臺灣博碩士論文加值系統

本研究選擇三元系鍶鋅磷酸鹽玻璃(SrO-ZnO-P2O5)作為研究的對象。研究之主要目的，在採用一般商用試藥級之原料，以製備高紫外穿透性之磷酸鹽玻璃；以SrO取代ZnO來探討對於磷酸鹽玻璃性質之改變與結構之變化。
本系玻璃之性質與組成有很密切的關係，當玻璃中SrO含量增加時，玻璃之密度、玻璃轉移溫度(Tg)、玻璃軟化溫度(Td)與熱膨脹係數(���w也隨之上升，而其化學耐久性獲得改善。利用一般試藥級可以熔煉出高紫外穿透度的磷酸鹽玻璃，於250 nm的波長仍有70 %的穿透度。隨著SrO含量增加，其紫外穿透度受到修飾劑離子半徑與場強的關係，導致其紫外穿透度下降。
添加Al2O3取代ZnO可以增加其化學耐久性，但由於鋁離子與磷酸分子產生Al-O-P鍵聯，造成其3s-3p能階變小，導致其穿透度隨著Al2O3增加而紫外穿透度下降。熔煉時間之改變也會影響到玻璃之結構與性質。將熔煉時間拉長，延長1.5小時其玻璃可以達到最低的含水量，隨著時間繼續拉長，其含水量會逐漸提高。而OH含量會影響紫外穿透度，隨著OH含量增多其紫外穿透度會隨之下降。
本研究利用霍氏轉換紅外光譜儀(FTIR)及固態核磁共振儀(31P MAS-NMR)來探討玻璃之結構。在P2O5含量為50與60 mole%之玻璃系統中，50 mole%的玻璃結構屬於長鏈狀的鍵聯形式，60 mole%則屬於環鏈狀的鍵聯形式。隨著SrO含量，P-O-P鍵聯不會被破壞，提高了玻璃網絡之鍵聯密度與強度。而使玻璃之Tg提高，化學耐久性獲得改善。在P2O5含量為40 mole%之玻璃系統中，PO3與PO-含量增多以及O-P-O遭到破壞，31P MAS-NMR顯示Q1含量增多，由FTIR中顯示P-O-P鍵聯受到修飾劑的SrO與ZnO的破壞，由此說明磷酸鏈鏈長之縮短。

The main objective of this thesis is to study the structure and properties of ternary strontium zinc phosphate (SrO-ZnO-P2O5) glass system in a systematic manner, in order to develop a UV-transmitting phosphate glass by using the reagent-grade raw materials.
The properties of this glass system are strongly composition dependent. Substitution of SrO for ZnO increases density, glass transition temperature (Tg), glass softening temperature (Td) and thermal expansion coefficient (���w of the glass. Besides, the chemical durability of the glasses was improved. The high UV-transmitting phosphate glass, which the light transmittance of 250 nm wavelength is over 70%, could be prepared by using the reagent-grade raw materials. The UV-transmitting of glasses is related with the cation radius and field strength of modifier. It is result in the UV light would be absorbed with increasing SrO content.
Substitution of Al2O3 for ZnO improved the chemical durability of glasses. The aluminium ions are bonded with phosphate molecules (Al-O-P). It would make the 3s-3p transition energy become lower to lead to the UV-transmittance of glasses is decreased with increasing Al2O3 content. The structure and properties of P2O5-ZnO-SrO glasses vary with melting time. When the melting time is 1.5 hour, the glasses have the lowest OH- content. With longer melting time, the OH- content of the glasses would be increased.
The structure of the glasses was examined by Fourier transformed infrared spectroscopy (FTIR) and 31P solid state nuclear magnetic resonance (31P MAS-NMR). In the 50 and 60 mole% P2O5 glass systems, The bonding structure of 50 mole% P2O5 glass is chain and 60 mole% P2O5 glasses is ring. In the two systems, the bond of P-O-P would be not destroyed with SrO content. It results in enhancing the strength and density of glass network. The chain or ring structure will be tighter leading to increased Tg and chemical durability of the glasses. In the 40 mole% P2O5 glass system, the content of PO3 and PO- bond will be increased and the O-P-O bond will be destroyed. The analysis of 31P MAS-NMR is indicated the content of Q1 is increased and the FTIR spectra is showed the content of P-O-P bond is destroyed by the modifier (SrO and ZnO). It lead to the chain length of phosphate shorten.

摘 要 ................................I
英文摘要 ................................III
目 錄 ................................V
表目錄 ................................IX
圖目錄 ................................X

第一章 緒論............................1
1-1 前言............................1
1-2 研究目的........................4

第二章 理論基礎與論文回顧..............6
2-1 玻璃結構........................6
2-1-1 玻璃的定義......................6
2-1-2 Zachariasen's無規則網絡學說.....7
2-1-3 鍵聯條件........................9
2-2 磷酸鹽玻璃......................11
2-2-1 磷酸鹽系玻璃的單元結構..........12
2-2-2 磷酸鹽玻璃之分類................15
2-3 磷酸鹽耐水性之研究..............19
2-4 鋅磷酸鹽玻璃之研究..............20

2-5 紫外線穿透與玻璃關係............22
2-5-1 何謂紫外線......................22
2-5-2 玻璃對紫外線的吸收效應..........25
2-5-3 影響玻璃紫外穿透的因素..........26
2-6 紫外穿透性於磷酸鹽系玻璃之研究..27

第三章 實驗方法與步驟..................31
3-1 SrO-ZnO-P2O5 系列玻璃之熔製.....31
3-1-1 實驗藥品........................31
3-1-2 實驗流程........................31
3-2 基本性質量測與分析..............35
3-2-1 XRD繞射分析.....................35
3-2-2 密度量測........................35
3-2-3 熱性質分析......................35
3-2-4 化學耐久性試驗..................36
3-2-5 玻璃之紫外穿透度檢測............36
3-3 結構分析........................37
3-3-1 FTIR光譜分析....................37
3-3-2 31P MAS-NMR光譜分析.............37
第四章 實驗結果........................38
4-1 玻璃系統配方確認................38
4-2 玻璃之性質......................39
4-2-1 玻璃密度........................42
4-2-2 Tg及Td..........................44
4-2-3 熱膨脹係數......................44
4-2-4 化學耐久性......................46
4-2-5 紫外線穿透與光能階(Eopt)........48
4-3 玻璃結構........................58
4-3-1 FTIR光譜分析....................58
4-3-2 31P MAS-NMR光譜分析.............65

第五章 討論............................68
5-1 玻璃組成與性質..................68
5-1-1 密度............................68
5-1-2 熱性質(Tg、Td、a)...............68
5-1-3 化學耐久性......................70
5-1-4 紫外可見光譜分析................71
5-2 鍶鋅磷酸鹽玻璃之結構............73
5-2-1 偏磷酸鹽玻璃(P2O5=50 mol%)......73
5-2-2 超磷酸鹽玻璃(P2O5> 50 mol%).....75
5-2-3 焦磷酸鹽玻璃(P2O5< 50 mol%).....76

第六章 結論............................80

參考文獻.................................82

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