. Nature 6581(1996) 381
32 S. Stassen, P. Tarte, A. Rulmont. The barium titano-disilicate BaTiSi2O7: a structural investigation by vibrational spectroscopy and X-ray powder diffraction Spectrochim. Acta Part A 84 (1998) 1423.
33 N. Ko¨ppen and A. Dietzel, Glastechn. Ber. 49 (1976)199 (JCPDS file 32-0089).
34 W. Cleek, E.H. Hamilton, J. Res. NBS 57 (1956) 317.
35 D.Q. Zhang, J.W. He, Residual Stress Analysis by X-ray Diffraction and its Functions, Press of Xi_an Jiaotong University, Xi_an, 1999 (in Chinese).
36 金志浩, 高积强, 乔冠军. 工程陶瓷材料. 西安交通大学出版社. 2000: 80.
37 田中哲朗. 压电陶瓷材料. 科学出版社，1982：50～60.
38 何金兰，杨克让，李小戈. 仪器分析原理. 科学出版社. 2002：94～96.
39 D.E. Rase and Rustum Roy. J. Am. Ceram. Soc. 1955:38[11] :198.
40 浙江大学，武汉工业大学，上海化工大学，华南理工学院. 硅酸盐物理化学. 中国建筑工业出版社. 323.
41 李余增. 热分析. 清华大学出版社. 1987：139～139.
42 S. Stassen, P. Tarte, A. Rulmont. The barium titano-disilicate BaTiSi2O7: a structural investigation by vibrational spectroscopy and X-ray powder diffraction. Spectrochimica Acta Part A 54 (1998) 1423-1431.
43 A. M. Coats, N. Hirose, J. Marr, and A. R. West. Tetrahedral Ti+4 in the Solid Solution Ba2Ti1+xSi2-xO8(0≦x≦0.14). Journal of Solid State Chemistry. 1996: 126 (105~107).
44 Halliyal A., Bhalla A.S., Newham R.E. and Cross L.E. J. Mater. Sci..1981, 16:1023.
45 Vogel W. Chemistry of Glass. Columbus Press，Ohio. 1985:215~280.
2 卢安贤, 卢仁伟, 严长舒. 电子陶瓷材料研究的一些新进展.中国陶瓷. Vol.31 No.3 June 1995
3 小西良弘. 电子陶瓷基础和应用. 1983年：12～59
4 Sheppard L M. Recent. Development and the outlook for electronic ceramics. Silicates Industrials. 1993: 5~6, 83~98
5 殷声编著. 现代陶瓷及应用. 北京科学技术出版社. 1990：88
6 Hank, Safari N A, Riman R. Colloidal processing for improved piezoelectric properties of flexible 0－3 ceramic polymer composites. J Am ceram soc. 1991: 74(7): 1699~1702.
7 （日）工业调查会编辑部编. 陈俊严译. 最新精细陶瓷技术. 北京：中国建筑工业出版社. 1988：54
8 Zhou L, Jiang Z, Zhang S. Electrical properties of Sr0.7Ba0.3TiO3 Ceramics doped with Nb2O5, 3Li2O·2SiO2, and Bi2O3.J Am ceram soc, 1991: 74（11）2825~2927
9 Li C, Chiu C, Desu S. Formation of lead in molten salt system J Am ceram soc. 1991: 74（1）42~47.
10 Ravindranathan P. Synthesis and dielectric properties of solution sol-gel-derived 0.9Pb(Mg1/3 Nb2/3)O3-0.1PbTiO3 Ceramics. J am ceram soc. 1991: 74（12）: 2996~2999.
11 Boufrou B. Degardin G. Raveau B. Tetragonal Tungsten Bronze Niodate, K0.2Sr0.4NbO3-a new material for capacitors with flat dielectric curves. J Am Ceram. 1991: 74(11) 2809~2814.
Ogama T. Highly functional and high-performance piezoelectric ceramics.
12 Ceramic Bulletin. 1991: 70(6) 1042~1048.
13 范福康. 几种电子陶瓷材料的研究与思考. 江苏省硅酸盐学会特种陶瓷专业委员会第17届学术年会论文集. 2000: 65~67.
14 宋英，王福平，周玉. 微波介质陶瓷材料的研究进展. 材料科学与工艺. 1998年，第六卷，第二期. 60～61.
15 高春华，黄新友. 微波介质陶瓷及其展望. 陶瓷. 2002，第1期：42～43.
16 何进，杨传仁. 微波介质陶瓷材料综述. 电子元件与材料. 1995: Vol.14 No.2 10.
17 苏建华，徐永利，陈汴琨. 高品质高稳定性压电陶瓷的发展与展望. 压电与声光. 1995: Vol. 17，No.3: 35～36.
18 Christian R?ssel. Oriented crystallization of glass. A review Journal of Non-Crystalline Solids 219(1997) 212~28.
19 乔冠军，金志浩. 微晶玻璃的发展—组成、性能及应用. 硅酸盐通报. 1994年第4期: 52~56.
20 张剑平，丁振亚；Ba2O-SrO-TiO2-SiO2系统压电微晶玻璃的研究 硅酸盐学报，Vol.19,No.5, October 1991: 431~436.
21 谢为民, 方承平. 极性微晶玻璃的恒温定向析晶. 硅酸盐学报. Vol.25, No.1, February 1997: 395~398.
22 段非, 方承平, 丁振亚. Ba2O-SrO-TiO2-SiO2透明极性微晶玻璃的研究. 硅酸盐学报. Vol.26.No.3, June 1998
23 Halliyal et al, New Glass Ceramics for Piezoelectric Devices. Journal of the American Ceramic Society. Vol 67, No.5.
24 朱满康, 王如志等. 极性微晶玻璃恒温场晶粒定向机理研究. 硅酸盐学报，5(2002).
25 G.Partridge. A review of surface crystallization in vitreous systems Glass Technology. Vol.28.No.1 February 1987.
V. N. Sigaev, P. D. Sarkia et al. Ferroelectric-Pyroelectric Texture Based on
26 Glass-Ceramic Stollwellite like Phase. Vol. 22, No. 2, 1996. p. 117-124.
27 朱满康, 邵明明, 孙诗兵等. BTS极性微晶玻璃显微结构及SAW特性研究.硅酸盐通报. No.2, 2002.
28 Halliyal et al; Grain-Oriented Glass-Ceramics for Piezoelectric Devices Journal of the American Ceramic Society. Vol. 67, No.5.
29 Chandra S.RAY, Delbert E.DAY. CRYTALLIZATION OF BRARIA-TITANIA-SILICA GLASSES Journal of Non-crystalline Solids. 81 (1986) 173~183.
30 Francois Farges. Coordination of Ti in crystalline and glassy frenoites: A high-resolution XANES spectroscopy study at the Ti K-edge. Journal of Non-Crystalline Solids 204 (1996) 53-64.
31 M.A. Roberts, G. Sankar, J.M. Thomas, et al. Nature 6581(1996) 381
32 S. Stassen, P. Tarte, A. Rulmont. The barium titano-disilicate BaTiSi2O7: a structural investigation by vibrational spectroscopy and X-ray powder diffraction Spectrochim. Acta Part A 84 (1998) 1423.
33 N. Ko¨ppen and A. Dietzel, Glastechn. Ber. 49 (1976)199 (JCPDS file 32-0089).
34 W. Cleek, E.H. Hamilton, J. Res. NBS 57 (1956) 317.
35 D.Q. Zhang, J.W. He, Residual Stress Analysis by X-ray Diffraction and its Functions, Press of Xi_an Jiaotong University, Xi_an, 1999 (in Chinese).
36 金志浩, 高积强, 乔冠军. 工程陶瓷材料. 西安交通大学出版社. 2000: 80.
37 田中哲朗. 压电陶瓷材料. 科学出版社，1982：50～60.
38 何金兰，杨克让，李小戈. 仪器分析原理. 科学出版社. 2002：94～96.
39 D.E. Rase and Rustum Roy. J. Am. Ceram. Soc. 1955:38[11] :198.
40 浙江大学，武汉工业大学，上海化工大学，华南理工学院. 硅酸盐物理化学. 中国建筑工业出版社. 323.
41 李余增. 热分析. 清华大学出版社. 1987：139～139.
42 S. Stassen, P. Tarte, A. Rulmont. The barium titano-disilicate BaTiSi2O7: a structural investigation by vibrational spectroscopy and X-ray powder diffraction. Spectrochimica Acta Part A 54 (1998) 1423-1431.
43 A. M. Coats, N. Hirose, J. Marr, and A. R. West. Tetrahedral Ti+4 in the Solid Solution Ba2Ti1+xSi2-xO8(0≦x≦0.14). Journal of Solid State Chemistry. 1996: 126 (105~107).
44 Halliyal A., Bhalla A.S., Newham R.E. and Cross L.E. J. Mater. Sci..1981, 16:1023.
45 Vogel W. Chemistry of Glass. Columbus Press，Ohio. 1985:215~280.