臺灣博碩士論文加值系統

本實驗研究Anatase相氧化鈦於高能行星式球磨中之相變態過程，Anatase相粉末首先使用不鏽鋼模具並添加酒精研磨0.1 - 12 hrs，並使用X光繞射儀(XRD)與解析式電子顯微鏡(AEM)進行相組成分析。XRD結果顯示研磨粉末中包含殘留的Anatase相、中間相TiO2-Ⅱ與最終產物Rutile相。其中，當研磨時間達到7 hrs時 TiO2-Ⅱ相比例增加至50~60 %。此外，AEM分析更在球磨粉末中觀察到第四種結構，單斜晶TiO2(B)相。此TiO2(B)相出現為單相的奈米粉粒或以薄層狀(厚度約為2 – 35 nm)出現在混相的Anatase-TiO2(B)、TiO2(B)-TiO2-II晶粒中。由繞射圖得知這些混相晶粒分別遵循以下晶向關係: Anatase - TiO2(B): <010>A ∥<010> B、{103}A ∥{-201} B；TiO2(B)-TiO2-Ⅱ: <-22-1>Ⅱ∥<010> B 、{10-2}Ⅱ∥{-20-2}B；TiO2-II – rutile : <010>II ∥<111>R，其可能是由高能球磨剪應力所造成。根據以上的發現，以及已知之TiO2-Ⅱ<-> Rutile之剪變形行為，證實在高能球磨中Anatase相變態進程為: anatase->TiO2(B)->TiO2-II->rutile。

The transformation pathway of anatase TiO2 in high-energy planetary ball-milling was studied. Anatase powders were first milled using stainless ball/jar with the additive of ethanol alcohol for 10 mins to 12 hrs, followed by structure characterization by X-ray diffractometer (XRD) and analytical electron microscope (AEM). XRD revealed complicated phase assemblages in all milled powders, including residue anatase, the transitional TiO2-II phase and the final product of rutile. In the powders milled for up to ~7 hrs, the TiO2-II phase contents could reach ~50-60%. In addition to the above three polymorphs, AEM further identified a fourth monoclinic TiO2 (B) phase in the as-milled TiO2 powders . This TiO2 (B) phase occurs either as isolated nanosized particles or as thin lamellae of ~2-35 nm in thickness in the mixed-phase anatase-TiO2 (B) or TiO2 (B)-TiO2-II particles. Electron diffraction patterns showed that the mixed-phase powders follow specific crystallographic orientation relationships: <010>A ∥<010> B、{103}A ∥{-201} B for anatase-TiO2 (B); <-22-1>Ⅱ∥<010> B 、{10-2}Ⅱ∥{-20-2}B for TiO2 (B)-TiO2-II; <010>II ∥<111>R for TiO2-II – rutile, all of which being formed by sequential shear deformation of TiO2 polymorphs in high-energy milling. These observations, together with the well-known shear transformation of TiO2-II to rutile, unequivocally establish the anatase to rutile transformation pathway during high-energy milling process as: anatase => TiO2 (B) => TiO2-II => rutile, and open the doorway for the future mass production of nano-sized mixed-phase TiO2 powders with various phase assemblages and unique photocatalyst properties.

第一章 前言 1
第二章 文獻回顧 3
2.1 二氧化鈦 (Titanium dioxide，TiO2) 的晶體結構 3
2.2 二氧化鈦之相變態 7
2.3 高能球磨法 10
2.3.1 高能球磨法參數控制 11
2.3.2 高能球磨對二氧化鈦的影響 13
2.4 二氧化鈦的應用 16
2.4.1 二氧化鈦光觸媒機制 16
2.4.2 光觸媒反應-亞甲基藍降解反應 18
2.5 X光繞射峰值變寬探討 19
2.6 解析式電子顯微鏡 (AEM) 20
第三章 實驗方法與步驟 21
3.1 實驗設備、藥品 21
3.2 行星式球磨 21
3.3 亞甲基藍降解實驗 24
3.3.1 光觸媒反應器 24
3.3.2 亞甲基藍降解步驟 25
3.4 分析方法 26
3.4.1 XRD分析 26
3.4.2 AEM試片製備 26
3.4.3 AEM顯微結構觀察 27
第四章 結果與討論 29
4.1 高能球磨製程 29
4.1.1 乾球磨 29
4.1.2 Binder之選用 31
4.1.3 Binder添加量 32
4.1.4球磨速度 33
4.1.5球磨時間 34
4.2 亞甲基藍降解 37
4.3 AEM分析 40
4.3.1 Ring pattern 41
4.3.2 Anatase 43
4.3.3 Anatase與TiO2(B)相 45
4.3.4純TiO2(B)相 52
4.3.5 TiO2–II相與 TiO2(B)相 56
4.3.6純TiO2–II相 59
4.3.7 TiO2–II相與Rutile相 60
4.3.8 Rutile相 61
4.3.9 AEM電子束溫度對相變態的影響 63
第五章 結論 67
5.1 Anatase高能球磨之相變化 67
5.2 AEM電子束溫度對相變態的影響 67
5.3 Anatase球磨粉末之光觸媒性質 67
參考文獻 69

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