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研究生: 邱信凱
Chiu, Hsin-Kai
論文名稱: 鎳金合金奈米粒子之製備與特性研究
Preparation and Characterization of Ni-Au Alloy Nanoparticles
指導教授: 陳東煌
Chen, Dong-Hwang
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2005
畢業學年度: 93
語文別: 中文
論文頁數: 98
中文關鍵詞: 合金奈米粒子
外文關鍵詞: alloy nanoparticles
相關次數: 點閱:98下載:1
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  •   本論文在water/CTAB/1-butanol/isooctane微乳化系統中,於65C下以聯氨還原氯化鎳及四氯金酸來製備鎳/金合金型及核殼型奈米粒子,探討其粒徑、光學特性、組成、結構、磁性、及生物毒性等,並觀察其在外加磁場下之磁自組行為。
      穿透式電子顯微鏡(TEM)分析顯示,不同組成( Ni/Au莫耳比= 1/0、3/1、1/1、1/3、0/1 )的鎳金合金奈米粒子,其平均粒徑小於20 nm,且隨著金含量比例增加而有逐漸變小的趨勢。比較合金與單金屬奈米粒子之UV/VIS吸收光譜,可知在微乳化系統中的確可製得不同組成的鎳金合金奈米粒子,且由X射線繞射儀(XRD)及電子繞射圖可知所製得之合金奈米粒子為面心立方結構。以原子吸收光譜儀(AAS)分析粒子整體組成,發現皆與反應液之金屬鹽組成相似,而能量分散光譜儀(EDX)分析更直接證明單顆鎳金合金奈米粒子的組成約略等於反應液之金屬鹽組成,說明了合金粒子的形成與組成的均勻性。利用超導量子干涉儀(SQUID)測量粒子的交換偏移場消失溫度(TB)、飽和磁化量(Ms)、殘留磁化量(Mr)和保磁力(Hc),可知隨著鎳含量的減少,粒徑逐漸變小,且磁性材料的特徵物理量均有減少的趨勢。這些現象可歸因於個別金屬成分的還原速率及其粒子形成速率與原子結構等差異。又在外加磁場下,磁性粒子可依磁場方向自組裝排列形成20~50m長的平行線。此外,由生物毒性測試得知,不同組成之鎳金合金奈米粒子的生物毒性皆較純鎳奈米粒子為低,但相關因素與機制則有待進一步研究。最後,本研究也以Ni3Au1合金奈米粒子為核,在其表面被覆不同厚度的金奈米殼層,製得核殼型金屬奈米粒子,並探討其組成、粒徑、結構、與光學特性。

      In this thesis, Ni/Au alloy and core-shell composite nanoparticles at various molar ratios were prepared by the hydrazine reduction of nickel chloride and hydrogen tetrachloroaurate in the microemulsion system of water/CTAB/1-butanol/isooctane at 65C. The size, optical property, composition, structure, magnetic property, and cytotoxicity of the resultant composite nanopartilces were investigated. Also, their self-organization at an external magnetic field was examined.
      The analysis by transmission electron microscopy (TEM) revealed that the mean diameters of Ni/Au alloy nanoparticles at various molar ratios (Ni/Au=1/0, 3/1, 1/1, 1/3, 0/1) were less than 20 nm and decreased with increasing the Au content. The comparison between the UV/VIS absorption spectra of monometallic and alloy nanoparticles suggested the formation of Ni/Au alloy nanoparticles at various molar ratios. The analyses of XRD patterns and electron diffraction pattern indicated that the resultant alloy nanoparticles possessed the face-centered cubic (f.c.c) structure. The composition analysis by atomic absorption spectrometer (AAS) showed the overall compositions of alloy nanoparticles were similar to those in the starting solutions. Also, the energy dispersive X-ray analysis (EDX) on a single particle indicated the composition of each alloy nanoparticle was consistent with the composition in the starting solutions. This suggested the formation of alloy nanoparticles and their uniformity in composition. The blocking temperature (TB), saturation magnetization (MS), remanent magnetization (Mr), and coercivity (Hc) of Ni/Au alloy nanoparticles at molar ratios were measured by the superconducting quantum interference device (SQUID) magnetometer. These physical quantities are affected by the particle size and magnetic molecular clusters. These phenomena could be referred to the differences in the reduction rate of each metallic particles, the formation rate of particles, and the atomic structure. At an external magnetic field, the magnetic nanoparticles were self-organized into the parallel lines of 20-50 m in length. In addition, the cytotoxicity evaluation revealed that Ni/Au alloy nanoparticles had lower cytotoxic activity than Ni nanoparticles. The related actors and mechanism need further investigations. Moreover, in this study, the Au nano-shells with various thicknesses were coated on the surface of Ni3Au1 alloy nanoparticles to yield a core-shell structure. Their composition, size, structure, and optical properties were also investigated.

    中文摘要 ………………………………………………………………… Ⅰ 英文摘要 ………………………………………………………………… Ⅱ 誌謝 ……………………………………………………………………… Ⅳ 總目錄 …………………………………………………………………… Ⅴ 表目錄 …………………………………………………………………… Ⅷ 圖目錄 …………………………………………………………………… Ⅸ 第一章 緒論 …………………………………………………………… 1 1.1 奈米材料與奈米技術 ……………………………………………… 1 1.1.1 前言 ……………………………………………………………… 1 1.1.2 奈米材料之特性 ………………………………………………… 3 1.1.3 奈米材料之製備 ………………………………………………… 6 1.2 金屬奈米粒子及合金型複合奈米粒子 …………………………… 11 1.2.1 金屬奈米粒子 …………………………………………………… 11 1.2.2 合金型複合奈米粒子 …………………………………………… 14 1.2.3 奈米材料之應用 ………………………………………………… 18 1.3 研究動機與內容 …………………………………………………… 20 第二章 理論部分 ……………………………………………………… 21 2.1 微乳化系統介紹 …………………………………………………… 21 2.1.1 前言 ……………………………………………………………… 21 2.1.2 正微胞、逆微胞與微乳化 ……………………………………… 21 2.1.3 逆微胞技術之應用 ……………………………………………… 29 2.1.4 逆微胞的優點 …………………………………………………… 32 2.2 磁性理論 …………………………………………………………… 33 2.2.1 磁性物質的種類 ………………………………………………… 33 2.2.2 磁性體與磁滯曲線之簡介 ……………………………………… 35 2.2.3 粒徑與磁性、磁區之關係……………………………………… 37 2.2.4 奈米微粒之磁性 ………………………………………………… 41 第三章 實驗部分 ……………………………………………………… 47 3.1 藥品、儀器與材料 ………………………………………………… 47 3.1.1 藥品與材料 ……………………………………………………… 47 3.1.2 儀器 ……………………………………………………………… 48 3.2 鎳金合金奈米粒子之製備 ………………………………………… 50 3.3 鎳金合金奈米粒子之磁自組 ……………………………………… 51 3.4 Ni3Au1@Au核-殼型奈米粒子之製備 ……………………………… 51 3.5 特性分析 …………………………………………………………… 54 第四章 結果與討論 …………………………………………………… 56 4.1 鎳金合金奈米粒子之合成與特性 ………………………………… 56 4.1.1 反應穩定時間 …………………………………………………… 56 4.1.2 粒徑分析 ………………………………………………………… 59 4.1.3 光學分析 ………………………………………………………… 61 4.1.4 結構分析 ………………………………………………………… 62 4.1.5 組成分析 ………………………………………………………… 66 4.1.6 磁性分析 ………………………………………………………… 69 4.1.7 粒子磁自組行為 ………………………………………………… 79 4.1.8生物毒性分析 …………………………………………………… 82 4.2 Ni3Au1@Au核-殼型奈米粒子之特性分析 ………………………… 83 4.2.1 粒徑分析 ………………………………………………………… 83 4.2.2 組成分析 ………………………………………………………… 83 4.2.3 光學分析 ………………………………………………………… 85 4.2.4 結構分析 ………………………………………………………… 85 第五章 結論 …………………………………………………………… 88 參考文獻 ………………………………………………………………… 90 附錄 ……………………………………………………………………… 95 自述 ……………………………………………………………………… 98

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