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研究生: 陳龍賓
論文名稱: 高分子對鈦酸鋇分散性能與電性之研究
指導教授: 許貫中
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 2008
畢業學年度: 96
語文別: 中文
論文頁數: 216
中文關鍵詞: 鈦酸鋇聚電解質分散合成介電性質
論文種類: 學術論文
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鈦酸鋇因具有強鐵電、壓電和介電等特性,為製造電容器、電感器、壓電感測器之重要原料。製程上鈦酸鋇粉末須先加入溶劑以配成漿料,目前所使用的溶劑分為水及有機溶劑兩類,基於環保與降低成本,近年來水系漿料的製備已引起矚目。為製備分散良好之漿體,常需加入聚電解質作為分散劑。隨著漿體pH值增加,高分子吸附量減少,但降低漿體pH值,高分子解離度降低、鋇離子溶出量增加。為了製備分散穩定的漿料,值得合成出具有良好分散效能且減少鋇離子溶出的高分子。
本研究主要合成兩種類水溶性高分子:一為陰離子型之聚(甲基丙烯醯胺/甲基丙烯酸鹽) (PMMN),係以甲基丙烯醯胺 (MAM) 及甲基丙烯酸 (MAN) 為單體,在鹼性環境下經自由基聚合反應所合成的共聚物。另一為兩性共聚物,先以氯醋酸鈉與N-(4-乙烯苯基)-N,N-二甲基胺製備一N-(4-乙烯苯基)-N,N-二甲基乙酸銨(DMVBAE)之兩性單體。以DMVBAE和甲基丙烯酸經聚合反應得到聚(N-(4-乙烯苯基)-N,N-二甲基乙酸銨/甲基丙烯酸鹽) (PVM);另外,DMVBAE與甲基丙烯醯胺、甲基丙烯酸可製得聚(N-(4-乙烯苯基)-N,N-二甲基乙酸銨/甲基丙烯醯胺/甲基丙烯酸鹽) (PVMM)。所得產物由IR、1H-NMR光譜確認其結構,GPC分析其分子量。利用電位滴定法得到高分子在不同pH值下的解離率及PMMN中單體組成比例。由PVM的1H-NMR光譜圖可知兩單體含量,而PVMM可經由元素分析法求得單體組成。
兩類型高分子添加於鈦酸鋇漿體,藉量測漿體黏度、記錄沈降行為、分析漿體粒徑、觀察生胚微結構及計算胚體密度來評估其分散效能並與PMAAN做為對照。結果顯示添加這些高分子可得到分散良好的漿體,最佳劑量均為2mg/g BT。由吸附實驗和粒子界達電位測定結果顯示PMMN(60)含60wt%甲基丙烯醯胺單體有最大的羧基吸附量及最低的界達電位值。PVM、PVMM為兩性高分子,在鹼性環境下較易吸附於粒子表面,其中PVMM含醯胺基更易吸附於粒子,吸附量大於PVM。這些高分子吸附於粒子上均可產生電荷斥力與立體阻障而使懸浮液達到穩定的狀態。引用DLVO理論計算粒子之總電位能,所得結果與實驗相符。IR、UV/vis光譜圖中官能基吸收峰的位移提供粒子與高分子交互作用的證據。量測溶液中鋇離子濃度, PMMN、PVM和PVMM結構中含四級胺和醯胺基等官能基較容易吸附於粒子上,吸附量增加或粒子表面有較大的高分子覆蓋率,可抑制鋇離子溶出,因此減少溶液中鋇離子濃度。添加PMMN、PVM及PVMM做為分散劑可得到較好的分散效果,粒子堆積緻密,經燒結後,可增加胚體介電常數值與降低介電損失值。

第一章 緒論..............................................................................................1 第二章 文獻探討......................................................................................4 2.1 鈦酸鋇簡介.......................................................................................4 2.1.1 鈦酸鋇的合成..............................................................................4 2.1.2 鈦酸鋇之相圖及結構.……………….…………………………5 2.1.3 鈦酸鋇電性之研究......................................................................5 2.2 水溶性高分子...................................................................................9 2.2.1 界面活性劑的種類與應用..........................................................9 2.2.2 高分子結構對陶瓷粉體分散性能的影響……………………10 2.2.3 共聚合反應的動力學…………………………………………12 2.2.4 高分子的解離與吸附構形……………………………………19 2.3 粒子與高分子的特性…………………………………………….23 2.3.1 粒子的凝聚……………………………………………………23 2.3.2 粒子本身表面電荷的來源……………………………………24 2.3.3 高分子的吸附使粒子帶電……………………………………24 2.3.4 Langmuir單層吸附模式……………………………………....25 2.4 分散機制………………………………………………………….28 2.4.1 靜電排斥穩定理論……………………………………………28 2.4.2 立體阻障效應…………………………………………………34 2.4.3 耗乏穩定………………………………………………………34 2.5 分散性能評估…………………………………………………….36 2.5.1 流變分析………………………………………………………36 2.5.2 沈降行為………………………………………………………38 2.5.3 粒子電位……………………………………………………....40 2.6 鋇離子溶出……………………………………………………….41第三章 實驗裝置與步驟……………………………………………....44 3.1 實驗材料與藥品.............................................................................44 3.1.1鈦酸鋇(BT)粉末……………………………………………….44 3.1.2藥品.............................................................................................44 3.2儀器設備…………………………………………………………..45 3.3 BT粉末之XRD圖……………………………………………….46 3.4 高分子結構鑑定及性質分析………………………………….....48 3.4.1 核磁共振(NMR)光譜………………………………………....48 3.4.2 紅外線(IR)光譜…………………………………………….....48 3.4.3 聚合物之單體組成及解離率………………………………....48 3.4.4 元素分析……………………………………………………....49 3.4.5 凝膠滲透層析(GPC)分析…………………………………….50 3.4.6 高分子固含量測量……………………………………………51 3.5 高分子對BT漿體分散性能與機制研究………..………………52 3.5.1 流變性質………………………………………………………52 3.5.2 沈降行為………………………………………………………52 3.5.3 粒徑分析………………………………………………………52 3.5.4 胚體密度………………………………………………………52 3.5.5 微結構觀察............................................................................... 53 3.5.6 吸附量…………………………………………………………53 3.5.7 界達電位………………………………………………………54 3.6 高分子對漿體鋇離子溶出量的影響…………………………….54 3.7 胚體介電常數與介電損失……………………………………….55 第四章 聚(甲基丙烯醯胺/甲基丙烯酸銨鹽)的合成及對鈦酸鋇漿 體分散性能與機制之研究........................................................57 4.1 共聚物的合成…………………………………………………….58 4.2 共聚物分析……………………………………………………….59 4.2.1 共聚物結構鑑定………………………………………………59 4.2.2 共聚物的反應機構……………………………………………62 4.2.3 共聚物的解離與組成分析……………………………………65 4.3 分散性能評估…………………………………………………….70 4.3.1 流變性質………………………………………………………70 4.3.2 流動性…………………………………………………………72 4.3.3 粒徑分析………………………………………………………75 4.3.4 沈降行為………………………………………………………79 4.3.5 生胚密度………………………………………………………88 4.3.6 微結構觀察……………………………………………………90 4.4 分散機制之研究………………………………………………….94 4.4.1 高分子吸附量…………………………………………………94 4.4.2 高分子對粒子界達電位的影響……………………………..112 4.4.3 高分子吸附於粒子之表面化學……………………………..120 4.4.4 DLVO理論之應用…….……………………………………..123 4.5 鋇離子溶出量…………………………………………………...129 4.6 燒結體之電性…………………………………………………...145 4.7 結論…………………………………………………...…………151 第五章 含芳香環之兩性共聚物的合成及對鈦酸鋇漿料穩定性之 研究..........................................................................................152 5.1 共聚物的合成…………………………………………………...152 5.1.1 聚(N-(4-乙烯苯基)-N,N-二甲基乙酸銨/甲基丙烯酸鹽) (PVM)的合成…………….……..……………………………152 5.1.2聚(N-(4-乙烯苯基)-N,N-二甲基乙酸銨/甲基丙烯醯胺/甲基 丙烯酸鹽)(PVMM)的合成…......……………….…………...153 5.2 共聚物分析……………………………………………………...155 5.2.1 共聚物結構鑑定……………………………………………..155 5.2.2 共聚物組成…………………………………………………..160 5.2.3 共聚物的解離行為…………………………………………..161 5.2.4 共聚物分子量………………………………………………..165 5.3 分散性能評估…………………………………………………...168 5.3.1 流變性質……………………………………………………..168 5.3.2 沈降行為……………………………………………………..171 5.3.3 粒徑分析……………………………………………………..174 5.3.4 微結構觀察…………………………………………………..177 5.3.5 生胚密度……………………………………………………..180 5.4分散機制之研究…………………………………………………181 5.4.1 高分子吸附量………………………………………………..181 5.4.2 高分子對粒子界達電位的影響……………………………..190 5.4.3 電雙層理論(DLVO)的應用………………………………….198 5.5 鋇離子溶出量…………………………………………………...204 5.6 介電性質………………………………………………………...210 5.7 結論…………………………………………………………….. 214 第六章 總結…………………………………………………………..215 參考資料…….………………………………………………………...217

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