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研究生:鄭梓民
研究生(外文):Tzu Min Cheng
論文名稱:以原子轉移活性自由基表面接枝技術開發磁性複合吸附材料之研究
論文名稱(外文):The Research and Application of a Novel Magnetic Composite with ATRP Surface Modification for Metal Adsorption
指導教授:陳志恆陳志恆引用關係
指導教授(外文):Jyh Herng Chen
口試委員:陳志恆廖義田林景崎徐治平吳震裕
口試日期:2016-07-29
學位類別:碩士
校院名稱:國立臺北科技大學
系所名稱:資源工程研究所
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2016
畢業學年度:104
語文別:中文
中文關鍵詞:貴金屬回收、磁性複合材料、原子轉移自由基聚合法、離子交換法
外文關鍵詞:Recovery of precious metalsmagnetic compositesatom transfer radical polymerizationion exchange
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  • 被引用被引用:1
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近年來化學鍍液之大量使用,特別是化學鎳的使用,產生大量廢液,而內含重金屬離子而無法直接排放。目前重金屬廢液處理已朝著金屬資源化回收的方向發展,不僅解決廢液處理問題,亦可達到資源化回收之目的。本研究主要研發可吸附鎳陽離子的磁性顆粒,並應用在含鎳廢液回收。本研究研發之磁性顆粒優點是將顆粒粉體投入液相,再以離子交換方式吸附完陽離子後能快速以磁力做分離。本研究以Fe3O4為核,利用sol-gel法進行SiO2的包覆,形成core shell之結構,再分別以無乳化聚合法進行聚丙烯酸(PAA)以及以原子轉移自由基聚合法(ATRP)進行聚丙烯酸鈉(PAAS)的表面高分子聚合。檢測結果證實了SiO2之包覆、CTCS、矽烷偶聯劑KH-570之表面修飾、聚丙烯酸(PAA)以及聚丙烯酸鈉PAAS之表面聚合。對於兩種磁性複合材料的應用能力研究上,以無乳化聚合法製備之複合材料對於鎳離子的吸附能力約為1 mg/g;以ATRP聚合法製備之複合材料對於鎳離子的吸附能力約為4.6 mg/g,證實本研究之磁性複合材料對於液相中之鎳離子有一定的吸附能力。
Spent Ni-plating wastewater contains large amount of valuable Ni metal. Metal recycling not only can solve the wastewater disposal problem, but also reach the purpose of resource conservation. Currently, various metal recycling technology have been proposed for the recycling of Ni-containing wastewater. The main goal of this study is to develop a new kind of material for Ni metal recovery. The mechanism of recovery is to absorb the nickel ion. The new material consists a core-shell structure with Fe3O4 as core and SiO2 as shell. The magnetic Fe3O4 provides the advantage of easy solid-liquid separation by magnetic force. The SiO2 shell, prepared by sol-gel method, provide a protection layer. Furthermore, the surface of the material is grafted with polyelectrolyte (poly sodium acrylate, PAAS) for Ni ion exchange reaction. In this study, surface modification can be achieved by two approaches: emulsion-free polymerization and ATRP polymerization of PAA and PAAS, respectively. For ATRP, the surface modification is realized first immobilized with CTCS, followed by surface polymerization using sodium acrylate as monomer by ATRP method. The properties of the particle is characterized based on the magnetism property, amount of coated polyelectrolyte. The Ni2+ adsorption capacity of Fe3O4@SiO2@CTCS@PAAS composite is about 4.6 mg/g.
中文摘要 i
英文摘要 ii
誌謝 iv
目錄 v
表目錄 vii
圖目錄 viii
第一章 緒論 1
1.1研究背景及動機 1
1.2研究目的 3
第二章 文獻回顧 7
2.1奈米材料 7
2.1.1小尺寸效應 8
2.1.2表面效應 11
2.1.3量子尺寸效應 12
2.2磁性奈米材料介紹 14
2.3核殼型奈米複合粒子的製備 15
2.4離子交換 18
2.4.1離子交換之發展 18
2.4.2 離子交換的基本原理 18
2.5無乳化劑乳化聚合法 20
2.6原子轉移自由基聚合(ATRP) 21
2.6.1原子轉移自由基聚合之介紹 21
2.6.2影響原子轉移自由基聚合之因素 22
第三章 研究方法 25
3.2實驗藥品 27
3.3實驗步驟 30
3.3.1四氧化三鐵保護層之包覆(MNPs@SiO2) 31
3.3.2 Fe3O4@SiO2表面無乳化聚合聚合反應 31
3.3.3 Fe3O4@SiO2表面原子轉移自由基聚合反應 33
3.3.4複合材料對鎳離子的吸附測試 34
3.3.5複合材料重複使用效果測試 34
第四章 結果與討論 35
4.1四氧化三鐵(MNPs)特性分析 35
4.2四氧化三鐵/SiO2核殼結構之製備(MNPs@SiO2) 41
4.2.1 二氧化矽包覆之最佳化 41
4.2.2 表面性質分析 51
4.2.3 二氧化矽保護層保護效果分析 52
4.3 Fe3O4@SiO2表面無乳化聚合聚合反應 53
4.3.1表面矽烷偶聯劑(KH-570)接枝 53
4.3.2丙烯酸的表面聚合及鈉性的改質 57
4.3.3以無乳化聚合法製備之複合材料吸附能力 61
4.4 Fe3O4@SiO2表面原子轉移自由基聚合反應 62
4.4.1表面起始劑(CTCS)的修飾 62
4.4.2丙烯酸鈉的表面聚合 66
4.4.3表面性質分析 69
4.4.4以ATRP聚合法製備之複合材料吸附能力 70
第五章 結論 71
參考文獻 72
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