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研究生： 李沛杰
Lee, Pei-Chieh
論文名稱： 以油酸分散膠體配合氣氛加熱製造奈米氧化鋯粉末之研究
Preparation of Nanometer-Sized Zirconia Powders by Calcining an Emulsion of Precursor and Oleic Acid
指導教授： 溫紹炳
Wen, Shaw-Bing
學位類別： 碩士
Master
系所名稱： 工學院 - 資源工程學系
Department of Resources Engineering
論文出版年： 2002
畢業學年度： 90
語文別： 中文
論文頁數： 69
中文關鍵詞： 相轉換 、熱去除 、乳膠 、奈米 、化學沈澱法
外文關鍵詞： transformation, thermal degration, emulsion, chemical precipitation, nano-meter
相關次數： 點閱：117  下載：3 
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    • 本論文提出一種加入界面活性劑於陶瓷微粉前導物中，在煆燒過程中利用殘碳作為阻斷結晶成長的製造方式，為陶瓷粉末製造提出一種新的思維模式。先以陶瓷粉末的膠體前導物與有機界面活性劑共同混合，乳化變成微小的微胞，再以這個乳化混合物置入控制氣氛的加熱爐之中，加熱過程中使有機界面活性劑分解而不燃燒，並遺留部份殘碳擔任微小粒子間的阻隔物，去除可能因相轉換過程中伴隨的粒子燒結或晶粒成長的發生以達成製造正方晶相奈米氧化鋯粉末的目的。
    研究結果顯示，以油酸混拌前導物並添加3mol%氧化釔作為穩定劑，煆燒至1200℃可得到結晶性良好且晶粒大小約為20nm的正方晶相氧化鋯粉末。煆燒的過程不論是改變何種條件，一開始出現的結晶相都是正方晶相，隨著溫度的升高，正方晶相開始轉換為單斜晶相。根據對粒徑的觀察可證實Garvie所提出30nm臨界粒徑的存在。

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    總目錄 摘要.................................................................................................................Ⅰ 誌謝.................................................................................................................Ⅱ 總目錄.............................................................................................................Ⅲ 表目錄.............................................................................................................Ⅴ 圖目錄............................................................................................................Ⅵ 第1章 緒論......................................................................................................1 1-1 前言....................................................................................................1 1-2 研究目的............................................................................................4 1-3 關於氧化鋯........................................................................................5 1-3-1 氧化鋯的基本認識................................................................5 1-3-2 氧化鋯的分類........................................................................8 1-3-3 相轉換韌化機構...................................................................11 1-3-4 氧化鋯的應用......................................................................14 1-4 文獻回顧..........................................................................................17 第2章 理論基礎............................................................................................19 2-1 氧化鋯前導物與界面活性劑形成乳膠的作用..............................19 2-1-1 膠體的吸附..........................................................................19 2-1-2 膠體的分散..........................................................................21 2-1-3 乳膠理論..............................................................................23 2-2 有機物的熱去除..............................................................................27 第3章 實驗方法與步驟................................................................................28 3-1 實驗材料與儀器..............................................................................30 3-1-1 實驗材料..............................................................................30 3-1-2 實驗之儀器..........................................................................33 3-2 性質分析..........................................................................................34 3-3 實驗流程與步驟..............................................................................36 3-3-1 氧化鋯起始膠之製備..........................................................36 3-3-2 氧化鋯微粉之製造..............................................................36 第4章 結果與討論........................................................................................39 4-1 由含水氧化鋯膠體製造氧化鋯粉末之結果..................................39 4-1-1 熱分析..................................................................................39 4-1-2 結晶相分析..........................................................................41 4-1-3 粒徑分析..............................................................................44 4-2 煆燒過程中低溫加熱之觀察結果..................................................48 4-3由含水氧化鋯膠體混拌油酸製造氧化鋯粉末之結果...................50 4-3-1 結晶相分析..........................................................................50 4-3-2 殘碳量分析..........................................................................53 4-3-3 粉末外形觀察......................................................................55 4-3-4 晶粒大小..............................................................................55 4-3-5 綜合討論..............................................................................59 第5章 結論與建議........................................................................................61 5-1 結論..................................................................................................61 5-2 建議..................................................................................................63 5-2-1 複合粉末與粉末之表面改質..............................................63 5-2-2 超塑性奈米陶瓷燒結體之製作與性質探討......................63 參考文獻.........................................................................................................65 表目錄 表1.1 氧化鋯粉末製造方法............................................................................3 表1.2 氧化鋯微粉的化學製造方式及特點....................................................3 表1.3 氧化鋯的主要晶相結構資料................................................................6 表1.4 氧化鋯三種晶相主要X-ray繞射峰之角度及相對強度.....................6 表1.5 氧化鋯未來發展用途和目前商用產品..............................................16 表2.1 不同種類乳化劑的HLB值………....................................................24 表2.2 不同HLB值乳化劑的應用.................................................................24 表3.1 實驗使用之化學試劑..........................................................................30 表4.1 實驗製得粉末之晶相與晶徑大小......................................................57 圖目錄 圖1.1 純氧化鋯相圖........................................................................................7 圖1.2 氧化鋯的結晶構造................................................................................7 圖1.3 氧化鋯-氧化釔系統相圖....................................................................10 圖1.4 氧化鋯從正方晶相到單斜晶相的應力誘導相變..............................12 圖1.5 應力激發相轉換韌化機構示意圖......................................................12 圖1.6 微裂縫韌化機構示意圖......................................................................13 圖2.1 界面藥劑的分散作用..........................................................................22 圖2.2 微胞結構示意圖…..............................................................................25 圖2.3 界面活性劑濃度改變導致微胞不同形狀結構..................................25 圖2.4 氧化鋯前導物與界面活性劑形成乳膠示意圖..................................26 圖3.1 研究構想示意圖..................................................................................29 圖3.2 氧化釔含量對Y-TZP(a)彎曲強度與(b)抗折強度的變化.................32 圖3.3 實驗流程圖..........................................................................................38 圖4.1含水氧化鋯膠體之熱差及熱重分析曲線...........................................40 圖4.2 添加3mol%氧化釔之含水氧化鋯膠體之熱差及熱重分析曲線.....40 圖4.3 實驗所用之煆燒程序..........................................................................41 圖4.4 含水氧化鋯膠體不同煆燒溫度樣品之X光繞射圖..........................42 圖4.5 添加3mol%氧化釔之含水氧化鋯膠體不同煆燒溫度樣品之X光繞. 射圖.....................................................................................................43 圖4.6 含水氧化鋯膠體不同煆燒溫度樣品之比表面積與比表面積徑關係.. 圖.........................................................................................................45 圖4.7 添加3mol%氧化釔之含水氧化鋯膠體不同煆燒溫度樣品之比表面. 積與比表面積徑關係圖.....................................................................45 圖4.8 添加3mol%氧化釔與純含水氧化鋯膠體不同煆燒溫度樣品之掃描. 式電子顯微鏡照片.............................................................................46 圖4.9 實驗時之照片......................................................................................49 圖4.10 含水氧化鋯膠體混拌油酸在氮氣爐中不同煆燒溫度樣品之X光繞 射圖...................................................................................................51 圖4.11 添加3mol%氧化釔之含水氧化鋯膠體混拌油酸在氮氣爐中不同煆 燒溫度樣品之X光繞射圖...............................................................51 圖4.12 不同氧化釔添加量的含水氧化鋯膠體混拌油酸在氮氣爐中煆燒樣 品之X光繞射圖...............................................................................52 圖4.13 添加3mol%氧化釔之含水氧化鋯膠體混拌油酸在氮氣爐中(全程 控制氣氛)煆燒1000℃樣品之熱差及熱重分析曲線.....................54 圖4.14 添加3mol%氧化釔之含水氧化鋯膠體混拌油酸在氮氣爐中(全程 控制氣氛)煆燒1000℃樣品殘碳燒除前後之X光繞射圖.............54 圖4.15 添加3mol%氧化釔與純含水氧化鋯膠體混拌油酸在氮氣爐中不同 煆燒溫度樣品之掃描式電子顯微鏡照片.......................................56 圖4.16 不同條件製備氧化鋯粉末之粒徑大小............................................58 圖4.17 單斜晶相與正方晶相氧化鋯之自由能與溫度關係示意圖............60

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