納米級氧化鋯結晶粒子之高濃度穩定懸浮液製備

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研究生：	陳光龍 Guo-Long Chen
論文名稱：	納米級氧化鋯結晶粒子之高濃度穩定懸浮液製備
指導教授：	蔣孝澈 A.S.T. Chiang
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程與材料工程學系 Department of Chemical & Materials Engineering
畢業學年度：	88
語文別：	中文
論文頁數：	69
中文關鍵詞：	穩定懸浮液、高濃度、納米結晶、氧化鋯
相關次數：	點閱：5 下載：0
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本研究主要目的有二：首先，是以較高濃度(~1M)的鋯鹽溶液，直接以水熱法製備出粒子小於20nm、具有結晶性之氧化鋯穩定粒子懸浮液。其次，是將上述之氧化鋯粒子添加有機界面劑，達到表面改質之目的使其能穩定懸浮於中性環境下。並能以可逆的程序聚集與分散。
有許多文獻是以氯氧鋯溶液直接水熱來合成氧化鋯微結晶，但若酸根濃度超過0.5M以上，四聚物間之雙氫氧橋便很難水解聚縮合形成氧化物了(o-x-o鍵)。所以我們改以共沈澱法合成出氫氧化鋯溶膠，洗去氯離子後再重新以酸來解膠，以降低溶液中酸根之含量，並比較不同酸/鋯比對其水熱合成結果之影響。研究結果得知欲將氫氧化鋯濾餅解膠之最小酸鋯比不得小於1，且製備氫氧化鋯之方式須以控制pH值於鹼性環境下滴定合成才能快速解膠。
在水熱過程中分別探討了溫度、加熱方式及酸鋯比之影響。由粒徑成長趨勢圖可知：1.高溫加快粒子之成核結晶及聚集；2.水熱系統中若含有熱對流或攪拌時，會增加粒子碰撞的頻率，增加粒子聚集成長的速率；3.愈低之酸/鋯比其Induction time愈短，且粒子成長速率亦較快。Zr/HNO3/H2O=1/1.05/65之組成，以96℃加熱30小時可製備出平均粒徑小於20nm，且為單斜晶(monoclinic)的氧化鋯結晶懸浮液。
於合成出之氧化鋯結晶懸浮液中添加有機酸等界劑，確實能有效的將表面改質及而產生穩定之作用。氧化鋯粒子之界面電位之改變隨著界劑帶有之羧基(-COOH)或羥基 (-OH)增加而加大。另外，IEP點偏移程度亦與界劑添加量成正比關係。其中雙酸或三酸如oxalic acid、tataric acid及citric acid視添加多寡可將氧化鋯懸浮液等電位(IEP)往酸偏移1~2.5個pH單位。
在較稀薄鋯離子濃度下，可於水熱前即先行加入界劑。可製備出不聚集、粒徑小於30nm，且結晶性較佳之氧化鋯懸浮液。此法不但簡化原本煩瑣之製備過程，也提高氧化鋯粒子之結晶性。

目錄
摘要----------------------------------------------------------------------------------------------Ⅰ
目錄----------------------------------------------------------------------------------------------Ⅱ
圖目錄-------------------------------------------------------------------------------------------Ⅴ
表目錄-------------------------------------------------------------------------------------------Ⅶ
第一章 研究背景---------------------------------------------------------------------------- 1
1-1 納米材料之特性及應用-----------------------------------------------------------------1
1-2 納米材料研究發展及商業應用現況--------------------------------------------------3
1-2.1納米材料研究發展現況-------------------------------------------------------------3
1-2.2納米材料商業應用現況-------------------------------------------------------------5
1-2.3納米材料未來發展趨勢-------------------------------------------------------------5
1-3 氧化鋯的基本認識----------------------------------------------------------------------- 5
1-4 氧化鋯的製法及應用-------------------------------------------------------------------- 6
1-4.1氧化鋯的應用-------------------------------------------------------------------------6
1-4.2氧化鋯的製法-------------------------------------------------------------------------7
第二章 文獻回顧-----------------------------------------------------------------------------9
2-1製備氧化鋯結晶粒子膠體之回顧------------------------------------------------------10
2-2氧化鋯表面改質(Surface Modified)之文獻回顧-------------------------------------15
2-2.1膠體及膠體粒子之穩定性----------------------------------------------------------15
2-2.1.1膠體之定義-----------------------------------------------------------------------15
2-2.1.2 DLVO理論(Deryagin-Landau-Verwey-Overbeek theory) ----------------16
2-2.1.3 立體效應之穩定(Steric Stabilization) --------------------------------------17
2-2.2 添加保護劑之目的------------------------------------------------------------------18
2-2.3 氧化鋯膠體粒子表面改質之相關文獻------------------------------------------19
2-2.3.1 合成後再添加界面劑之性質探討------------------------------------------19
2-2.3.2 合成前添加界面劑之性質探討--------------------------------------------- 20
2-3 研究方向-----------------------------------------------------------------------------------22
第三章 納米級氧化鋯結晶懸浮液製備------------------------------------------------- 24
3-1 氫氧化鋯之製備及解膠條件-----------------------------------------------------------24
3-1.1 實驗方法------------------------------------------------------------------------------25
3-1.2 氫氧化鋯製備方法之探討---------------------------------------------------------26
3-1.3 以氯氧鋯為酸液解膠---------------------------------------------------------------27
3-1.4 結果與討論---------------------------------------------------------------------------28
3-2 水熱溫度及時間之影響-----------------------------------------------------------------29
3-2.1 水熱溫度對粒徑大小及結晶性之影響------------------------------------------29
3-2.2 水熱時間對結晶性之影響---------------------------------------------------------31
3-3 不同水熱方法對粒子聚集成長之影響-----------------------------------------------32
3-4 不同酸鋯比對水解速度及粒子聚集速率之影響-----------------------------------34
3-4.1 實驗方法------------------------------------------------------------------------------34
3-4.2 實驗結果------------------------------------------------------------------------------36
3-4.2.1 DLS結果-------------------------------------------------------------------------36
3-4.2.2 TEM結果-------------------------------------------------------------------------38
3-4.3 結果與討論---------------------------------------------------------------------------43
3-4.3.1 成核結晶------------------------------------------------------------------------ 43
3-4.3.2 聚集成長------------------------------------------------------------------------ 44
3-5 結論-----------------------------------------------------------------------------------------45
第四章 氧化鋯之表面改質(Surface Modification)-----------------------------------47
4-1 界劑及其添加量對界面電位之影響--------------------------------------------------47
4-1.1 實驗方法------------------------------------------------------------------------------47
4-1.2 實驗結果------------------------------------------------------------------------------48
4-1.2.1 界劑添加量之影響------------------------------------------------------------ 49
4-1.2.1不同有機酸對界面電位之影響---------------------------------------------- 53
4-1.3 結果與討論---------------------------------------------------------------------------53
4-2 氧化鋯粒子之表面改質-----------------------------------------------------------------53
4-2.1 實驗方法------------------------------------------------------------------------------54
4-2.2 結果與討論---------------------------------------------------------------------------54
4-3 水熱前添加界面劑-----------------------------------------------------------------------57
4-3.1 不同解膠方法之比較---------------------------------------------------------------57
4-3.2 不同濃度之影響---------------------------------------------------------------------58
4-4 結論-----------------------------------------------------------------------------------------60
第五章 結論---------------------------------------------------------------------------------- 62
參考文獻----------------------------------------------------------------------------------------63
附錄一 實驗所使用之相關藥品------------------------------------------------------------68
附錄二 實驗所使用之相關儀器設備------------------------------------------------------69

                                

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