臺灣博碩士論文加值系統

本論文採用化學共沉法製備Fe3O4磁性奈米粒子。將氨水滴入三價鐵和二價鐵混合液中，在氮氣的保護下加熱與攪拌，得到磁性奈米粒子。最後，採用溶膠凝膠法，在鹼性室溫環境下催化四乙氧基矽烷(TEOS)，水解製備SiO2包覆Fe3O4(Fe3O4＠SiO2)，核殼結構奈米複合粒子。本論文用環境掃描式電子顯微鏡(ESEM與EDS)探討Fe3O4奈米粒子與Fe3O4＠SiO2奈米複合粒子之表面形貌與成份，用x-ray繞射儀(XRD)探討Fe3O4奈米粒子的結晶情況，用穿透式電子顯微鏡(TEM)探討粒徑大小與改質狀況。結果顯示，粒子與粒子間因相互吸引而聚集，且磁性奈米粒子尺寸很小，當添加5 ml氨水的粒徑大小為10.303 nm，而添加20 ml氨水的粒徑大小為8.86 nm，結果顯示20 ml氨水粒徑較小。利用TEM觀察SiO2包覆Fe3O4奈米磁性粒子微結構，證明二氧化矽成功地包覆於Fe3O4粒子表面。

In this paper, the magnetic nanoparticles of Fe3O4 were prepared with a chemical co-precipitation method. The Fe3+ and Fe2+ solution was mixed with NH4OH by heating and stirring and using N2 to protect the reaction, after that the Fe3O4 magnetic nanoparticles were obtained. Next, the core-shell structures of SiO2 coated with Fe3O4 nanocomposite particles were prepared by sol-gel method, in which the hydrolysis of TEOS was conducted on the surface of Fe3O4 with the aid of basic catalyst at room temperature. In this study, the surface shape and component of Fe3O4 nanoparticles and Fe3O4 coated SiO2 nanocomposite particles were studied by ESEM, EDS and TEM. The crystal structure was studied by use of XRD. The magnetic nano-particles size before and after the modification with TEOS were studied with TEM. The results indicated that the magnetic nanoparticles were aggregate due to the particles attraction each other, and the magnetic nanoparticles had very small size. The average particles size of addition 5 ml ammonia solution were 10.303 nm and addition 20 ml ammonia solution was 8.86 nm. The results indicate that the Fe3O4 magnetic nano-particles size is smaller with addition of 20 ml ammonia solution. After Fe3O4 coated with SiO2 were observed by use of TEM, it was confirmed that the SiO2 were successfully coated on the surface of Fe3O4 magnetic nanopraticles.

摘 要................................................................... i
ABSTRACT............................................................... ii
致 謝.................................................................. iii
目　錄.................................................................. iv
表 目 錄................................................................ vi
圖 目 錄......................................... ........................vii
符號說明................................................................. x
第1章 緒論............................................................... 1
1-1前言................................................................. 1
1-2研究動機與目的......................................................... 1
1-3研究架構.............................................................. 3
第2章 文獻回顧............................................................ 4
2-1奈米材料.............................................................. 4
2-2磁性流體.............................................................. 4
2-3磁性流體的應用......................................................... 5
2-4磁性奈米粒子之基本特性................................................... 7
2-5磁性奈米粒子之磁滯曲線........................... ........................8
2-6磁性奈米粒子之穩定性.................................................... 9
2-7磁性奈米粒子之表面披覆界面活性劑.......................................... 13
2-8二氧化矽包覆磁性奈米粒子................................................. 13
第3章 實驗過程與原理....................................................... 16
3-1實驗藥品、儀器與設備.................................................... 16
3-2 Fe3O4 磁性奈米粒子製備原理............................................. 17
3-2.1 Fe3O4 磁性奈米粒子製備過程........................................... 17
3-2.2傾析法............................................................. 19
3-3水基磁性流體製備....................................................... 20
3-4溶膠凝膠法(sol-gel)，於Fe3O4 nanoparticles 外包覆二氧化矽................ 21
3-5高週波加熱器，對奈米粒子進行加熱測試...................................... 22
3-6表面電位(Zeta potential)之原理........................................ 23
3-6.1表面電位(Zeta potential)之酸鹼液製備................................. 24
3-6.2表面電位(Zeta potential)之酸鹼液製備................................. 24
3-7 ESEM與EDS微結構分析.................................................. 25
3-8 X光繞射原理......................................................... 26
3-9穿透式電子顯微鏡(TEM)................................................. 27
第4章 結果與討論......................................................... 28
4-1溫度、氨水濃度對化學共沉法的影響......................................... 28
4-2黑色磁性流體............................................................29
4-3溫度、攪拌速度與攪拌時間對水基磁性流體之影響..................................30
4-4二氧化矽披覆Fe3O4粒子之實驗數據分析........................................33
4-5 Fe3O4粒子之 ESEM微結構分析..............................................33
4-6 Fe3O4粒子之 EDS成份分析.................................................40
4-7 XRD之晶體結構與晶粒大小分析...............................................43
4-8 TEM粒徑觀察、量測.......................................................45
4-9高週波加熱器對磁性奈米粒子進行加熱測試........................................51
4-10界達電位(zeta potential)...............................................53
4-11超導量子干涉(squid).....................................................54
第5章 結論.................................................................56
第6章 建議.................................................................56
參考文獻...................................................................58
簡歷......................................................................62

參考文獻
[1].Mohamed Abbas, B. Parvatheeswara Rao, Md. Nazrul Islam, S.M. Naga, Migaku Takahashi and Cheolgi Kim, “Highly stable-silica encapsulating magnetite nanoparticles (Fe3O4/SiO2) synthesized using single surfactantless-polyol process,” Ceramics International, 2013
[2].Zhao Yuanbi, Qiu Zumin and Huang Jiaying, “Preparation and analysis of Fe3O4 magnetic nanoparticles used as targeted-drug carriers,” Chinese Journal of Chemical Engineering, 16(3) pp. 451-455, 2008
[3].Jianhua Meng, Guiqin Yang, Lemei Yan and XiuYu Wang “Synthesis and characterization of magnetic nanometer pigment Fe3O4,” Dyes and Pigments 66, pp. 109-113, 2005
[4].Lingyun Chen, Zhengxiong Xu, Hong Dai and Hong Dai, “Facile synthesis and magnetic properties of monodisperse Fe3O4/silica nanocomposite microspheres with embedded structures via a direct solution-based route,” Journal of Alloys and Compounds 497, pp. 221-227, 2010
[5].Di Li, Deli Jiang, Min Chen, Jimin Xie, Yinyin Wu, Shengchun Dang and Jianxin Zhang, “An easy fabrication of monodisperse oleic acid-coated Fe3O4 nanoparticles,” Materials Letters 64, pp. 2462-2466, 2010
[6].Yunjin Yao, Shiding Miao, Shaoming Yu, Li Ping Ma, and Shaobin Wang, “Fabrication Fe3o4/SiO2 core/shell nanoparticles attached to grapheme oxide and its use as an adsorbent,” Journal of Colloid and Interface Science 379, pp. 20-26, 2012
[7].Dong Liu, Yi Li, Jianping Deng and Wantai Yang, “Synthesis and characterization of magnetic Fe3O4-silica-poly composite microspheres,” Reactive & Functional Polymers 71, pp. 1040-1044, 2011
[8].Yufang Hu, Jiaxing Li, Zhaohui Zhang, Huabin Zhang, Lijuan Luo and Shouzhuo Yao, “Imprinted sol-gel electrochemical sensor for the determination of benzylpenicillin based on Fe3O4＠SiO2 / multi- walled carbon nanotubes-chitosans nanocomposite film modified carbon electrode,” Analytica Chimica Acta 698, pp. 61-68, 2011
[9].Shengxiao Zhang, Yuanyuan Zhang, Junshen Liu, Qiang Xu, Huaqing Xiao, Xinyu Wang, Hui Xu and Jing Zhou, “Thiol modified Fe3O4@SiO2 as a robust, high effective, and recycling magnetic sorbent for mercury removal,” Chemical Engineering Journal 226, pp. 30-38, 2013
[10].Ziyang Lu, Gang Wang, Jiaqi Zhuang and Wensheng Yang, “Effects of the concentration of tetramethylammonium hydroxide peptizer on the synthesis of Fe3O4/SiO2 core/shell nanoparticles,” Colloids and Surfaces A：Physicochem. Eng. Aspects 278, pp. 140-143, 2006
[11].Baoliang Lv, Yao Xu, Hong Tian, Dong Wu and Yuhan Sun, “Synthesis of Fe3O4\SiO2\Ag nanoparticles and its application in surface – enhanced Raman scattering,” Journal of Solid State Chemistry 183, pp. 2968-2973, 2010
[12].Ruo-Yu Hong, Jian-Hua Li, Shi-Zhong Zhang, Hong-Zhong Li, Ying Zheng, Jian-min Ding and Dong-Guang Wei, “Preparation and characterization of silica–coated Fe3O4 nanoparticles used as precursor of ferrofluids,” Applied Surface Science 255, pp. 3485-3492, 2009
[13].李昆峰，高肇鴻，陳錚誼，趙啟民，桌慧如，林玉娟，2006，“磁性奈米粒子於生醫領域之應用”，科儀新知，28卷，1期，頁61-69，8月。
[14].葉冠妏，2009，合成SiO2-Fe3O4中空多孔奈米粒子及其在藥物釋放之應用，中原大學，碩士論文。
[15].陳人豪，2006，磁性奈米粒子製備及其於電磁波遮蔽之應用，國立中央大學，碩士論文。
[16].江佩馨，超順磁性氧化鐵顯影劑於磁振造影診斷醫學上之技術發展及產業概況，工業技術研究院，台灣，2006
[17].郭曉婷，吳明昌，2009，“磁性粒子於醫療及酵素固定化、純化之應用”，台灣農業化學與食品科學，47卷，2期，頁87-95，4月。
[18].A Jordan, R. Scholz, P. Wust, H. Fahling and R. Felix﹕Magnetic Fluid Hyperthermia (MFH)﹕Cancer Treatment with AC Magnetic Field Induced Excitation of Biocompatlble Superparamagnetic Nanoparticles. J. Magnet. And Magn. Mater, 201﹕413-419 (1999).
[19].J. K. Yang, J. H. Yu, J. Kimc and Y. H. Choaa﹕Preparation of Superparamagnetic Nanocomposite Particles for Hyperthermia Therapy Application. Mater﹕Sci. Eng. A﹕477-479 (2007).
[20].J. S. Lin, Y. S. Lin, S. T. Kuo, C. M. Jiang and M. C. Wu﹕Purification of soybean amylase by superparamagnetic particles. Food Chem. (accepted) (2009).
[21].賴瓊鈺，盧集政，趙葉訪，宋德坤，2000，鐵磁流體的製備及穩定性研究，機械工業出版社。
[22].鄭豐裕，2006，四氧化三鐵磁性奈米粒子之製備及其在生物醫學上的應用，國立成功大學，博士論文。
[23].趙俊榮，2009，磁性奈米粒子/團聯共聚物複合材料的製備與特性研究，國立成功大學，碩士論文。
[24].馬振基，奈米材料科技原理與應用，全華科技圖書股份有限公司，2003
[25].鄭景軒，2003，磁性奈米微粒之二氧化矽被覆技術之研究，國立成功大學，碩士論文。
[26].張家誠，2008，氧化鋅奈米粒子之光致螢光性質研究，國立中央大學，碩士論文。
[27].邱信菖，2005，攪拌系統中膠體顆粒凝絮機制與穩態分析，國立中央大學，碩士論文。
[28].London, L. D. and E. M. Liftshitz, “Statistical physicals”, Pergamon, Oxford (1969).
[29].陳宇君，2009，碳化矽粒子於乙二醇中之行為研究探討，國立中央大學，碩士論文。
[30].蔡長書，蕭楺剛，徐維駿，2012，“金奈米粒子之製備與特性研究及其在生物醫學應用之探討”，慈濟技術學院學報，19期，頁17-42，7月。
[31].Challa, R., A. Ahuja, et al., “Cyclodextrins and their pharmaceutical applications.” International Journal of Pharmaceutics, 329 (1-2)：1-11, 2007
[32].黃佳琪，許梅娟，2007，“製備磷脂質修飾之奈米磁性顆粒及鑑定”，化工專輯，54卷，6期，頁92-111。
[33].R. A. Williams, Colloid and surface engineering﹕applications in the process industries, B-H Ltd, Oxford, 1992
[34].王惠君，2004，以回應曲面法探討溶膠-凝膠法製備奈米二氧化矽之參數影響，中原大學，碩士論文。
[35].S. Santra, R. Tapec, N. Theodoropoulou, J. Dobson, A. Hebard, W. Tan, Synthesis and characterization of silica-coated iron oxide nanoparticles in microemulsion﹕the effect of nonionic surfactants, Langmuir, 17, 2900-2906, 2001
[36].Y.H. Deng, C.C. Wang, J.H. Hu, W.L. Yang, S.K. Fu, Investigation of formation of silica-coated magnetite nanoparticles via sol-gel approach, Colloids and Surfaces A﹕Physicochemical and Engineering Aspects, 262, 87-93, 2005
[37].毛賢為，2007，以環糊精修飾之二氧化矽-磁性奈米粒子包覆披落卡藥物之探討，國立成功大學，碩士論文。
[38].http://tw.knowledge.yahoo.com/question/question?qid=1608072104676
[39].陳慶村，2012，添加Ni對Sn-3.5Ag無鉛銲料機械性質與顯微組織之影響，國立高雄應用科技大學，碩士論文。
[40].http://www.ncku.edu.tw/~facility/facility/index.htm
[41].http://www.bio.fju.edu.tw/excel/content05/html/41.htm
[42].林麗娟，1994，“X光繞射原理及其應用”，工業材料，86期，頁100-109，2月。
[43].http://deptpic.ccu.edu.tw/ytem.htm