臺灣博碩士論文加值系統

本研究以反應燒結法製備(1-x)ZnNb2O6-xTiO2與NiNb2O6-yTiO2微波介電陶瓷。x=0.5，y=1時直接燒結混合原料即可以獲得單一相的Zn0.5Ti0.5NbO4(ZTN)與Ni0.5Ti0.5NbO4(NTN)陶瓷，且密度皆可達理論密度之99%以上。ZTN燒結在1200℃持溫2小時有較佳微波介電特性：Q×f=35000GHz，εr =32.6和τf =-48.38 ppm/℃。NTN燒結在1170℃持溫6小時有較佳微波介電特性：Q×f=3568GHz，εr =53.8和τf =+103.68 ppm/℃。在ZnNb2O6與NiNb2O6陶瓷中分別加入適當量之TiO2可使τf值接近0 ppm/℃，x=0.6時可得較佳微波介電特性：Q×f=19000GHz，εr =49.9和τf =0 ppm/℃，y=0.1時可得Q×f=18700GHz，εr =29.3和τf =-0.05 ppm/℃。添加0.5wt%CuO於ZTN與NTN可以成平飢C燒結溫度，分別於在1070℃/4 h與1130℃/4 h可獲得較佳微波介電特性：Q×f=32000GHz，εr =31.5和τf =-40.89 ppm/℃與Q×f=3579GHz，εr =53.2和τf =+93.81 ppm/℃。

(1-x)ZnNb2O6-xTiO2 and NiNb2O6-yTiO2 ceramics produced using a reaction-sintering process were investigated. Without any calcination involved, pure Zn0.5Ti0.5NbO4 (ZTN) and Ni0.5Ti0.5NbO4 (NTN) phases could be obtained successfully after sintering the pellets with x=0.5, y=1. Pellets with >99% of theoretical density could be obtained. Microwave dielectric properties Q×f=35000GHz, εr =32.6, and τf=-48.38 ppm/oC in ZTN sintered at 1200oC for 2 h and Q×f=35000GHz, εr =32.6, and τf=-48.38 ppm/oC in NTN sintered at 1170oC for 6 h were found. As TiO2 was added into ZnNb2O6 and NiNb2O6 τf values approach 0 ppm/oC could be found. Microwave dielectric properties Q×f=19000GHz, εr =49.9, and τf =0 ppm/oC in pellets with x=0.6 and Q×f=18700GHz, εr =29.3, and τf =-0.05 ppm/oC in pellets with y=0.1 were obtained. With CuO addition, the sintering temperature was lowered to 1070oC for ZTN and 1130oC for NTN. The microwave dielectric properties Q×f=32000GHz, εr =31.5 and τf =-40.89 ppm/oC for ZTN were found. Q×f=3579GHz, εr =53.2 and τf =+93.81 ppm/oC for NTN were found.

中文摘要-------i
英文摘要---------ii
誌謝-----------iii
目錄--------iv
表目錄--------ix
圖目錄-------x
第一章 緒論-------1
第二章 原理-----3
2.1微波介電材料-------3
2.1.1 介電常數---------4
2.1.2介電品質因數-----7
2.1.3 共振頻率溫度係數--------10
2.2 微波介電共振器理論-----11
2.3 微波特性量測-------13
2.3.1 介電常數量測-------13
2.3.2 Qd值量測-------16
2.3.3共振頻率溫度係數量測-----18
2.4 燒結原理-------19
2.4.1 再結晶和晶粒成長----20
2.4.2燒結原理和液相燒結------21
第三章 文獻回顧-------26
第四章 實驗步驟與分析----29
4.1 試片之製備------29
4.1.1 研究之材料----29
4.1.2 製程參數------29
4.1.3 燒結條件----31
4.2 特性量測與分析----31
4.2.1 XRD分析------31
4.2.2 SEM分析-------32
4.2.3密度之量測----------33
4.2.4微波特性量測----34
第五章 結果與討論-------35
5.1 ZTN-----------35
5.1.1 ZTN反應機制分析-------35
5.1.2 XRD分析-------36
5.1.3相對直徑收縮率百分比分析--------36
5.1.4密度分析----------------37
5.1.5 SEM分析---------38
5.1.6 介電常數分析------39
5.1.7 品質因數與共振頻率之乘積分析-----40
5.1.8共振頻率溫度係數分析--------41
5.2 ZTN+0.5wt%CuO----41
5.2.1 XRD分析---------41
5.2.2相對直徑收縮率百分比分析------42
5.2.3密度分析-------42
5.2.4 SEM分析----43
5.2.5介電常數分析----44
5.2.6品質因數與共振頻率之乘積分析----44
5.2.7共振頻率溫度係數分析--------45
5.3 0.4ZnNb2O6-0.6TiO2---------46
5.3.1 XRD分析---------47
5.3.2相對直徑收縮率百分比分析------47
5.3.3密度分析-------48
5.3.4 SEM分析--------48
5.3.5介電常數分析------49
5.3.6品質因數與共振頻率之乘積分析-------50
5.3.7共振頻率溫度係數分析-----51
5.4 NTN---------52
5.4.1 NTN反應機制分析-----------52
5.4.2 XRD分析------53
5.4.3相對直徑收縮率百分比分析-------54
5.4.4密度分析---------55
5.4.5 SEM分析----------55
5.4.6 介電常數分析--------57
5.4.7 品質因數與共振頻率之乘積分析--------57
5.4.8共振頻率溫度係數分析-------58
5.5 NTN+0.5wt%CuO---------59
5.5.1 XRD分析----------59
5.5.2相對直徑收縮率百分比分析-------59
5.5.3密度分析------60
5.5.4 SEM分析----60
5.5.5介電常數分析----61
5.5.6品質因數與共振頻率之乘積分析------62
5.5.7共振頻率溫度係數分析-------62
5.6 NiNb2O6+8~10 mol%TiO2 -------63
5.6.1 XRD分析----------63
5.6.2相對直徑收縮率百分比分析------64
5.6.3密度分析---------65
5.6.4 SEM分析------65
5.6.5介電常數分析-----66
5.6.6品質因數與共振頻率之乘積分析-----67
5.6.7共振頻率溫度係數分析------68
第六章 結論-----69
參考文獻-------72
表4.1 ZTN燒結條件------------77
表4.2 ZTN+0.5wt% CuO燒結條件--------77
表4.3 0.4ZnNb2O6-0.6TiO2燒結條件-----------78
表4.4 NTN燒結條件-------------78
表4.5 NTN+0.5wt% CuO燒結條件------79
表4.6 NiNb2O6+8~10 mol%TiO2燒結條件-----------79
表5.1 ZTN在不同燒結溫度和持溫時間的平均晶粒大小(單位：μm)-80
表5.2 ZTN+0.5wt% CuO在不同燒結溫度和持溫時間的平均晶粒大小(單位：μm)---------------80
表5.3 0.4ZnNb2O6-0.6TiO2在不同燒結溫度和持溫時間的平均晶粒大小(單位：μm)----------80
表5.4 NTN在不同燒結溫度和持溫時間的平均晶粒大小(單位：μm)-81
表5.5 NTN+0.5wt% CuO在不同燒結溫度和持溫時間的平均晶粒大小(單位：μm)-------------81
表5.6 NiNb2O6+8~10 mol%TiO2在不同燒結溫度和持溫時間的平均晶粒大小(單位：μm)--------81
圖2.1四種極化機構-------------82
圖2.2頻率對極化機構的影響--------83
圖2.3共振波峰的頻譜示意圖--------83
圖2.4 (A)TE01δ Mode電場及磁場示意圖；(B)TM01δ Mode電場及磁場示意圖；(C)HEM01δ電場與磁場示意圖-----84
圖2.5 DR量測夾具----------85
圖2.6 DR量測夾具實體圖------85
圖2.7介電係數測量之量測系統-------86
圖2.8在TE模式下DR電場之分佈區域------86
圖4.1實驗流程--------87
圖5.1 ZTN加熱至各溫度不持溫之XRD分析圖---88
圖5.2 ZTN加熱至 (a)700℃；(b)800℃；(c)900℃；(d)1000℃；(e)1100℃溫度下不持溫之SEM圖---89
圖5.3 ZTN DSC-TGA分析圖----------90
圖5.4 ZTN在1200℃及1250℃和1300℃燒結2小時之XRD分析圖-90
圖5.5 ZTN在各溫度燒結之收縮率曲線圖-------91
圖5.6 ZTN在各溫度燒結之密度及相對密度曲線圖--91
圖5.7 ZTN在 (a)1050℃；(b)1100℃；(c)1150℃；(d)1200℃；(e)1250℃持溫2小時的SEM圖-------92
圖5.8 ZTN在 (a)1050℃；(b)1100℃；(c)1150℃；(d)1200℃；(e)1250℃持溫4小時的SEM圖-------93
圖5.9 ZTN在各溫度燒結之介電常數曲線圖-----94
圖5.10 ZTN在各溫度燒結之Q×f曲線圖------94
圖5.11 ZTN在各溫度燒結之τf曲線圖-----95
圖5.12 ZTN+0.5wt% CuO在1050℃及1100℃燒結2小時之XRD分析圖------96
圖5.13 ZTN+0.5wt% CuO在各溫度燒結之收縮率曲線圖-------97
圖5.14 ZTN+0.5wt% CuO在各溫度燒結之密度相對密度曲線圖-----97
圖5.15 ZTN+0.5wt% CuO在 (a)1000℃；(b)1030℃；(c)1050℃；
(d)1070℃；(e)1100℃持溫2小時的SEM圖-----98
圖5.16 ZTN+0.5wt% CuO在 (a)1000℃；(b)1030℃；(c)1050℃；(d)1070℃；(e)1100℃持溫4小時的SEM圖---99
圖5.17 ZTN+0.5wt% CuO在各溫度燒結之介電常數曲線圖---100
圖5.18 ZTN+0.5wt% CuO在各溫度燒結之Q×f曲線圖---100
圖5.19 ZTN+0.5wt% CuO在各溫度燒結之τf曲線圖--101
圖5.20 0.4ZnNb2O6-0.6TiO2在1200℃及1250℃和1300℃燒結2小時之XRD分析圖-------102
圖5.21 0.4ZnNb2O6-0.6TiO2在各溫度燒結之收縮率曲線圖----103
圖5.22 0.4ZnNb2O6-0.6TiO2在各溫度燒結之密度相對密度曲線圖-103
圖5.23 0.4ZnNb2O6-0.6TiO2在 (a)1050℃；(b)1100℃；(c)1150℃；(d)1200℃；(e)1250℃；(f)1300℃持溫2小時的SEM圖--------104
圖5.24 0.4ZnNb2O6-0.6TiO2在(a)1050℃；(b)1100℃；(c)1150℃；(d)1200℃；(e)1250℃；(f)1300℃持溫4小時的SEM圖--------105
圖5.25 0.4ZnNb2O6-0.6TiO2在各溫度燒結之介電常數曲線圖-------106
圖5.26 0.4ZnNb2O6-0.6TiO2在各溫度燒結之Q×f曲線圖--------------106
圖5.27 0.4ZnNb2O6-0.6TiO2在各溫度燒結之τf曲線圖------------------107
圖5.28 NTN加熱至各溫度不持溫之XRD分析圖-----108
圖5.29 NTN加熱至 (a)700℃；(b)800℃；(c)900℃；(d)1000℃；(e)1100℃溫度下不持溫之SEM圖-----109
圖5.30 NTN DSC-TGA分析圖-------110
圖5.31 NTN在1200℃及1250℃和1300℃燒結2小時之XRD分析圖-----------110
圖5.32 NTN在各溫度燒結之收縮率曲線圖----111
圖5.33 NTN在各溫度燒結之密度相對密度曲線圖----111
圖5.34 NTN在 (a)1200℃；(b)1230℃；(c)1250℃；(d)1270℃；(e)1300℃持溫2小時的SEM圖---112
圖5.35 NTN在 (a)1200℃；(b)1230℃；(c)1250℃；(d)1270℃；(e)1300℃持溫4小時的SEM圖-----113
圖5.36 NTN在 (a)1130℃；(b)1150℃；(c)1170℃；(d)1200℃；(e)1230℃持溫6小時的SEM圖-----114
圖5.37 NTN在各溫度燒結之介電常數曲線圖---115
圖5.38 NTN在各溫度燒結之Q×f曲線圖-----115
圖5.39 NTN在各溫度燒結之τf曲線圖----116
圖5.40 NTN+0.5wt% CuO在1070℃及1100℃燒結2小時之XRD分析圖----117
圖5.41 NTN+0.5wt% CuO在各溫度燒結之收縮率曲線圖------118
圖5.42 NTN+0.5wt% CuO在各溫度燒結之密度相對密度曲線圖---118
圖5.43 NTN+0.5wt% CuO在 (a)1070℃；(b)1100℃；(c)1130℃；(d)1150℃；(e)1170℃持溫2小時的SEM圖--119
圖5.44 NTN+0.5wt% CuO在 (a)1070℃；(b)1100℃；(c)1130℃；(d)1150℃；(e)1170℃持溫4小時的SEM圖--120
圖5.45 NTN+0.5wt% CuO在各溫度燒結之介電常數曲線圖---------121
圖5.46 NTN+0.5wt% CuO在各溫度燒結之Q×f曲線圖--121
圖5.47 NTN+0.5wt% CuO在各溫度燒結之τf曲線圖122
圖5.48 NNT8在1200℃及1250℃及1270℃和1300℃燒結2小時之XRD分析圖----123
圖5.49 NNT9在1200℃及1250℃及1270℃和1300℃燒結2小時之XRD分析圖---124
圖5.50 NNT10在1200℃及1250℃及1270℃和1300℃燒結2小時之XRD分析圖---125
圖5.51 NNT8及NNT9和NNT10在各溫度燒結2小時之收縮率曲線圖------126
圖5.52 NNT8及NNT9和NNT10在各溫度燒結2小時之密度曲線圖---------126
圖5.53 NNT8在 (a)1170℃；(b)1200℃；(c)1230℃；(d)1250℃；(e)1270℃；(f)1300℃持溫2小時的SEM圖-------127
圖5.54 NNT9在 (a)1170℃；(b)1200℃；(c)1230℃；(d)1250℃；(e)1270℃；(f)1300℃持溫2小時的SEM圖----128
圖5.55 NNT10在 (a)1170℃；(b)1200℃；(c)1230℃；(d)1250℃；(e)1270℃；(f)1300℃持溫2小時的SEM圖-----129
圖5.56 NNT8及NNT9和NNT10在各溫度燒結2小時之介電常數曲線圖----------130
圖5.57 NNT8及NNT9和NNT10在各溫度燒結2小時之Q×f曲線圖-----------130
圖5.58 NNT8及NNT9和NNT10在各溫度燒結2小時之τf曲線圖-------131

[1]R.D. Richtmyer, “Dielectric Resonator”, Jpn. J. Appl. phys. 10 (1939) 391-398.
[2]H.J. Lee, I.T. Kim, K.S. Hong, “Dielectric Properties of AB2O6 compounds at microwave frequencies (A=Ca, Mg, Co, Ni, Zn, and B=Nb, Ta)”, Jpn. J. Appl. Phys. 36(10A) (1997) 1318-1320.
[3]H.J. Lee, K.S. Hong, S.J. Kim, I.T. Kim, “Dielectric Properties of MNb2O6 compounds (Where M=Ca, Mn, Co, Ni, or Zn)”, Mater. Res. Bull. 32(7) (1997) 847-855.
[4]C.S. Hsu, C.L. Huang, J.F. Tseng, C.Y. Huang,“ Improved high-Q microwave dielectric resonator using CuO-doped MgNb2O6 ceramics”, Mater. Res. Bull. 38 (2003) 1091-1099.
[5]S.H. Wee, D.W. Kim, S.I. Yoo, “Microwave Dielectric Properties of Low-Fired ZnNb2O6 Ceramics with BiVO4 Addition”, J. Am. Ceram. Soc. 87(5) (2004) 871-875.
[6]Y.C. Zhang, Z.X. Yue, Z.L. Gui, L.T. Li, “Effects of CaF2 addition on the microstructure and microwave dielectric properties of ZnNb2O6 ceramics”, Ceram. Int. 29 (2003) 555-559.
[7]W.X. Cheng, A.L. Ding, P.S. Qiu, Y.C. Zhang, X.Y. He, X.Sh. Zheng, “Properties of preferential (Zr0.8, Sn0.2)TiO4 thin films prepared by if magnetron sputtering for microwave application“, Micro. Eng. 66 (2003) 648-653.
[8]G.H. Huang, D.G. Zhou, J.M. Xu, X.P. Chen, D.L. Zhang, W.H. Lu, B.Y. Li, “Low-temperature sintering and microwave dielectric properties of (Zr, Sn) TiO4 ceramics”, Mater. Sci. & Eng. B99 (2003) 416-420.
[9]C.L. Huang, C.L. Pan, J.F. Hsu, “Dielectric properties of (1-x)(Mg0.95Co0.05)TiO3-xCaTiO3 ceramic system at microwave frequency”, Mater. Res. Bull. 37 (2002) 2483-2490.
[10]D. Kajfez, P. Guillon, "Dielectric resonators", Norwood, MA, Artech House, Inc. (1986) 547.
[11]吳朗, “電子陶瓷-介電”, 全欣科技圖書. (1994) 268-275.
[12]D.M Pozar, “Microwave Engineering”, J. Wiley & Sons, Inc. (1998) ch2.
[13]B.W. Hakki, P.D. Colemean, “A Dielectric Resonator Method of Measuring Inductive Capacities in the Millimeter Range”, IRE Trans. MTT-8 (1960) 402-410.
[14]W.E. Courtney, “Analysis and evaluation of a method of measuring the complex permittivity and permeability of microwave insulators”, IEEE Trans. MTT-18 (1970) 476-485.
[15]Y. Kobayashi, N. Katoh, “Microwave Measurement of Dielectric Properties of Low-Loss Materials by Dielectric Rod Resonator Method”, IEEE Trans. MTT-33 (1959) 220-228.
[16]翁敏航, 楊茹媛, 洪政源, 李義傑, 洪茂峰, “高介電材料之微波特性量測(一) ”, 奈米通訊, 第11期, 31-39.
[17]W.J. Huppmann, G. Petzow, “The Elementary Mechanisms of Liquid Sintering”, Sintering Process, Plenum Press. (1979) 189-202.
[18]H.S. Cannon, F.V. Lenel, “Proceedings of the Plan see Seminar”, Metallwerk Plansee, Reutte. (1953) 106-121.
[19]R. Raj, C.K. Chyung, “Solution Reprecipitation Creep in Glass Ceramics”, Acta Metall. (1980) 159-166.
[20]V.N. Eremenko, Y.V. Naidich, I.A. Lenko, ”Liquid Consolation New York”, (1970) ch4.
[21]K.S. Hwang, Phd. Thesis, “Rensselaer Ploytechnic in Troy”, (1984).
[22]J.W. Cahn, R.B. Heady, J. Am, “Analysis of Capillary Forces in Liquid-Phase Sintering of Jagged Particles”, J. Am. Ceram. Soc. (1970) 406-409.
[23]W.J. Huppmann, G. Petzow, “Sintering process, Edited by G.C. Kuczynski”, Plenum Press, New York. (1980) 189-202.
[24]W.J. Huppmann, G. Petzow, “The Role of Grain and Phase Boundaries in Liquid Phase Sintering”, Ber. Bunnsenges Phys. 82 (1978) 308-312.
[25]R.M. German, “Liquid Phase Sintering”, Plenum Press, New York. 119 (1985) ch4.
[26]R.B. Heady, J.W. Cahn, “An Analysis of the Capillary Forces in Liquid-Phase Sintering of Spherical Particles”, Metal. Trans. 1 (1970) 185-189.
[27]R.B. Heady, J.W. Cahn, “Analysis of Capillary Forces in Liquid-Phase Sintering of Jagged Particles”, J. Am. Ceram. Soc. 7 (1970) 406-409.
[28]陳皇均, “陶瓷材料概論’’, 曉園, 台北市, (1992) 3版.
[29]D.W. Kim, K.H. Ko, K.S. Hong, “Influence of Copper(II) Oxide Additions to Zinc Niobate Microwave Ceramics on Sintering Temperature and Dielectric properties”, J. Am. Ceram. Soc. 84(6) (2001) 1286-1290.
[30]L.B. Kong, J. Ma, H. Huang, R.F. Zhang, T.S. Zhang, “Zinc niobate derived from mechanochanochemically activated oxides”, J. All. & Comp. 347 (2002) 308-313.
[31]R.C. Pullar, K. Okeneme, N.M. Alford, “Temperature compensated niobate microwave ceramics with the columbite structure, M2+Nb2O6”, J. Eur. Ceram. Soc. 23 (2003) 2479-2483.
[32]A. Templeton, X. Wang, S.J. Penn, S.J. Webb, L.F. Cohen, N.M. Alford, “Microwave dielectric loss of titanium dioxide ”, J. Am. Ceram. Soc. 83(1) (2000) 95-100.
[33]Y.C. Zhang, J. Wang, Z.X. Yue, Z.L. Gui, L.T. Li, “Effects of Mg2+ substitution on microstructure and microwave dielectric properties of (Zn1-xMgx)Nb2O6 ceramics ”, Ceram. Int. 30 (2004) 87-91.
[34]D.W. Kim, H.B. Hong, K.S. Hong, “Structural Transition and Microwave Dielectric Properties of ZnNb2O6-TiO2 Sintered at Low Temperatures”, Jpn. J. Appl. Phys. 41(3A) (2002) 1465-1469.
[35]D.W. Kim, K.H. Ko, D.K. Kwon, K.S. Hong, “Origin of Microwave Dielectric Loss in ZnNb2O6-TiO2”, J. Am. Ceram. Soc. 85(5) (2002) 1169-1172.
[36]D.W. Kim, D.Y. Kim, K.S. Hong, “Phase relations and microwave dielectric properties of ZnNb2O6-TiO2”, J. Mater. Res. 15(6) (2000) 1331-1335.
[37]宋月倫, “ZnNb2O6與MgNb2O6微波介電陶瓷製程及其特性之研究”, 崑山科技大學電子系碩士論文, (2005).
[38]Y.C. Zhang, Z.X. Yue, Z.L. Gui, L.T. Li, “Microwave dielectric properties of (Zn1-xMgx)Nb2O6 ceramics”, Mater. Lett. 57 (2003) 4531-4534.
[39]薛朝陽, “Columbite之MNb2O6(M=Ni,Ca)微波介電陶瓷製程及其特性之研究”, 崑山科技大學電子系碩士論文, (2005).
[40]S. Ananta, R. Brydson, N.W. Thomas, “Synthesis, formation and characterisation of MgNb2O6 Powder in a columbite-like phase”, J. Eur. Ceram. Soc. 19 (1999) 355-362.
[41]Y.C. Liou, C.Y. Shih, C.H. Yu, “Stoichiometric Pb(Fe1/2Nb1/2)O3 perovskite ceramics produced by reaction-sintering process”, Mater. Lett. 57 (2003) 1977-1981.
[42]J.H. Chen, Y.C. Liou, K.H. Tseng, ”Stoichiometric perovskite lead magnesium niobate ceramics produced by reaction-sintering process”, Jpn. J. Appl. Phys. 42(1A) (2003) 175-181.