臺灣博碩士論文加值系統

本研究探討多殼層導電性與感磁性奈米複合材料之製備與性質。此多殼層複合材料中心部分為四氧化三鐵顆粒、中間部分為PMMA、最外層為PANI，利用多殼層結構增加複合材料之功能性。首先利用自組裝將CTCS改質於四氧化三鐵表面，TGA顯示起始CTCS濃度越高，表面接枝濃度越高。從Zeta potential測量發現添加32.5 mM CTCS時，表面改質CTCS接枝量達飽和。由FTIR顯示，可利用ATRP活性自由基聚合法將短鏈段之PMMA接枝於四氧化三鐵表面，以達到穩定化氧化鐵懸浮液，使四氧化三鐵可穩定懸浮於MMA單體中而不易沉降。再利用溶液聚合法將PMMA包覆於四氧化三鐵表面，形成Fe3O4-PMMA核-殼結構。由TGA顯示，Fe3O4/PMMA比例越高所形成之複合材料的熱穩定性越佳。實驗結果顯示，選擇Fe3O4/PMMA為0.02可保持其形貌為完整球狀，同時也達到提升熱穩定性之效果。
本研究接著利用溶液聚合法製做PMMA-PANI核-殼結構之聚合物，以了解製備過程中反應物之作用與添加量對PMMA-PANI核-殼結構聚合物之影響，添加之反應物有界面活性劑SDS、分散劑hydroquinone、氧化劑Ammonium persulfate。經由研究之後得到最佳參數為： SDS 0.5克、hydroquinone 0.0154 克、Aniline/ Ammonium persulfate比例為1.25，所獲得的導電度為1.843×10-2 S/cm。利用前述之最佳參數，於Fe3O4-PMMA核-殼結構表面進一步聚合PANI以形成多殼層導電性與感磁性奈米複合材料，經由VSM測試其飽和磁化(saturation magnetization)為0.6emu/g與矯頑磁力(coercive force)為60 Oe，導電性為2.32×10-2 S/cm。

In this study, a multilayer nanocomposite material with electroconductive and magnetic characteristics was successfully synthesized. The multi-shell composite materials central part with the iron oxide particles, middle part was PMMA, outer layer was PANI. First, iron oxide surface was modified by using self-assembled CTCS. TGA shows that increasing CTCS concentration can increasing the amount of immobilized CTCS. Zeta potential indicated that with 32.5 mM CTCS, the surface was saturated with CTCS. FTIR shows that PMMA short-chain can be grafted onto the surface of the iron oxide by ATRP polymerization. The PMMA short-chain can stabilize the iron oxide particles in MMA monomer solution. The PMMA covered iron oxide surface was further covered with PMMA to form Fe3O4-PMMA core-shell structure by solution polymerization. TGA analysis showed that increase the ratio of Fe3O4/PMMA increase the thermal stability of composite. With Fe3O4/PMMA ratio 0.02, the composite can have a complete spherical morphology and good thermal stability.
PMMA-PANI composite with core-shell structure can be synthesized by solution polymerization in order to understand the effects of the reactants to the formation and properties of PMMA-PANI composite, including surfactant (SDS), dispersant (hydroquinone) and oxidant (ammonium persulfate). The optima parameters are SDS 0.5 grams, hydroquinone 0.0154 grams and Aniline /Ammonium persulfate ratio 1.25. The resulting composite has conductivity 1.843×10-2 S/cm. Adopting this optimum parameters. a multilayer nanocomposite material with electroconductive and magnetic can be prepared with the Fe3O4-PMMA-PANI core-shell structure. VSM analysis showed that the composite has saturation magnetization 0.6 emu/g, the magnetic coercivity 60 Oe and conductivity 2.32 × 10-2 S / cm.

目 錄

中文摘要 .i
英文摘要 .iii
目錄 .v
表目錄 ..vii
圖目錄 ..viii
第一章 緒論…………………………………………………….…….…….….1
1.1 奈米材料…………………………………………….………………1
1.2 奈米粒子的特性…………………………………….…….…..…….2
1.3 奈米複合材料……………………………………….…………..…..5
1.4 研究目的與架構…………………………………….…………..…..7
第二章 文獻回顧…………………………………………………….……..….10
2.1 磁性氧化物材料的粉體製備………………………………...……10
2.1.1 四氧化三鐵之基本性質…......................................................10
2.1.2 磁性氧化物粉體製備………………………………..………11
2.2 磁性氧化物材料的粉體改質……………………………...………12
2.2.1 表面改質……………………………………………………..12
2.2.2 磁性氧化物的表面改質……………………………….…….15
2.3 原子轉移活性自由基聚合反應原理…………………………..….18
2.4 導電高分子……………………………………………………...…21
2.4.1 導電高分子發展史………………………………………..…21
2.4.2 聚苯胺…………………………………………………….….23
2.4.3 苯胺及其衍生物之聚合機制…………………………….….25
2.5 PMMA奈米複合材料………………………………………..……26
2.5.1 PMMA基本性質…………………………………...………..26
2.5.2 高分子複合材料……………………………………………..27
第三章 實驗方法與步驟……………………………………………...……….30
3.1 實驗材料……………………………………………………….…..30
3.2 實驗儀器設備……………………………………………………...33
3.2.1 X-ray 分析儀………………………………………..……….33
3.2.2 掃描式電子顯微鏡 scanning electron microscope (SEM)….34
3.2.3 傅立葉紅外線光譜 Fourier Transform Infrared Spectroscopy (FTIR)……………………………………………….….…….34
3.2.4 示差掃描熱量分析儀 Differential Scanning alorimetry (DSC)……………………………………………………..….35
3.2.5 熱重分析儀Thermogravimetry Analyzer (TGA)......……….35
3.2.6 奈米粒徑分析儀 (Zetasizer)…………………………….…..35
3.2.7 振動樣品磁力儀 (VSM)……………………………….……35
3.2.8 四點探針…………………………………………………..…36
3.3 實驗步驟……………………………………………………...……36
3.3.1 改質磁性奈米氧化鐵(Fe3O4)粉體……………………..……37
3.3.2 MP-CTCS接枝短鏈段MMA…………………………….….37
3.3.3 溶液聚合法製備MP-PMMA核-殼(core-shell)結構高分子..40
3.3.4 乳化聚合法製備多殼層結構之P-PMMA-PAni顆粒…...….41
第四章 結果與討論………………………………………………………..…43
4-1 MP-CTCS-PMMA核-殼結構之球型高分子…………….……….43
4.1.1 奈米氧化鐵(Fe3O4)粉體特性分析……………………….….43
4.1.2 利用CTCS進行奈米氧化鐵表面改質……………….……..46
4.1.3 CTCS濃度對氧化鐵粉末表面性質之影響……………..….49
4.1.4 MP-CTCS接枝短鏈段MMA………………………….…….50
4.1.5 製備MP-CTCS-PMMA核-殼結構之球型高分子……...…..52
4.2 PMMA-PANI導電複合材料………………………………….…...55
4.2.1 利用Aniline單體進行多殼層復合材料製備…………….....55
4.2.2 利用Aniline Hydrochloride進行多殼層復合材料製備….…62
4.3 MP-PMMA-PANI多殼層導電性與感磁性奈米複合材料……….69
4.3.1 四氧化三鐵奈米顆粒為核製備多殼層複合材料………..…..70
4.3.2 多殼層材料外層添加四氧化三鐵顆粒………………….….71
第五章 結論……………………………………………………………………73
參考文獻………………………………………………………………………..75

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