臺灣博碩士論文加值系統

本研究是以鋅鉍氯磷酸鹽(P2O5‒Bi2O3‒ZnO‒ZnCl2)玻璃系統作為研究對象，以不同的成分組成以及不同的熔融條件(熔融溫度的變化、持溫時間變化)，來探討其改變對玻璃光學性質、熱性質及化學耐久性等之影響。以霍氏轉換紅外光譜儀(FTIR)、拉曼光譜儀(RAMAN)以及X光光電子能譜儀(XPS)來分析玻璃之結構，了解玻璃結構對玻璃各項性質的影響。
實驗結果指出鋅鉍磷酸鹽25P2O5‒20Bi2O3‒55ZnO玻璃系列具有高折射率(nD≧1.8)，具有良好的耐水性，當玻璃系統以ZnCl2取代ZnO含量增加至3 mole%時，體密度隨之降低、玻璃轉移溫度(Tg)增高，近紫外光學穿透性往短波長移動，光能隙變大，折射率也隨極性改變而有變小的趨勢。在ZnCl2的含量超過3 mole%時，則各性質的變化趨勢相反。
隨著Bi2O3的取代ZnO含量越多，體密度、熱膨脹係數、折射率會隨之升高，Tg和阿貝數會隨之減少，其玻璃轉換溫度大約在430 ~ 460oC，折射率約在1.8~2.0之間。
鋅鉍氯磷酸鹽玻璃系統，在熔融溫度提高的條件下，玻璃外觀會呈現紅棕色或黑色而使玻璃穿透率變差。由XPS實驗結果顯示玻璃外觀變深的現象，是Bi離子還原成Bi原子所造成的，外摻氧化劑(CeO2、Sb2O3)能有效的氧化Bi0，達到良好的消色效果以及改善玻璃穿透率。

In this study, glasses of the system zinc-bismuth chlorophosphate (P2O5‒Bi2O3‒ZnO‒ZnCl2) have been prepared. The optical properties, thermal properties, and chemical durability of glass were investigated by varying the glass compositions and the melting conditions (melting temperature and melting time). In addition, the structure of the glasses were examined by Fourier transformed infrared spectroscopy (FTIR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), to clarify the affection of glass characteristics by structure altered with variable composition.
Experimental results show that zinc-bismuth chlorophosphate glasses have high refractive index and strongly water resistance. The density and refractive index of the glass decrease; while the glass transition temperature and the UV-transmittance increase with increasing ZnCl2 content up to around 3mol%. However, as the ZnCl2 content in glasses increased to more than 3mol%, the tendencies in property variation of the glasses are opposite to those of glasses with ZnCl2 content less than 3mol%.
With Bi2O3 content increased, the glass density, thermal expansion coefficient and refractive index would increase; while the glass transition temperature and Abbe number would decrease. The range of glass transition temperature is 430~460oC, and refractive index is 1.8 to 2.0.
In the other hand, glass of the systems zinc-bismuth chlorophosphate has darkening effect (black coloration). The colors of the glasses change in all cases from pale yellow to deep brown or black as the melting temperature increase. The reduction of Bi ions to Bi atoms is observed by XPS Bi4f spectra. The addition of CeO2、Sb2O3 can eliminate the darkening color and increase the optical transmittance of the glasses by oxidizing Bi atoms to Bi ions.

致謝
中文摘要
Abstract
目錄
表目錄
圖目錄
第一章 緒論
1-1 前言
1-2 研究目的
第二章 理論基礎與文獻回顧
2-1 玻璃形成與結構
2-1-1 玻璃的定義
2-1-2 Zachariasen’s 無規則網絡學說
2-1-3 玻璃之鍵結
2-2 磷酸鹽玻璃
2-2-1 磷酸鹽系玻璃之單元結構
2-2-2 磷酸鹽玻璃之結構分類
2-3 玻璃的光學性質
2-3-1 折射率
2-3-2 分散
2-4 玻璃的紫外光吸收
2-4-1 紫外光
2-4-2 玻璃對紫外線吸收效應
2-4-3 影響玻璃紫外線穿透之因素
2-5 含鉍玻璃文獻回顧
第三章 實驗步驟及方法
3-1玻璃成分及製程設計
3-2玻璃的熔製
3-3 基本性質分析測量
3-3-1體密度量測
3-3-2熱性質分析
3-3-3化學耐久性試驗
3-3-4紫外-可見光譜
3-3-5折射率
3-4玻璃結構分析
3-4-1 X光繞射分析
3-4-2 FTIR光譜分析
3-4-3 Raman 光譜分析
3-4-4 XPS
第四章 結果與討論
4-1 鋅鉍氯磷酸鹽玻璃外觀與製程條件之關係
4-2 鋅鉍氯磷酸鹽玻璃之基本性質
4-2-1 體密度
4-2-2 熱性質
4-2-3 化學耐久性
4-3 鋅鉍氯磷酸鹽玻璃光學性質
4-3-1 折射率
4-3-2 紫外可見光譜
4-4 鋅鉍氯磷酸鹽玻璃結構
4-4-1 XRD
4-4-2 FTIR
4-4-3 RAMAN
4-4-4 XPS
4-5 鋅鉍磷酸鹽玻璃著色問題探討
4-5-1 添加氧化劑對鋅鉍磷酸鹽玻璃之影響
第五章 結論
參考文獻

1. Horst Scholze, “Glass-nature, structure and properties”, translated by M. J. Lakin, Springer-Verlage, New York, (1991).
2. I. W. Donald, B. L. Metcalfe, D.J. Bradley, M. J. C. Hill, J. L. Mcgrath andA. D. Bye, “The preparation and properties of some lithium borate basedglasses”, J. Mater. Sci., 29, (1994) 6379-6396.
3. D. Ehrt, P. Ebeling and U. Natura, “UV Transmission and radiation-induced defects in phosphate and Fluoride-phosphate glasses”, J. Non-Cryst. Solids,263&264, (2000) 240-250.
4. D. Moncke, D. Ehrt, “Photoionization of As, Sb, Sn, and Pb in metaphosphate glasses”, J. Non-Cryst. Solids, 345&346, (2004) 319-322.
5. B. Karmakar, P. Kundu and R. N. Dwivedi, “Effect of vacuum dehydroxylation on the UV transparency and structure of metaphosphate glasses”, Mater. Lett., 47, (2001) 371-375.
6. N. Kitamura , K. Fukumi , J. Nakamura, T. Hidaka , T. Ikeda , H. Hashima, J. Nishii ,Optical properties of fluorine substituted zinc bismuth phosphate glasses, J.Non-Cryst Solids 357 (2011) 1188–1192.
7. J. E. Shelby, “Introduction to glass science and technology”, ch1,RSC Paperbacks, Inc., USA, 1997.
8 Y. B. Peng and D. E. Day, “High thermal expansion phosphate glasses part Ι”,Glass Technol., 32[5] (1991) 214-219.
9.W. H. Zachariasen, “The atomic arrangement in glass”, J. Am. Chem. Soc., 54(1932) 3841-3851.
10.A. Z. Dietzel, Z. Eletrochem., 48 (1942) 9-23.
11. 盧安賢, “新型功能玻璃材料”, 中南大學出版社, (2005).
12. J. V. Wazer, “Phosphorus and its compounds”, vol 1, New York, 1958.
13. R. K. Brow, “Section 1. Structure Review ： the structure of simple phosphate glasses”, J. Non-Cryst. Solids., 4, 263&264 (2000) 1-28.
14. T. Kanazawa, “Inorganic phosphate materials”, Elsevier New York, 1989.
15. J.E. Shelby, “Introduction to glass science and technology”, Royal Society of Chemistry, (2005).
16.泉谷徹郎著, 高正雄譯, “光學玻璃” 復漢出版社, (1985).
17. http://aeea.nmns.edu.tw/2006/0608/ap060805.html, 天文教育資訊館
18. J.A. Duffy, “Ultraviolet transparency of glass – a chemical approach in terms of band theory polarisability and electronegativity”, Phys. Chem. Glasses, 42(3)(2001) 151-157.
19. D. Ehrt, “UV-absortion and radiation effects in different glasses doped with iron and tin in the ppm range”, C.R. Chimie, 5 (2002) 679-692.
20. S.M. Abo-Naf, M. S. El-Amiry, A. A. Abdel-Khalek, “FT-IR and UV-Vis optical absorption spectra of γ-irradiated calcium phosphate glasses doped with Cr2O3,V2O5 and Fe2O3”, Optical Materials, 30 (2008) 900-909.
21. P. Gray and L. C. Klein, “Optical spectra of sodium phosphate glasses”, J.Non-Cryst. Solids., 61[1] (1984) 75-86.
22. B. Karmakar, P. Kundu and R. N. Dwivedi, “Effect of vacuum dehydroxylation on the UV transparency and structure of metaphosphate glasses”, C. R. Chimie, 5(2000) 679-692.
23. Y. C. Ratnakaram and A. V. Reddy, “Eletronic spectra and optical band gap studies in neodymium chlorophosphate glasses”, J. Non-Cryst. Solids., 277(2000) 142-154.
24. B. C. Sales, J. U. Otaigbe, G. H. Beall, L. A. Boatner, J. O. Ramey,
“Structure of zinc polyphosphate glasses”, J. Non-Cryst. Solids, 226,
(1998) 287-293.
25. R. K. Brow, D. R. Tallant, S. T. Myers, C. C. Phifer “The short-range
structure of zinc polyphosphate glass”, J. Non-Cryst. Solids, 191, (1995) 45-55.
26. J. W. Wiench, M. Pruski, B. Tischendorf, J. U. Otaigbe, B. C. Sales
“Structural studies of zinc polyphosphate glasses by nuclear magnetic
resonance”, J. Non-Cryst. Solids, 263&264, (2000) 101-110.
27. J. Y. Song, T. J. Park, S. Y. Choi, “Preparation and characterization of CuO doped Bi2O3–B2O3–BaO–ZnO glass system for transparent dielectriclayer”, J. Non-Cryst. Solids, 352, (2006) 5403-5407.
28. Y. B. Peng, D. E. Day, “High thermal expansion phosphate glasses – partI”, Glass tech., 32, (1991) 166-173.
29. Ch. Srinivasu , V. Sathe , A.M. Awasthi , Syed Rahman , “Structural and transport properties of quaternary glass system: LiF–Li2O–SrO–Bi2O3” J. Non-Cryst. Solids 357 (2011) 1051–1055.
30. W.H. Dumbaugh, “Heavy metal oxide glasses containing Bi2O3” Phys. Chem. Glasses 27 (1986) 119.
31. A. Shaim, M. Et-tabirou, L. Montagne and G. Palavit, “Role of Bimuth and Titanium in Na2O−Bi2O3−TiO2−P2O5 glasses and a model of structural units”, Mater. Res. Bull., 37, (2002) 2459-2466.
32. I. Ardelean, V. Ioncu, “Structural investigation of CuO-Bi2O3-B2O3 glasses by FT-IR, Raman and UV-VIS spectroscopies” J OPTOELECTRON ADV M Vol. 8, No. 5, October 2006, p. 1843 – 1847.
33. R. Iordanova, y. Dimitriev, V. Dimitrov, S. Kassabov and D. Klissurski, “Glass formation and structure in the V2O5−Bi2O3−Fe2O3 glasses”, J. Non-Cryst. Solids, 204, (1996) 141-150.
34. A. Chahine, M. Et-tabirou and J.L. Pascal, “FTIR and Raman spectra of the Na2O–CuO–Bi2O3–P2O5 glasses”, Mater. Lett., 58, (2004) 2776-2780.
35. B. V. R. Chowdari and Z. Rong, “The role of Bi2O3 as a network modifier and a network former in x Bi2O3−(1-x)LiBiO2 glass system”, Sol. Stat. Ion., 90, (1996) 151-160.
36. L. Baia, R. Stefan, W. Kiefer and S. Simon, “Structural characteristics of B2O3–Bi2O3 glasses with high transition metal oxide content”, J. Raman Spectrosc., 36, (2005) 262-266.
37.O. Sanz, E. Haro-Poniatowski , J. Gonzalo, J.M. Fernandez Navarro, “Influence of the melting conditions of heavy metal oxideglasses containing bismuth oxide on their optical absorption”,J.Non-Cryst Solids, 352 (2006)761–768.
38. 翁啟儒, 鋅磷酸鹽玻璃的去烃效應,國立聯合大學材料科學研究所碩士論文,(2008).
39. Y. H. NA, N. J. KIM, S. H. IM, J. M. CHA ,B. K. RYU ,Effect of Bi2O3 on structure and properties of zinc bismuth phosphate glass, J. Cera. Soc. JP ,117 [11] (2009)1273-1276.
40. I.Dyamant , D.Itzhak , J.Hormadaly,Thermal properties andglass formation in the SiO2–B2O3–Bi2O3–ZnO quaternary system,J.Non-Cryst Solids, 351 (2005) 3503–3507.
41. S. H. Im , Y. H. Na , N. J. Kim , D. H. Kim , C. W. Hwang , B. K. Ryu ,Structure and properties of zinc bismuth phosphate glass , J. Thin Solid Films 518 (2010) e46–e49.
42. 許漢民, 鍶鋅磷酸鹽系紫外穿透玻璃之研究, 國立聯合大學材料科學研究所碩士論文,(2007).
43. Y.C. Ratnakaram , A. V. Reddy, Electronic spectra and optical band gap studies in neodymium chlorophosphate glasses, J. Non-Cryst Solids, 277 (2000) 142-154.
44. M. A. Chaudhry and M. Altaf, “Optical Absortion Studies of Sodium Cadmium Phosphate Glasses”, Mater. Letters, 34 (1998) 213-216.
45. A. S. Shawoosh and A. A. Kutub, “An investigation of the electrical,optical and DSC properties of a copper-phosphate glass composition”,J. Mater. Sci. 28 (1993) 5060-5064.
46. J. M. Arzeian and C. A. Hogarth, “Some structural, electrical andoptical properties of copper phosphate glasses containing the
rare-earth europium”, J. Mater. Sci. 26 (1991) 5553-5366.
47. H Fan. G Wang. L Hua. Infrared, “Raman and XPS spectroscopic studies of Bi2O3–B2O3–Ga2O3 glasses” , SOLID STATE SCI 11 (2009) 2065–2070.
48. R. Iordanova, Y. Dimitriev, V. Dimitrov, S. Kassabov and D. Klissurski , “Glass formation and structure in the V2O5−Bi2O3−Fe2O3 glasses”, J. Non-Cryst. Solids, 204, (1996) 141-150.
49. A. Chahine, M. Et-tabirou, “Structural study of (50-x) Na2O–xCuO–10Bi2O3–40P2O5 glasses”, Mater. Res. Bull., 37, (2002) 1973-1979.
50. P. Y. Shih,Thermal, “chemical and structural characteristics of erbium-doped sodium phosphate glasses”, Mater. Chem.Phy., 84, (2004) 151–156.
51. N. Kitamura, K.Fukumi,J.Nakamura, T. Hidaka, H. Hashima, Y. Mayumi, J. Nishii , “Optical properties of zinc bismuth phosphate glass”, MAT SCI E B 161 (2009) 91–95351 (2005) 3503–3507.
52. G. Lin, D. Tan, F. Luo, D. Chen, Q. Zhao, J. Qiu, “Linear and nonlinear optical properties of glasses doped with Bi nanoparticles” , J. Non-Cryst. Solids 357 (2011) 2312–2315.
53. P. Y. Shih, S. W. Yung, T. S. Chin, “Thermal and corrosion behavior of P2O5-NazO-CuO glasses”, J. Non-Cryst. Solids, 224 (1998) 143-152.
54. P. Y. Shih, S. W. Yung, T. S. Chin, “FTIR and XPS studies of P2O5-Na2O-CuO glasses”, J. Non-Cryst. Solids, 244 (1999) 211-222.
55. B. Oprea, T. Radu, S. Simon, “XPS investigation of atomic environment changes on surface of B2O3–Bi2O3 glasses”, J. Non-Cryst. Solids, 379 (2013) 35–39.
56. 周洪萍, 曾人杰, “CuO對ZnO-Bi2O3-B2O3 系玻璃結構及熱處理結果影響” 陶業學報 2278 (2010) 0568-0575.
57. H. S. Liu, T. S. Chin, S. W. Yung, “FTIR and XPS studies of low melting PbO-ZnO-P2O5 glasses”, Mater. Chem. Phys., 50, (1997) 1-10.
58. K. Meyer, “Characterization of the structure of binary zincultraphosphate glasses by infrared and Raman spectroscopy”, J. Non-Cryst. Solids, 209, (1997) 227-239.
59. G. P. Singh, D. P. Singh, “Spectroscopic study of ZnO doped CeO2–PbO–B2O3 glasses”, Physica B, 406, (2011)3402–3405.
60. S. P. Singh, R. P. S. Chakradhar, J. L. Rao, B. Karmakar, “EPR FTIR, optical absorption and photoluminescence studies of Fe2O3 and CeO2 doped ZnO–Bi2O3–B2O3 glasses”, J. Alloys Compd, 493, (2010) 256–262.
61 G. P. Singh, P. Kaur, S. Kaur, D. P. Singh, “Investigation of structural,physical and optical properties of CeO2–Bi2O3–B2O3 glasses”, Physica B, 407, (2012) 4168–4172.
62. G. P. Singh, D. P. Singh, “Effect ofWO3 on structural and optical properties of CeO2–PbO–B2O3 glasses”, Physica B, 406, (2011) 640–644.