本論文介紹矽油基磁流體的製備與性質分析。以矽油界面活性劑OTEOS包覆Fe3O4奈米顆粒，使Fe3O4奈米顆粒分散於載體溶液。先利用TEOS的水解作用在Fe3O4奈米顆粒表面包覆SiO2，OTEOS可以進一步和SiO2反應並對矽油有良好的相容性，因此可以形成Fe3O4奈米顆粒和矽油的懸浮溶液。Fe3O4奈米顆粒的結構由XRD分析可確認為反尖晶石結構；由TEM可發現Fe3O4奈米顆粒平均尺寸約在10 nm；Fe3O4奈米顆粒和界面活性劑間的交互作用以FTIR、Raman、TGA分析；也會討論磁性、包覆性等性質。經過一系列實驗探討，以1 ml的TEOS和3 ml的OTEOS進行反應，可以得到混和效果最好的矽油基磁流體。

Ferro-fluid (FF) is a kind of colloidal dispersion consisting of magnetic nanoparticles, appropriate surfactant, and carrier fluid. FF has attracted a great attention due to its unique properties and thus it has been used in industry, such as sealing, inertia damper, heat transfer for several decades, and even some biomedical applications nowadays. In this research, silicone oil based ferro-fluid which is made from tetraethoxysilane and triethoxycaprylylsilane is introduced. The crystal structure is inverse spinel which is determined by XRD. Dimension and morphology of nanoparticles are studied using TEM and other approaches. Interaction between nanoparticles and surfactant is characterized by FTIR、Raman、TGA. VSM and acidic corrosion are also tested. Silicone oil based FF made by 1 ml of TEOS and 3 ml of OTEOS display an optimal dispersion in silicone oil.

1 文獻回顧 1
1-1 磁流體簡介 1
1-2 磁性奈米顆粒 2
1-2-1 磁性奈米顆粒的種類 2
1-2-2 磁性奈米顆粒的製程 2
1-2-3 磁性奈米顆粒的尺寸 3
1-2-4 磁性奈米顆粒的磁性質 5
1-2-5 共沉積法製備磁性奈米顆粒 8
1-3 奈米顆粒的表面修飾 10
1-4 界面活性劑 11
1-4-1 界面活性劑的作用機制 11
1-4-2 界面活性劑的種類 13
1-4-3 陰離子界面活性劑 14
1-4-4 陽離子界面活性劑 16
1-4-5 兩層式界面活性劑 17
1-5 載體溶液之選擇 18
1-6 法向量場不穩定性 18
2 研究動機 20
3 實驗流程 21
3-1 實驗流程圖 22
3-2 藥品及儀器 23
3-2-1 實驗藥品與材料 23
3-2-2 實驗設備與器材 23
3-3 實驗步驟 24
3-3-1 共沉積法合成Fe3O4奈米顆粒 24
3-3-2 TEOS進行表面修飾 ( Fe3O4 / SiO2 ) 24
3-3-3 OTEOS 作為界面活性劑 ( Fe3O4 / SiO2 / OTEOS ) 25
3-3-4 真空乾燥並將乾燥粉末和矽油混和 25
3-4 材料分析與量測方法 27
3-4-1 X光繞射分析 ( XRD, X-ray Diffraction ) 27
3-4-2 場發射掃描式電子顯微鏡 (Field-emission Scanning Electron Microscope, FE-SEM ) 27
3-4-3 穿透式電子顯微鏡 ( Transmission Electron Microscope, TEM ) 27
3-4-4 能量散佈光譜儀 ( Energy-dispersive X-ray Spectroscopy, EDS ) 28
3-4-5 熱重分析 ( Thermogravimetric Analysis, TGA ) 28
3-4-6 傅立葉轉換紅外線光譜 ( Fourier-transform Infrared Spectroscopy FTIR ) 28
3-4-7 拉曼光譜 ( Raman spectroscopy ) 29
3-4-8 震動樣品磁量儀 ( Vibrating Sample Magnetometer, VSM ) 29
3-4-9 耐酸性(包覆性)量測分析[56] 29
4 結果與討論 31
4-1 Fe3O4奈米顆粒合成 31
4-2 Fe3O4 / SiO2材料分析 34
4-2-1 XRD 34
4-2-2 VSM 35
4-2-3 TEM 38
4-3 OTEOS作為界面活性劑之效果 39
4-3-1 XRD 41
4-3-2 EDS 42
4-3-3 FTIR 43
4-3-4 Raman 44
4-3-5 TGA 45
4-3-6 TEOS對磁流體的影響 46
4-3-7 顆粒濃度影響 48
4-3-8 TEM 50
4-3-9 耐酸性(包覆性)測試 53
5 結論 54
6 未來工作 55
參考資料 56

[1] Söffge, F., and E. Schmidbauer. "AC susceptability and static magnetic properties of AN Fe3O4 ferrofluid." Journal of Magnetism and Magnetic Materials 24.1 (1981): 54-66.
[2] First4magnets available from :
https://www.first4magnets.com/other-c89/efh1-ferrofluid-magnetic-liquid-science-art-p3849#ps_0_4037|ps_1_2340
[3] Massart, Rene. "Preparation of aqueous magnetic liquids in alkaline and acidic media." IEEE transactions on magnetics 17.2 (1981): 1247-1248.
[4] Chagnon, Mark S. "Stable ferrofluid compositions and method of making same." U.S. Patent No. 4,356,098. 26 Oct. 1982.
[5] Raj, K., and R. Moskowitz. "Commercial applications of ferrofluids." Journal of Magnetism and Magnetic Materials 85.1-3 (1990): 233-245.
[6] Moskowitz, Ronald, Philip Stahl, and Walter R. Reed. "Inertia damper using ferrofluid." U.S. Patent No. 4,123,675. 31 Oct. 1978.
[7] Lajvardi, Maryamalsadat, et al. "Experimental investigation for enhanced ferrofluid heat transfer under magnetic field effect." Journal of Magnetism and Magnetic Materials 322.21 (2010): 3508-3513.
[8] Lübbe, Andreas Stephan, et al. "Preclinical experiences with magnetic drug targeting: tolerance and efficacy." Cancer research 56.20 (1996): 4694-4701.
[9] Hiergeist, R., et al. "Application of magnetite ferrofluids for hyperthermia." Journal of Magnetism and Magnetic Materials 201.1-3 (1999): 420-422.
[10] Kim, Eun Hee, et al. "Synthesis of ferrofluid with magnetic nanoparticles by sonochemical method for MRI contrast agent." Journal of Magnetism and Magnetic Materials 289 (2005): 328-330.
[11] Sharma, V. K., and F. Waldner. "Superparamagnetic and ferrimagnetic resonance of ultrafine Fe3O4 particles in ferrofluids." Journal of Applied Physics 48.10 (1977): 4298-4302.
[12] Sen, Surajit, Marian Manciu, and Felicia S. Manciu. "Ejection of ferrofluid grains using nonlinear acoustic impulses—A particle dynamical study." Applied physics letters 75.10 (1999): 1479-1481.
[13] Bacri, Jean-Claude, et al. "Ionic ferrofluids: a crossing of chemistry and physics." Journal of Magnetism and Magnetic Materials 85.1-3 (1990): 27-32.
[14] Wagner, Joachim, Tina Autenrieth, and Rolf Hempelmann. "Core shell particles consisting of cobalt ferrite and silica as model ferrofluids [CoFe2O4–SiO2 core shell particles]." Journal of magnetism and magnetic materials 252 (2002): 4-6.
[15] WU KT, K. U. O. P. C., and YD YAO. "Magnetic and optical properties of Fe 3 O 4 nanoparticle ferrofluids prepared by coprecipitation technique [J]." IEEE Transactions on Magnetics 37.4 (2001): 2651-2653.
[16] Deng, Yong-Hui, et al. "Investigation of formation of silica-coated magnetite nanoparticles via sol–gel approach." Colloids and Surfaces A: Physicochemical and Engineering Aspects 262.1-3 (2005): 87-93.
[17] Kim, Eun Hee, et al. "Synthesis of ferrofluid with magnetic nanoparticles by sonochemical method for MRI contrast agent." Journal of Magnetism and Magnetic Materials 289 (2005): 328-330.
[18] Wang, Jun, et al. "One-step hydrothermal process to prepare highly crystalline Fe3O4 nanoparticles with improved magnetic properties." Materials research bulletin 38.7 (2003): 1113-1118.
[19] Hong, R. Y., et al. "Rheological properties of water-based Fe3O4 ferrofluids." Chemical Engineering Science 62.21 (2007): 5912-5924
[20] Makovec, Darko, et al. "The synthesis of spinel–ferrite nanoparticles using precipitation in microemulsions for ferrofluid applications." Journal of magnetism and magnetic materials 289 (2005): 32-35.
[21] Clark, Noel A., Joseph H. Lunacek, and George B. Benedek. "A study of Brownian motion using light scattering." American Journal of Physics 38.5 (1970): 575-585.
[22] Edward, John T. "Molecular volumes and the Stokes-Einstein equation." Journal of Chemical Education 47.4 (1970): 261.
[23] Stuhler, Jürgen, et al. "Observation of dipole-dipole interaction in a degenerate quantum gas." Physical Review Letters 95.15 (2005): 150406.
[24] Levitt, Malcolm H. Spin dynamics: basics of nuclear magnetic resonance. John Wiley & Sons, 2013.
[25] Scherer, Claudio, and Antonio Martins Figueiredo Neto. "Ferrofluids: properties and applications." Brazilian Journal of Physics 35.3A (2005): 718-727.
[26] ENCYCLOPAEDIA BRITANNICA available from :
https://www.britannica.com/science/magnetism
[27] Lin, Chia-Lung, Chia-Fen Lee, and Wen-Yen Chiu. "Preparation and properties of poly (acrylic acid) oligomer stabilized superparamagnetic ferrofluid." Journal of Colloid and Interface Science 291.2 (2005): 411-420.
[28] PROBE, HALL. "TOMáš ŠČEPKA."
[29] Chen, Wai Kai. The electrical engineering handbook. Elsevier, 2004.
[30] Zhi, Jia, et al. "In situ preparation of magnetic chitosan/Fe3O4 composite nanoparticles in tiny pools of water-in-oil microemulsion." Reactive and Functional Polymers 66.12 (2006): 1552-1558.
[31] Wu, Shen, et al. "Fe3O4 magnetic nanoparticles synthesis from tailings by ultrasonic chemical co-precipitation." Materials Letters 65.12 (2011): 1882-1884.
[32] Meng, Haining, et al. "Orthogonal optimization design for preparation of Fe3O4 nanoparticles via chemical coprecipitation." Applied Surface Science 280 (2013): 679-685.
[33] Fu, Lei, Vinayak P. Dravid, and D. Lynn Johnson. "Self-assembled (SA) bilayer molecular coating on magnetic nanoparticles." Applied Surface Science 181.1-2 (2001): 173-178.
[34] 劉陽橋. 奈米粉體的分散及表面改性. 五南圖書出版股份有限公司, 2005.
[35] Kango, Sarita, et al. "Surface modification of inorganic nanoparticles for development of organic–inorganic nanocomposites—A review." Progress in Polymer Science 38.8 (2013): 1232-1261.
[36] Stöber, Werner, Arthur Fink, and Ernst Bohn. "Controlled growth of monodisperse silica spheres in the micron size range." Journal of colloid and interface science 26.1 (1968): 62-69.
[37] Chen, Lingyun, et al. "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 497.1-2 (2010): 221-227.
[38] Gao, Meizhen, et al. "Synthesis and characterization of superparamagnetic Fe3O4@ SiO2 core-shell composite nanoparticles." World Journal of Condensed Matter Physics 1.2 (2011): 49-54.
[39] Chen, H. J., et al. "Preparation and characterization of silicon oil based ferrofluid." Applied surface science 257.24 (2011): 10802-10807.
[40] Swisher, Robert Donald. Surfactant biodegradation. Vol. 18. CRC Press, 1986.
[41] Wang, Xiaoyong, et al. "Properties of mixed micelles of cationic gemini surfactants and nonionic surfactant triton X-100: effects of the surfactant composition and the spacer length." Journal of colloid and interface science 286.2 (2005): 739-746.
[42] Abrikosov, Alekseĭ Alekseevich, Lev Petrovich Gorkov, and Igor Ekhielevich Dzyaloshinski. Methods of quantum field theory in statistical physics. Courier Corporation, 2012.
[43] French, Roger H. "Origins and applications of London dispersion forces and Hamaker constants in ceramics." Journal of the American Ceramic Society 83.9 (2000): 2117-2146.
[44] VOCUS available from :
https://vocus.cc/@jayden_MSMF/5c318c5dfd89780001d010e7
[45] . Rapp, Bastian E. Microfluidics: modeling, mechanics and mathematics. William Andrew, 2016.
[46] Johansson, Ingegard, and Ponisseril Somasundaran, eds. Handbook for Cleaning/decontamination of Surfaces. Elsevier, 2007.
[47] Wang, Steven S-S., Kuan-Nan Liu, and Tzu-Chiang Han. "Amyloid fibrillation and cytotoxicity of insulin are inhibited by the amphiphilic surfactants." Biochimica et Biophysica Acta (BBA)-Molecular Basis of Disease 1802.6 (2010): 519-530.
[48] Raj, Kuldip, Ronald E. Rosensweig, and Lutful M. Aziz. "Stable polysiloxane ferrofluid compositions and method of making same." U.S. Patent No. 5,851,416. 22 Dec. 1998.
[49] Wang, Shenghai, Chuncheng Yang, and Xiufang Bian. "Magnetoviscous properties of Fe3O4 silicon oil based ferrofluid." Journal of magnetism and magnetic materials 324.20 (2012): 3361-3365.
[50] Borduz, Lucian, and Kuldip Raj. "Stable ferrofluid composition and method of making and using same." U.S. Patent No. 4,604,222. 5 Aug. 1986.
[51] Boyer, François, and Eric Falcon. "Two-dimensional melting of a crystal of ferrofluid spikes." Physical review letters 103.14 (2009): 144501.
[52] Selimefendigil, Fatih, and Hakan F. Öztop. "Numerical study of natural convection in a ferrofluid-filled corrugated cavity with internal heat generation." Journal of Heat Transfer 138.12 (2016).
[53] Kadau, Holger, et al. "Observing the Rosensweig instability of a quantum ferrofluid." Nature 530.7589 (2016): 194-197.
[54] Chen, Ching-Yao, and Z-Y. Cheng. "An experimental study on Rosensweig instability of a ferrofluid droplet." Physics of Fluids 20.5 (2008): 054105.
[55] Andelman, David, and Ronald E. Rosensweig. "The phenomenology of modulated phases: From magnetic solids and fluids to organic films and polymers." Polymers, liquids and colloids in electric fields: interfacial instabilities, orientation and phase transitions. 2009. 1-56.
[56] Tsuda, Shiro, Yasutake Hirota, and Hisao Suzuki. "Composition and method of making a ferrofluid having an improved chemical stability." U.S. Patent No. 6,261,471. 17 Jul. 2001.
[57] Malega, Ferni, I. P. Indrayana, and Edi Suharyadi. "Synthesis and characterization of the microstructure and functional group bond of fe3o4 nanoparticles from natural iron sand in Tobelo North Halmahera." Jurnal Ilmiah Pendidikan Fisika Al-Biruni 7.2 (2018): 13-22.
[58] Quy, Dao Van, et al. "Synthesis of silica-coated magnetic nanoparticles and application in the detection of pathogenic viruses." Journal of Nanomaterials 2013 (2013).
[59] Xu, Jiakun, et al. "Synthesis and characterization of magnetic nanoparticles and its application in lipase immobilization." Bull. Korean Chem. Soc 34.8 (2013): 2408-2412.
[60] Ta, Thi Kieu Hanh, et al. "Synthesis and surface functionalization of Fe3O4-SiO2 core-shell nanoparticles with 3-glycidoxypropyltrimethoxysilane and 1, 1′-carbonyldiimidazole for bio-applications." Colloids and Surfaces A: Physicochemical and Engineering Aspects 504 (2016): 376-383.
[61] INFRARED ANALYSIS OF ORGANOSILICON COMPOUNDS : SPECTRA-STRUCTURE CORRELATIONS
Complied by Philip J. Launer, Updated by Barry Arkles
[62] Yew, Yen Pin, et al. "An eco-friendly means of biosynthesis of superparamagnetic magnetite nanoparticles via marine polymer." IEEE Transactions on Nanotechnology 16.6 (2017): 1047-1052.
[63] Shebanova, Olga N., and Peter Lazor. "Raman spectroscopic study of magnetite (FeFe2O4): a new assignment for the vibrational spectrum." Journal of Solid State Chemistry 174.2 (2003): 424-430.
[64] Galeener, Frank L., and J. C. Mikkelsen Jr. "Vibrational dynamics in O 18-substituted vitreous Si O 2." Physical Review B 23.10 (1981): 5527.