臺灣博碩士論文加值系統

　　近幾年來，在合成材料中控制形貌和大小的研究引起相當大的關注，由於形貌和大小在材料的物性與化性扮演重要的角色。相較於四氧化三鐵奈米顆粒，次微米顆粒在磁共振影像、感測器和靶向給藥等領域有極大的潛力。四氧化三鐵常見的化學合成方式有熱分解法、共沉澱法、水熱法、電化學法、微乳液法和溶膠凝膠法等。本研究主要探討利用添加劑於水熱法中合成四氧化三鐵次微米結構之研究。本研究採用水熱法，以硫酸亞鐵銨為前驅物，加入環六亞甲基四胺當鹼源，並加入不同種類添加劑：PEG-6000和氟化鈉，放入壓力釜當中，以水熱法合成四氧化三鐵；經由改變反應條件，包括環六亞甲基四胺濃度、添加劑量、反應時間和反應溫度，可合成出次微米級球狀、八面體形狀的四氧化三鐵。最後探討反應條件與不同添加劑對鐵氧化物形貌的影響。結果發現，當添加劑為PEG-6000時，四氧化三鐵形貌主要為球體結構；當添加劑為氟化鈉時，四氧化三鐵形貌主要為八面體結構。不同形貌之四氧化三鐵具有不同的磁性特性。

Due to that morphology and size play very important roles in determining chemical and physical properties of materials, in recent years, there is increasing attentions on the development of synthesis method to control the morphology and size of particles. Comparing with Fe3O4 nanoparticle, Fe3O4 submicroparticle has potential applications in the fields of magnetic resonance imaging, sensors, targeted drug delivery and color displays. The preparation of micro Fe3O4 particle with well defined nanostructure and morphology is of particular interest of this study. The synthesis of submicro Fe3O4 particle including thermal decomposition, co-precipitation, hydrothermal, electrochemical method, micro-emulsion method and sol-gel methods. In this study, we focused on the hydrothermal method to control the morphology and size of particles. The effect of additives, such as soft template PEG-6000 and NaF salt, on the synthesis of Fe3O4 micro-structure were investigated. It was demonstrated that two kinds of shapes of Fe3O4, including micro-spheres and micro-octahedron, can be prepared by adjusting the hexamethylenetetramine concentration, the amount of additive, reaction time and reaction temperature. The morphology of Fe3O4 were spheres-like with PEG-6000. The morphology of Fe3O4 were octahedron-like with sodium fluoride.

中文摘要 i
英文摘要 ii
致謝 iv
目錄 v
表目錄 vii
圖目錄 viii
第一章 緒論 1
1.1 前言 1
1.2 四氧化三鐵的結構與性質 1
1.3 次微米四氧化三鐵的應用 3
1.3.1 核磁共振成像 4
1.3.2 塗料 4
1.3.3 鋰離子負極材料 5
1.4 研究目的 6
第二章 文獻回顧 7
2.1 四氧化三鐵常見的製備方法 7
2.1.1 沉澱法 7
2.1.1.1 共沉澱法 7
2.1.1.2 氧化沉澱法 8
2.1.1.3 還原沉澱法 9
2.1.2 溶膠凝膠法 9
2.1.3 微乳液法 10
2.1.4 水熱/溶劑熱法 11
2.1.5 熱分解法 12
2.1.6直流電弧等離子體法 13
2.2 次微米級四氧化三鐵的製備方法 14
2.3 控制形貌的方法與原理 16
2.3.1 通過控制晶體生長條件控制顆粒形狀 16
2.3.2 通過改變反應條件控制顆粒形狀 17
2.3.3 通過聚集作用控制顆粒形狀 17
2.3.4 通過自組裝控制顆粒形狀 18
第三章 實驗方法 20
3.1 實驗藥品 20
3.2 分析儀器 22
3.3 實驗步驟 25
第四章 結果與討論 29
4.1 鹼源對於四氧化三鐵形貌與結構之影響 29
4.1.1 NaOH作為鹼源 29
4.1.2 尿素作為鹼源 31
4.1.3 環六亞甲基四胺作為鹼源 32
4.1.4 鹼源種類對四氧化三鐵產率之影響 34
4.2 添加劑對四氧化三鐵形貌與結構之影響 36
4.2.1 PEG添加劑 36
4.2.2 NaF添加劑 38
4.3 製備條件對四氧化三鐵形貌與結構之影響 39
4.3.1 鹼源量對四氧化三鐵形貌與結構之影響 39
4.3.1.1 PEG-6000 39
4.3.1.2 NaF 42
4.3.2 添加劑量對四氧化三鐵形貌與結構之影響 45
4.3.2.1 PEG-6000 45
4.3.2.2 NaF 52
4.3.3 反應溫度對四氧化三鐵形貌與結構之影響 59
4.3.3.1 PEG-6000 59
4.3.3.2 NaF 66
4.3.4 反應時間對四氧化三鐵形貌與結構之影響 74
4.3.4.1 PEG-6000 74
4.3.4.2 NaF 82
4.4 四氧化三鐵之生長機制 91
4.4.1 PEG-6000 91
4.4.2 NaF 92
4.4.3 製備條件對生長機制之影響 92
4.5 四氧化三鐵在不同形貌下的磁性性質 101
第五章 結論與建議 106
參考文獻 107

1.李玉寶主編，奈米生醫材料，五南出版社，2006年。
2.K.H. Choi, et al., “A Facile Fabrication of Fe3O4/ZnO Core-Shell Submicron Particels with Controlled Size”, IEEE Trans. Magn. 47(10), 2011, pp. 3369-3372.
3.S. Wang, et al., “Fe3O4 submicron spheroids as anode materials for lithium-ion batteries with stable and high electrochemical performance”, J. Power Sour. 195, 2010, pp. 5379-5381.
4.B. Hamm, et al., “Contrast-enhanced MR imaging of liver and spleen: first experience in humans with a new superparamagnetic iron oxide”, J. Magn. Reson. Imaging, 4(5), 1994, 659-668.
5.I. Koh, et al. “Magnetic Iron Oxide Nanoparticles for Biorecognition: Evaluation of Surface Coverage and Activity”, J. Phys. Chem. B , 110, 2006, pp. 1553-1558.
6.S.K. Banerjee, et al., “Ferrimagnetic properties of magnetite, in Magnetite Biomineralization and Magnetoreception in Organisms: A New Magnetism”, edited by J. L. Kirschvink, and et. al., Plenum Publishing Corporation, 1985, pp. 17-41.
7.邱瑞宗，導電性及導磁性之電磁波屏蔽複合材料研究，碩士論文，國立臺北科技大學，台北，2006。
8.杜怡君、張毓娟、翁乙壬、蘇怡帆、陳世毓、梁哲銘、葉巧雯、吳信璋、卓育泯，磁性基本特性及磁性材料應用，國立台灣大學化學系，台北。
9.R. Weissleder, et al., “Polyclonal human immunoglobulin G labeled with polymeric iron oxide: antibody MR imaging”, Radiology, 180(1), 1991, pp. 245-249.
10.唐萌編著，氧化鐵納米材料生物效應與安全應用，科學出版社，2010年2月
11.X.Y. Wang, et al., “Synthesis of strong-magnetic nanosized black pigment ZnxFe(3-x)O4”, J. Dyes and Pigments, 74, 2007, 269-272.
12.吳宇平、戴曉兵、馬軍旗、程預江編著，鋰離子電池－應用與實踐，化學工業出版社，2004年3月。
13.于文廣、張同來、張建國、郭金玉、吳瑞鳳，「納米四氧化三鐵(Fe3O4)的製備和形貌」，化學進展，第19券，第6期，2007，第884-891頁。
14.馬千里、董相廷、王進賢、劉佳霞、于文生，「納米四氧化三鐵的化學製備方法研究進展」，化工進展，第31券，第3期，2012，第562-573頁。
15.Y. Zhao, et al., “Preparation and Analysis of Fe3O4 Magnetic Nanoparticles Used as Targeted-drug Carriers”, Chinese J. Chem. Eng., 16(3), 2008, pp. 451-455.
16.D. Thapa, et al., “Properties of magnetite nanoparticles synthesized through a novel chemical route”, Mater. Lett., 58, 2004, 2692-2694.
17.W. Yu, et al., “The synthesis of octahedral nanoparticles of magnetite”, Mater. Lett., 60(24), 2006, 2998-3001.
18.S. Qu, et al., “Magneite Nanoparticles Prepared by Precipitation from Partialy Reduced Ferric Chloride Aqueous Solutions”, J. Colloid Interface Sci., 215(1), 1999, pp. 190-192.
19.A. Bernardo, Sol-gel technology: "THE NANO-SONS''S BIG MUM", 2010.
20.Y.K. Gun’ko, et al., “Magnetic nanoparticles and nanoparticle assemblies from metallorganic precursors”, J. Mater. Sci. Mater. Electro., 12, 2001, pp. 299-302.
21.J. Vadal-Vadal, et al., “Synthesis of monodisperse maghemite nanoparticles by the microemulsion method”, Colloids Surf. A, 288(1-3), 2006, pp. 44-51.
22.Y.B. Khollam, et al., “Microwave hydrothermal preparation of submicron-sized spherical magnetite (Fe3O4) powders”, Mater. Lett., 56, 2002, pp. 571-577.
23.L. Diamandescu, et al. “Hydrothermal synthesis and structural characterization of some substituted magnetites”, Mater. Lett., 37, 1998, pp. 340-348.
24.N. Pinna, et al., “Magnetite Nanocrystals: Nonaqueous Synthesis, Characterization, and Solubility”, Chem. Mater., 17, 2005, pp. 3044-3049.
25.S. Si, et al., “Magnetic Monodisperse Fe3O4 Nanoparticles”, Cryst. Growth Des., 5(2), 2005, pp. 391-393.
26.D.W. Lee, et al., “Enhanced Oxidation Resistance of Iron Nanoparticles via Surface Modification in Chemical Vapor Condensation Process”, J. Mater. Sci. Technol., 26(4), 2010, pp. 367.370.
27.L. Chen, et al., “Controlled synthesis of Fe3O4 nanosheets via one-step pyrolysis of EDTA ferric sodium salt”, J. Alloys Compd., 504(2), 2010, pp.46-50.
28.Z. Li, et al., “One-Pot Reaction to Synthesize Water-Soluble Magnetite Nanocrystals”, Chem. Mater., 16(8), 2004, pp. 1391-1393.
29.S. Sun, et al., “Size-Controlled Synthesis of Magnetite Nanoparticles”, J. Am. Chem. Soc., 124(28), 2002, pp. 8204-8205.
30.L. Wang, et al., “Monodispersed core-shell Fe3O4@Au nanoparticles”, J. Phys. Chem. B, 109(46), 2005, pp. 21593-21601.
31.Z. Xu, et al., “Magnetic Core/Shell Fe3O4/Au and Fe3O4/Au/Ag Nanoparticles with Tunable Plasmonic Properties”, J. Am. Chem. Soc., 129(28), 2007, pp. 8698-8699.
32.周長華、李曉民、司紅磊、郭軼、徐力、張治軍、李林松，相轉移方法製備水溶性Fe3O4納米晶，化學學報，第69券，第12期，2011，第1381-1386頁。
33.C. Balasubramaniam, et al., “DC thermal arc-plasma preparation of nanometric and stoichiometric spherical magnetite (Fe3O4) powders”, Mater. Lett., 58, 2004, pp. 3958-3962.
34.S. Ni, et al., “Size controlled and morphology tuned fabrication of Fe3O4 nanocrystals and their magnetic properties”, J. Alloys and Compd., 505, 2010, pp. 727-732.
35.B. Jia, et al., “Fabrication of Fe3O4 core-shell polyhedron based on a mechanism analogue to Ostwald ripening process”, J. Cryst. Growth, 303, 2007, pp. 616-621.
36.Y. Lv, et al., “Synthesis,characterization and growing mechanism of monodisperse Fe3O4 microspheres”, J. Cryst. Growth, 311, 2009, pp. 3445-3450.
37.H. Bi, et al, “Synthesis of Fe3O4 hollow microsphere chains and their magnetic properties”, J. Solid State Comm. 149, 2009, pp. 2115-2119.
38.J. Zhang, et al., “Formation, characterization, and magnetic properties of Fe3O4 microoctahedrons”, J. Cryst. Growth, 308, 2007, pp. 159-165.
39.B. Rodriguez-Gonzalez, et al., “Rough and Hollow Spherical Magnetite Microparticles: Revealing the Morphology, Internal Structure, and Growth Mechanism”, J. Phys. Chem. C, 117, 2013, pp. 5397-5406.
40.李霄，過渡金屬氧化物、硫化物納米結構的形貌控制及性能研究，碩士論文，浙江理工大學，中國浙江，2010。
41.J. Ao, et al., “Crystal Structure and Properties of Chemical Bath Deposited CdS Thin Films”, Chinese J. Semiconductors, 26(7), 2005, pp. 1347-1352.
42.S. Fullam, et al., “Carbon Nanotube Templated Self-Assembly and Thermal Processing of Gold Nanowires”, Adv. Mater., 12(19), 2000, pp. 1430-1432.
43.G.S Cheng, et al., “Large-scale synthesis of single crystalline gallium nitride nanowires”, Appl. Phys. Lett., 76(16), 1999, pp. 2455-2457
44.H. Zhang, et al., “Preparation of ZnO nanorods through wet chemical method”, Mater. Lett., 61, 2007, pp. 5202-5205.
45.C. Wu, et al., “Controllable ZnO morphology via simple template-free solution route”, Mater. Chem. Phys., 102, 2007, pp. 7-12.
46.Z.R. Tian, et al., “Complex and oriented ZnO nanostructures”, Nat. Mater., 2, 2003, pp. 821-826.
47.Y. Cheng, et al., “Controllable synthesis and magnetic properties of Fe3O4 and Fe3O4@SiO2 microspheres”, J. Mater. Sci. 45, 2010, pp. 5347-5352.
48.X.L. Lin, et al., “Atmospheric Pressure Chemical Vapor Deposition: An Alternative Route to Large-Scale MoS2 and WS2 Inorganic Fullerene-like Nanostructures and Nanoflowers”, Chem. Eur. J., 10(23), 2004, pp. 6163-6171.
49.J. Chen, et al., “Synthesis of open-ended MoS2 nanotubes and the application as the catalyst of methanation”, Chem. Commun., 2002, pp. 1722-1723.
50.G.M. Whitesides, et al., “Molecular self-assembly and nanochemistry: a chemical strategy for the synthesis of nanostructures”, Science, 254, 1991, pp. 1312-1319.
51.高倩，張吉林，洪廣言，倪嘉纘，不同形貌的Fe3O4微-納米粒子的溶劑熱合成，高等學校化學學報，第32券，第3期，2011，第552-559頁。
52.焦淑紅，徐東升，許荔芬，張曉光，金屬氧化物納米材料的電化學合成與形貌調控研究進展，物理化學學報，第28券，第10期，2010，第2436-2446頁。
53.V.G. Pol, et al., “Solvent-Free Fabrication of Ferromagnetic Fe3O4 Octahedra”, Ind. Eng. Chem. Res., 49, 2010, pp. 920-924.
54.S. Ni, et al., “Low temperature synthesis of Fe3O4 micro-spheres and its microwave absorption properties”, Mater. Chem. Phys. 124, 2010, pp. 353-358.