奈米磁粒或磁流體已被廣泛應用在各個工程領域中，但效率始終難以提升，問題的癥結在於目前的製備技術無法產出像生物體(如感磁菌)一樣，尺寸均一、形狀特異、穩定分散、可有序組裝的奈米磁粒，並且對奈米磁粒與其自組裝結構的諸多性質也不甚清楚。有鑒於此，本研究基於仿生觀點，提出了一套針對均散性奈米磁粒的製備、自組裝與特性分析等三個方面之實作與理論分析方法，試圖找出提升仿生磁粒應用效能之系統製備與應用參數，再以印證方法確定其可行性。
針對磁粒製備及其基本磁性分析方面，本文採用熱裂解法進行不同結構組成、粒徑大小與幾何形狀之均散性氧化鐵奈米粒子製備，並對其基本磁性作分析，主要結果有下列幾點。(1)便宜且天然赤鐵礦粉體可做為起始反應物，以製備粒徑為8 ~ 22 nm之均散性氧化鐵奈米磁粒，且晶體生長過程符合溶解再結晶機制；梅森保光譜分析顯示粒子的組成會與粒徑有關，當粒徑小於10.6 nm時為γ-Fe2O3，當大於12.1 nm時為γ-Fe2O3與Fe3O4之混合物，且隨著粒徑變大，Fe3O4的含量亦會增加。(2)以孔洞形赤鐵礦粉體先行製作油酸鐵錯合物，然後再拿它進行熱裂解反應，可縮短奈米磁粒的製造時間約2~3 小時。(3)將油酸鐵錯合物於油酸溶劑中高溫(380 ℃)反應2小時，可得FeO奈米磁粒，且磁粒之結構組成(如FeO、FeO/Fe3O4、Fe3O4與γ-Fe2O3)可藉由不同程度之氧化控制；(4)於熱裂解反應中添加不同濃度之CTAB (cetyl trimethyl ammonium bromide)，可產出不同粒徑(10 ~ 120 nm)之八面體奈米磁粒。(5)當粒徑越小時，粒子磁矩與飽和磁化量有顯著的縮小趨勢，此現象主要源自於表面自旋傾斜的影響。(6) FeO/Fe3O4核殼奈米粒子會產生磁交換異向性效應(exchange anisotropy)，且TN = 206 K趨近於塊材FeO之值；(7)八面體形奈米磁粒之超順磁臨界尺寸約為31 nm，以及最佳感磁尺寸約為66 nm。
針對自組裝方面，本研究使用溶劑乾燥法與磁場誘發法製作奈米薄膜與定向超晶格結構。理論方面則由粒子間之勢能模型出發，以粒子結構與能量差異探討結構形成之機理。結果發現: (1)以凡得瓦爾力為主的自組裝超晶格結構，距離原點周圍粒子的排列狀態掌握了大部份的能量，屬於短程力的作用；另外也發現粒子並非完美的球形，它的表面仍具有許多少晶面，而這些晶面會影響最終的粒子排列狀態。(2)以磁偶極矩為主的自組裝結構，顯示粒子磁矩往<110>方向排列會比<100>方向來的穩定，且原點附近的粒子能量並無太大的差異性，只有當粒子遠離中心點後才開始出現差異，故推論此結構的成因為長距離有序(long-range order)作用所主導。
針對特性分析方面，磁性部份主要自組裝結構形式對磁特性之影響；力學部分則是利用奈米壓痕技術分析薄膜成形品質。結果發現(1)自組裝薄膜的矯頑力會因為粒子-粒子磁偶極矩的作用而產生加強效果；(2)由於易軸磁化的效果，自組裝奈米鏈的長軸會比短軸容易磁化；(3)磁性薄膜的硬度與彈性模數分佈高低差約在1~3倍之間，且薄膜的變性主要是由較軟的表面界面活性劑分子所貢獻。
針對仿感磁菌磁粒鏈組裝及其物性分析方面，本研究利用蒙地卡羅法模擬相關製程參數對組裝微結構之影響，並分析結構幾何尺寸對磁性與力學特性分影響，以建立感磁菌奈米鏈之設計法則。結果發現(1)對奈米磁粒子而言，所採用之粒徑必須大於16 nm與磁場強度必須大於於0.005 T以上，粒子才易組裝成鏈；(2)當鏈的長度越長時，矯頑力也會隨之增加，且當鏈長n > 10以後，矯頑力已趨近於飽和值；(3)使用大粒徑或高彈性係數之介面活性劑分子進行奈米鏈之製造，可有效增加鏈長，進而增加地磁之感測靈敏度。
將本文之結果與文獻比對，發現所建立的實驗與理論方法，已可模仿生物體所能製造之極限，除了能便宜且大量製造尺寸均一的粒子之外，還能對大小、形狀、介面、組成與膠體穩定性進行控制。再則，將所建立之理論與實作進行整合並應用於感磁菌奈米鏈之設計上，顯示理想的磁粒尺寸範圍為48~70 nm之間，鏈長範圍為10~31顆，順磁浮游效率可達90 %，且當選用D = 70 nm與n = 10時，可達成高感磁與定向效率之雙重目標，顯示本文之理論推估與實作流程可有效提升地磁感測效率。

Magnetic nanoparticles (NPs) or magnetic fluids have already been extensively applied to various engineering fields in recent years. However, the efficiency is still difficult to improve all the time, mainly because the present technology can not simulate the organism, such as magnetotactic bacteria (MTB) to produce magnetic NPs with mono-size, shape peculiar one, well disparity, order assembly, and also not very clear about their properties of the isolated NPs and assembled nanostructures. In view of this, this research proposes an experimental and theoretical approach for the preparation, self-assembly, and properties characterization of the monodisperse magnetic NPs from a bionic viewpoint. Moreover, the method is also used to find out the system parameters and to improve application efficiency on bionic magnetic NPs, in addition to confirm the feasibility.
In order to prepare the magnetic NPs, and study their basic magnetic properties, this research adopted a thermally-decomposed method to synthesize mono-disperse magnetic iron oxide nano-particles (MMIONPs) with controllable structural compositions with various sizes and shapes to character their basic magnetic properties. The results indicate that (1) the relatively inexpensive natural hematite (α-Fe2O3) powders can be used as a starting material to prepare MMIONPs by following dissolution-recrystallization mechanism. The compositions of the MMIONPs were determined first by Mssbauer spectroscopy. It appears that the compositions are dependent on the NP sizes. As the size is smaller than 10.6 nm, it is in pure γ-Fe2O3 phase. As the size goes beyond 12.1 nm, it becomes the mixture of both γ-Fe2O3 and Fe3O4 phases; (2) by using porous hematite to prepare iron oleate complexes (IOCs), and then using IOCs to thermally decompose into MMIONPs, the manufacture time can save 2~3 hours; (3) the mono-disperse FeO NPs is then synthesized by decomposition of IOCs in hot oleic acid as the solvent at 380 ℃ for 2 hours, and the composition, such as FeO/Fe3O4, Fe3O4, γ-Fe2O3 can be controlled by various degree of oxidation; (4) by adding CTAB (cetyl trimethyl ammonium bromide) ligand for thermally-decomposed reaction can yield octahedral MMIONPs. The particle size can be controlled by adjusting the reaction temperature and the ratio of CTAB to precursors; (5) the saturated magnetization and moment of the NP is clearly found decreased as the NP size decreased due to surface spin canting; (6) FeO/Fe3O4 Core-Shell NPs can produce exchange anisotropic phenomenon, and the TN of FeO core is about 206 K, which is close to bulk; (7) the super-paramagnetic limited size of octahedral MMIONPs is about 31 nm, and the best magnetic recording sizes are in the range of 66 nm.
In order to self-assemble the magnetic NPs, the present work employs a dry-mediated method and a magnetic-induced method to fabricate nano-membranes and directional super-lattice nanostructures. The theory is set out by the inter-particle potential model for finding the mechanism of structural formation by probing into the relation of assembled structures and energy difference. The results indicate that (1) the van der Waals force is a short range interaction. Its energy is a major contributor to attract neighboring NPs to form the NP core. On the other hand, the NPs are not perfectly sphere, it consists of many crystal facets, and the crystal facets will influence of NP arrangement; (2) When the formation of the nano-strucutes is due to magnetic dipole force, it shows that the <110> direction structure of magnetic dipole is more stable than that of the <100> directional arrangement. Moreover, the system energy calculated near the NP core does not have too much difference, except those which are far away from the core center. Thus, it can be concluded that the mechanism for the nanostructure formation is mainly of the long-range interaction.
In order to characterize the nanostructure properties, we used the SQUID (superconducting quantum interference device) technique to analyze magnetic properties with different structural forms, and also used nano-indenter technique to analyze the mechanical properties to understand the quality of nano-membrane. The results show (1) the coercive force of self-assembled nano-menbrane can be increased by interaction of magnetic dipole; (2) the long axis of the nano-chains can be easily magnetization than that of the short axis of nano-chains due to the effect of easy-axis magnetization; (3) The distribution of the hardness and elastic modulus of magnetic membrane is varied approximately 1~3 times. The deformation of the membrane is mainly contributed by softer surface-protected ligands of the NPs.
In order to chain-assemble bionic MTB NPs, and to character the properties of the nano-chain, this research used Monte Carlo simulation to find the relation of manufacturing parameters and assembled micro-structures first, and then analyze the effect of chain-geometric factors on the mechanical and magnetic properties for coming up a set of design rules for the MTB nano-chains. The results indicate that (1) if the assembly of nano-chains uses magnetic NPs, the adopted NP size must be larger than 16 nm, and the adopted strength of magnetic filed must be larger than 0.005 T, that ensures the formation of NP chain-assembly; (2) The coercive force is increased as the chain length increased, and coercive force reaches saturation as the chain length becomes larger than 10 NPs; (3) effective chain length and sensitivity of magnetic recording can be improved either by using a larger NP size or by using a higher elastically modulus of surface-protected ligands of NPs.
When compared our research results with those of referenced data, it is found that the experimental and theoretical approach proposed by this study agrees favorably with MTB by using a sort of cheaper manufacture mono-disperse NPs with tunable size, shape, interface, and good colloidal stability. Moreover, by applying the proposed theoretical and experimental approach to design MTB nanochain with geomagnetic recording efficiency of 90 %, the ideal NP size is found to be around 48 ~ 70 nm, and the ideal chain length is found to be around 10 ~31. When the NP size of 70 nm and the chain length of 10 are used to design MTB nanochain, it presents higher efficiency of geomagnetic recording and orientation time. The results indicate that the proposed experimental and theoretical approach presented in this study is accurate and effective.

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