微奈米多孔陣列二氧化鈦薄膜之製程探討與應用研究

Synthesis and applications of porous nano TiO2 array on titanium substrate

蔡馨惠(Shin-Hui Tsai)

指導教授 ： 楊永欽

國立臺北科技大學/工程學院/材料科學與工程研究所/碩士(2012年)

摘要

本研究中分成三個部份討論，第一部分為利用自組合成反應(Evaporation Induced Self Assembly)於鈦基板上合成中孔洞二氧化鈦薄膜，以三嵌段共聚塊界面活性劑產生之微胞作為模板，形成有機之自組裝體，以旋轉塗佈(spin-coating)於鈦基板上形成三維中孔洞結構之二氧化鈦薄膜；藉由有機界面活性劑(P123)與無機前趨物(TBOT)的含量改變對於孔洞形成的影響，熟化時間變化影響孔洞狀態和煆燒溫度作用下探討孔洞規則性。實驗結果顯示在熟化時間48小時，煆燒溫度250°C，對於中孔洞二氧化鈦長程序化之排列明顯提升；當P123/TBOT莫耳比為0.6，由SEM分析所形成二氧化鈦薄膜具有二維垂直通道之中孔洞形態，透過TEM觀察二氧化鈦薄膜橫截面明顯看到中孔洞之橫條紋；當莫耳比增加到0.9時(具有平行奈米通道之中孔洞二氧化鈦薄膜)，TEM影像呈現為二維六方堆積排列中孔洞結構，透過電子繞射圖譜(Electron Diffraction patteren)證明莫耳比0.6和莫耳比0.9皆為多晶形態。
第二部分主要為體外試驗(in vitro)之分析，實驗結果顯示試片經由3天到28天之模擬體液浸泡，具有平行通道之二氧化鈦薄膜較佳氫氧基磷灰石骨生長之能力。第三部分利用水熱法於試片表面成長氫氧基磷灰石，實驗結果顯示於表面披覆二氧化鈦薄膜對於成長球狀六方晶氫氧基磷灰石有較佳成核能力。

關鍵字

中孔洞 ； 二氧化鈦 ； 氫氧基磷灰石

並列摘要

In this study, we have three topics to discuss. First part is the preparation of mesoporous TiO2 was based on an evaporation induced self assembly (EISA) method using the Pluronic P123 as the structure-directing agent and the TBOT as the titanium source. Then,the three dimensional mesoporous titania thin film was prepared on the Ti substrate by the spin coating. A study amount on the basis of the interactions between inorganic-organic to form meso-structured composites.The reaction temperature is relatively order of mesostructure.The pore condition of mesoporous materials depend on the temperature changing of a micells. The result showns that aging time for 48 hrs and calcined at 250°C to synthesis the long range ordered mesoporous TiO2. By the SEM analysis, the ratio of P123/TBOT was 0.6 with two dimensional vertical channel shapes. And the TEM observation, it can clearly see the horizontal stripes by TiO2 thin film cross-section.When P123/TBOT was 0.9 (mesoporous TiO2 thin film with parallel channel), these results were confirmed by TEM, it reveals 2D-hexagonal arrangement mesoporous structure. And the electron diffraction patterns shows that the molar ratio of 0.6 and 0.9 are polycrystal.
Second part is in vitro bioactivity appraisement. The results shown that apatite was formed on the coating surface after immersion in simulated body fluid for 3 days to 28 days which indicates that the mesoporous film has the potential to chemical bonding with bone tissue.
Third part major discusses three parameters (mesoporous TiO2 thin film with vertical channel, parallel channel and pure titanium) to grow hydroxyapatite by hydrothermal method. The result shows that parallel channel mesoporous TiO2 thin film has better nucleation potential to grow hexagonal hydroxyapatite.

並列關鍵字

Mesoporous ； TiO2 ； Hydroxyapatite

參考文獻

[1]鄭信忠，陳長志，謝家倫，蔡明宏，歐耿良，李勝揚，施永勳，鈦基植體表面生成奈米多孔性二氧化鈦層之機制研究，中華牙誌，2007，第26期，26–32

[2]鄭信忠，詹宗瑾，李勝揚，林哲堂，歐耿良，經電化學處理之鈦金屬表面奈米多孔性氧化層之研究，中華牙誌，2006，第25期，96–102

[3]吳玉祥，黃建瑋，水熱法合成氫氧基磷灰石之鈣磷比研究，中華科技大學學報，2010，第45期，1–14

[33]賴映竹，具垂直通道之中孔洞氧化矽薄膜製備於基板與其性質研究，臺灣大學，化學研究所，99

[5]Yuan-Yuan Zhang, Jie Tao, Ying-Chun Pang, Wei Wang, Tao Wang, “Electrochemical deposition of hydroxyapatite coatings on titanium”, Trans. Nonferrous Met. SOC. China , 2006, 16, 633–637