臺灣博碩士論文加值系統

本研究主要探討鈦酸鋇改變鋇鈦比及添加不同量的氟化鋰與硼矽酸鹽玻璃如何影響其燒結緻密度及介電性質。
在燒結溫度超過氟化鋰熔點(842oC)時，氟化鋰會產生液相來加速燒結緻密程度，介電性質亦會明顯提昇。氟化鋰和鈦酸鋇會形成固溶體，燒結後仍屬鈣鈦礦結構。另外在非計量組成鋇鈦比大於1也有使緻密度提高 之情形發生。
另外在鈦酸鋇添加不同量的硼矽酸玻璃，在燒結過程中雖然緻密度隨著燒結溫度升高而增加，但由於鈦酸鋇與硼矽酸鹽玻璃內的SiO2會在750℃燒結溫度以上會反應成BaTiSiO5、 BaTi(BO3)2、Ba2TiSi2O8 和BaTiSi3O9這些低介電常數的固溶相，而影響介電性質。

In the present study, two liquid-phase sintering aids, lithium fluoride (LiF) and a borosilicate glass were added into barium titanate to reduce its sintering temperature. The Ba/Ti ratio of the BaTiO3 powder was either higher or lower than unity. The effects of the liquid-phase sintering aids on the sintering behavior and dielectric properties of the BaTiO3 were investigated.
The densification rate of barium titanate was significantly enhanced as the sintering temperature was raised above 842℃, the melting point of LiF. When the Ba/Ti ratio was higher than unity, the densification rates was much higher than that of the powder small Ba/Ti ratio.
The addition of the borosilicate glass could also lower the sintering temperature of BaTiO3. However, the borosilicate glass reacted with BaTiO3 to form BaTiSiO5, Ba2TiSi2O8, BaTiSi3O9 and BaTi(BO3)2. The dielectric constant of the reaction phases was low so that dielectric property of sintered BaTiO3 was thus degraded.

第一章 前言…………………………………………………………...1
第二章 文獻回顧.........................................2
2.1 鈦酸鋇的性質……………………………………………………….2
2.2影響介電常數的因素………………………………………………..7
2.2.1介電常數與孔洞關係……………………………………………...7
2.2.2介電常數與晶粒大小關係…………………………………………8
2.3.3 影響介電損失的因素…….…………………………………….....8
2.3 低溫燒結……………………………………………………...……10
2.3.1 液相燒結…………………………………………………………11
2.3.2低溫陶瓷電容器………………………………………………….16
第三章 實驗步驟………………………...………………………….21
3.1 材料………………………………………………………………...21
3.2 BaTiO3/LiF和 BaTiO3/硼矽酸鹽玻璃 組成製備…….…………..21
3.2.1 BaTiO3/LiF 組成製備…………………………………………....21
3.2.2 BaTiO3/硼矽酸鹽玻璃組成製備……………………...…………..24
3.3 試樣製備…………………………………………………………...24
3.4 性質測量…………………………………………………………...24
4.3.1 密度………………………………………………………………24
4.3.2 XRD 相鑑定………………………………………………………25
4.3.3 SEM微結構觀察………………………………………………….25
4.3.4 電性測量………………………...……………………………….25
4.3.5 熱膨脹儀測量……………………………………………………26
4.3.6 粒徑分析…………………………………………………………26
第四章 結果與討論………………………………………………...29
4.1 BaTiO3/LiF各性質結果與討論……………………………………..29
4.1.1粒徑分析…………………………………………………………..29
4.1.2 熱分析…………………………………………………………….30
4.1.3 XRD相鑑定…………………………………..………………...….31
4.1.4 燒結溫度與緻密度關係.................................................................35
4.1.5 燒結溫度與線收縮量關係……………………………………….38
4.1.6 SEM微結構觀察………………………………………………….46
4.1.7 燒結溫度與介電性質關係……………………………………….54
4.2 BaTiO3/硼矽酸鹽玻璃 各性質結果與討論…………..…..………..66
4.2.1 XRD相鑑定………………………………………………………66
4.2.2 燒結溫度與緻密度關係…………….……………………….…..69
4.2.3 燒結溫度與線收縮率關係…………..……………………….….71
4.2.4 SEM微結構觀察……………………………………………….....73
4.2.5 燒結溫度與介電性質關係…………………………………….....77
4.3 BaTiO3/LiF與BaTiO3/硼矽酸鹽玻璃之燒結比較………………..81
第五章 結論………………………………………………………….83
參考文獻………………………………………………………………85

1. J. N. Lin, T. B. Wu, “Wetting Reaction between Lithium Fluoride and Barium Titanate, J. Am. Ceram. Soc., 72﹝9﹞1709-12, 1989
2. J. M. Haussonne, G. Desgardin, PH. Bajolet, and B. Raveau, ”Barium Titanate Perovskite Sintered with Lithium Fluoride”, J. Am. Ceram. Soc., 66﹝11﹞801-7, 1983
3. D. E. Rase , Rustum Roy, ”Phase Equilibria in the System BaO-TiO2”, J. Am. Ceram. Soc.,38﹝3﹞102-13, 1955
4. A.Potin , ”Liquid-Phase Sintering of Barium Titanate with Lithium Fluoride”,J. Am. Ceram. Soc.,2﹝4﹞485-8, 1987
5. Yasuyuki Baba, Hiroshi Ochi, Shigetoshi Segawa “High Reliability Internal Capacitor of LTCC”, IEEE, 600-604, 1994
6. B. E. Walker,“Densification and Strength of
BaTiO3 with LiF and MgO Additives” ,Am. Ceram. Soc. Bull., 55 [3] 274-76 & 284-85 , 1976
7. Kevin W, Kirby and Barry A, Wechsier, ”,Phase Relation in the Barium Titanate-Titanium Oxide System”,J. Am. Ceram. Soc.,74﹝8﹞1841-47, 1991
8. C.A. Randall, S. F. Wang, D. Laubscher, J. P. Dougherty, and W. Huebner, “Structure Property Relationships in Core-shell BaTiO3-LiF Ceramics”,J. Mater. Res. 8 [4] 871-879 , 1993
9. Chen LS, Fu SL, Lin WK, Huang KD, ”Dielectric properties of internal capacitors in co-fired ceramic substrates”,Japan. J. Applied Physics 39 [5A] 2675-79 , 2000
10. 黃冠達, “利用乾式法在LTCC多層結構中形成埋入電容”,義守大學電機工程研究所碩士論文,1998
11. 吳秀真, “鈦酸鋇厚膜電容介電特性之研究”,義守大學電子工程所碩士論文,2001
12.B. Yu. Kormilovich, N. A. Ovamenko, and F. D. Ovcharenko, Dokl. Akad. Nauk SSSR, 261 [3] 635-636, 1981: Dokl. Chem. (Engl. Transl.), 26[3] 503-504 , 1981
13. Lih-Shan Chen, Shen-li Fu and Kwan-Dar Huang,” Capacitors
Embedded in the Low Temperature Cofired Ceramics”, IEMT/IMC Proceedings 59-63 , 1998
14. Jung-Kun Lee and Kug-Sun Hong,” Roles of Ba/Ti Ratios in the Dielectric Properties of BaTiO3 Ceramics “ J. Am. Ceram. Soc. 84 [9]
2001-2006 , 2001
15. D. E. Rase and Rustum Roy “ Phase Equilibria in the System BaTiO3-SiO2 “, J. Am. Ceram. Soc. 38 [3] 389-395 , 1955
16. Valmor R. Mastelaro and R. Keding, “ X-ray absorption spectroscopy investigation of Ba2TiSi2O8+xSiO2 glasses “ J. Non-Crystalline Solids 282 181-187, 2001
17. 饒瑞珠, “ LTCC用內埋式電容塗料的發展趨勢“, 工業材料162期 163-169, 2000
18. 許晉榮, 許正源, “ 積層式通訊元組件陶瓷生胚製程技術“, 工業材料 143期 126-130, 1998
19. 陳聰文, 傅坤福, “LTCC材料多層製程開發及其應用“, 工業材料 148期 120-132, 1999
20. 林文寬, 蔡志欽, “可低溫燒結之陶瓷電容 “, 中華民國陶業研究學會會刊 第18卷 第四期 13-20
21. Yasuyuk, Hiroshi Ochi, Shigetoshi Segawa, “High reliability Internal Capacitor of LTCC IEEE T COMPON PACK A 18 (1): 170-173 Mar. ,1995
22. Sea-Fue Wang, Thomas C.K.Yang, Yuh-Ruey Wang, Yoshirou Kuromitsu, “Effect of glass composition on the densification and dielectric properties of BaTiO3 ceramics” Ceramics International 27 1157-162, 2001
23. Detlev F. K. Hennings, B. Seriyati Schreinemacher, and Herbert Schreinematcher, “Solid-state Preparation of BaTiO3-Based Delectrics, Using Ultrafine Raw Materials” J. Am. Ceram. Soc. 84 [12] 2777-82, 2001
24. Detlev F. K. Hennings, Rolf Janssen, and Piet J. L. Reynen “Control of Liquid-Phase-enhanced Discontinuous Grain Growth in Barium Titanate” J. Am. Ceram. Soc. 70 [1] 23-27, 1987
25. Hyo Tae Kim, Sahn Nahn, and Jac Dong Byun “Low-Fired (Zn,Mg)TiO3 Microwave Dielectric” J. Am. Ceram. Soc. 82 [12] 2376-80, 1999
26. Cristina Sillgradi and Maria Cristina D’Arrigo and Cristina Leonelli, “Sintering Behavior of Glass-Ceramic Frits” The Amercain Ceramic Society Bulletin, pp.88-92 September, 2000
27. Sea-Fue Wang, and Yung-Fu Hsu, “electrical conductivity and thermal expansion coefficient of internal phases occurring in multilayer ceramic structure” Ceramics International [26] 669-671, 2000
28. Heli Jantunen, Risto Rautioaho, Antti UnsimKi, Seppo Leppavuori “Compositions of MgTiO3-CaTiO3 ceramic with two borosilicate glasses for LTCC technology” Journal of the European Ceramic Society [20] 2331-2336, 2000
29. O. Dernovsek, A. Naeini, G. Preu, W. Wersing, M. Eberstein, W. A Schiller, “LTCC glass-ceramic composites for microwave application”, Journal of the European Ceramic Society [21] 1693-1697, 2001
30. K. Lichtenecker, “Dielectric Constant of Natural and Synthetic Mixture” , Phys.Z. P: 115, 1926
31. Jona F. and Shirance G., “Barium Titanate “, PP. 108-215 in Ferroelectric Crystals, Pedaman Press, Oxford, 1962
32. Moulson, A.J. and Herbert, J.M., Electroceramics: Materials, Properties and Application. PP.5-85, Chapman and Hall, 1990
33. G. Arlt, D. Hennings, G. de With, “dielectric properties of fine-grained barium titanate ceramics”, J. Appl. Phys. 58 (4), 15 August, 1985
34. R. J. Brook, “The Impurity-Drag Effect and Grain Growth Kinetics”, Scripta metal.,2[7], 375-78 , 1968
35. K. Ramesh Chowdary and E. C. Subbarao, “Liquid Phase Sintered BaTiO3”, Ferroelectrictrics, vol. 37 689-692,1981
36. T. Yamamoto"Influence of small Ba/Ti non-stoichiometry on grain growth behavior in barium titanate" Br. Ceramic. Trans., 94 [5],196-200 , 1995
37. J. S. Choi, and H. G. Kim," Influence of stoichiometry and impurity on the sintering behavior of barium titanate ceramics", J. Mat. Sci., 27 1285-1290 (1992).
38. L. K. Templeton and J. A. Pask, " Formation of BaTiO3 from BaCO3 and TiO2 in Air and in CO2 ", J.am. ceram. soc., 42 [5] 212-216 , 1959
39. A. Amin, M. A. Spears and B. M.Kulwicki, " Reaction of anatase and rutile with barium titanate ", J.Am. Ceram. Soc. 66 [10] 733-738 , 1983
40. P.P. Phule,and S. H. Risbud, "Review Low-temperature synthesis and processing of electronic materials in the BaO-TiO2 system" J. Mat. Sci., 25 1169-1183, 1990.
41.段維新, 連智偉 “氧化鋁對硼矽玻璃燒結行為與介電性質的影響”國立台灣大學材料科學與工程學研究所 碩士論文, 2002
42. G. Izquierdo and A. R. West, Mater. Res. Bull., 15[11]1655-1660 , 1980
43. Milton Ohring “Engineering Materials Science” p.595, 1995