臺灣博碩士論文加值系統

本研究分為三大部分：(1)利用低溫浸泡腐蝕方式，在Ti-6Al-4V 合金 (Ti-64)表面製備多孔性氧化層 (porous oxide layer; POL)；(2)表面機械加工及後續低溫浸泡腐蝕方式 (sand-blast, large grit and acid etched; SLA)，製備 Ti-64表面多孔性氧化層；(3)在腐蝕溶液中以電化學方式腐蝕，製備 Ti-64表面多孔性氧化層。本研究除了利用掃描式電子顯微術 (scanning electron microscopy; SEM)及表面輪廓儀 (α-step)分析POL表面形貌及表面粗糙度外，並利用拉曼光譜術 (Raman scattering spectroscopy; RSS)及洛氏硬度計 (HR15N)分析POL形成前後Ti-64表面結構及特性之變化情形。從中挑選出較具代表性之試片進行人類成骨細胞 (human osteoblast)貼附測試。結果發現：利用三種方法皆能在Ti-64表面製備出POL，但綜合所有測試數據與細胞貼附測試結果發現：以電化學方式腐蝕能得到最佳的多孔性氧化層與細胞貼附效果。希望能將此製程推廣應用於人工植牙之Ti-64牙根，預期在Ti-64牙根表面獲致加速骨整合之多孔性氧化層。

This study is divided into three parts：(1) Preparation of porous oxide layer (POL) on Ti-6Al-4V (Ti-64) surface by low temperature immerse corrosion. (2) Preparation of porous oxide layer on Ti-64 surface by SLA (sand blast, large grit and acid etched) process. (3) Preparation of porous oxide layer on Ti-64 surface by electrochemical corrodes in different etching solution. In this study, not only use of scanning electron microscopy (SEM) and α-step analysis POL surface topography and roughness, but also use of Raman spectroscopy and Rockwell hardness (HR15N) analysis before and after the formation of Ti-64 changes in surface structure and characteristics of the situation. Selected from the sample representative for human osteoblast adhesion test. The results showed that: Using three methods have received in the Ti-64 surface preparation of POL, but all test data and cell adhesion test results showed that: electrochemical corrosion can be the optimum preparation of porous oxide layer and the cell adhesion. Hope to promote this process applied to the Ti-64 dental implants, ,and the expected implant surface in the Ti-64 was caused by accelerated osseointegration of porous oxide layer.

摘要 V
Abstract VI
目錄 VII
表目錄 IX
圖目錄 X
第一章 緒論 1
1.1前言 1
1.2研究目的 2
第二章 理論基礎與文獻回顧 3
2.1生物醫用金屬材料簡介 3
2.2鈦合金分類 4
2.2.1 α型鈦合金 4
2.2.2 α-β型鈦合金 5
2.2.3 β型鈦合金 6
2.3鈦合金表面機械加工處理 6
2.4腐蝕與電化學之關係 9
2.5表面粗度與細胞貼附 10
第三章 實驗方法與流程 12
3.1 實驗藥品 12
3.2實驗方法與實驗流程 13
3.2.1試片製備 13
3.2.2電化學腐蝕 14
3.2.3腐蝕液製備 15
3.2.4實驗流程 19
3.3實驗儀器 20
3.3.1金相光學顯微鏡 (Metallographic Optical Microscopy) 20
3.3.2掃描式電子顯微鏡 (Scanning Electron Microscopy) 21
3.3.3拉曼散射光譜儀 (Raman Scattering Spectrometer) 22
3.3.4薄膜厚度輪廓測度儀 (α-step) 23
3.3.5 Rockwell硬度試驗機 (Rockwell Hardness Test) 24
3.3.6冷卻循環水槽 (Recirculating chillers) 25
3.3.7細胞貼附測試 26
第四章 結果與討論 27
4.1表面粗糙度與表面形貌變化 27
4.1.1浸泡腐蝕與噴砂後浸泡腐蝕 27
4.1.2珠擊後浸泡腐蝕 33
4.1.3電化學腐蝕 36
4.2表面硬度變化 46
4.3表面結構變化 47
4.4細胞貼附成果 57
第五章 結論 60
第六章 參考文獻 61

1.W. F. Smith, Structure and Properties of Engineering Alloy, 1st ed., McGraw-Hill Books Company, N.Y., pp. 411-457., 1981.
2.H. Kimura, O.Izumi, eds., Titanium’80 Science and Technology, Proc. 4th International Conference on Titanium, Kyoto, Japan, May 19-22, pp. 2205-2330, 1980.
3.F. H. Froes, I. L. Caplan, eds., Titanium’92 Science and Technology, Proc. 7th World Titanium Conference, San Diego, USA, June 29-July 2, pp. 793-956, 1992.
4.B. Gong, C. B. Zhang, Z. H. Lai, Improvement of Superplastic Properties of Ti-6Al-4V Alloy by Temporary Alloying with Hydrogen, J.Mater. Sci. Let., vol. 13, pp. 1561-1563, 1994.
5.P. Allen, Advanced Materials and Processes, Vol. 150, No. 4, pp. 35-37, 1996.
6.T. I. Wu, C. T. Liu and J. K. Wu, The Use of Thiourea to Inhibit Hydrogen Incorporation in Titanium and Ti-6Al-4V Alloy, Materials Letters, Vol.30, pp.377-383, 1997.
7.R. G. Vogt, F. H. Froes, D. Eylon and L. Levin, in Titanium Net Shape Technologies, TMS. Warrendale, PA, pp.145-153, 1984.
8.W. H. Kao, D. Eylon, C. F. Yolton and F. H. Froes, Progress in, Powder Metallurgy Vol.37, J. M. Capus and D. L. Dyke eds., MPIF, Princeton, NJ, pp.289-301, 1982.
9.張正中，「鈦合金動物實驗研究」，碩士論文，國立成功大學材料科學及工程研究所，2004.
10.T. Akahori and M. Niinomi, Fracture Characteristics of Fatigued Ti-6Al-4V ELI as an Implant Material, MSE, A243 pp.237-243, 1998.
11.L. L. Guehennec, A.Soueidan, P. Layrolle, Y. Amouriq, Surface treatments of titanium dental implants for rapid osseointegration, DENTAL MATERIALS, 23 pp.844-854, 2007
12.S. A. Cho, K. T. Park, The removal torque of titanium screw inserted in rabbit tibia treated by dual acid etching, Biomaterials, 24 pp.3611-3617, 2003.
13.劉宜勇, 生物醫用鈦材料及其表面改性, 化學工業出版社, 2009.
14.E. K. Molchanova, Phase diagrams of titanium alloys transl. of Atlasdiagram sostoyaniya titanovyk splavov, Israel program for scientifictranslations, Jerusalem, 1965.
15.D. L. Cochran, R. K. Schenk, A. Lussi, F. L. Higginbottom, D. Buser, Bone response to unloaded and loaded titanium implants with a sandblasted and acid-etched surface: a histometric study in the canine mandible. J Biomed Mater Res, 40:1–11, 1998.
16.A. Wennerberg, C. Hallgren, C. Johansson, S. Danelli, A histomorphometric evaluation of screw-shaped implants each prepared with two surface roughnesses, Clin Oral Implants Res 9:11–9,1998.
17.T. Testori, L. Wiseman, S. Woolfe, S. Porter, A prospective multicenter clinical study of the Osseotite implant: four-year interim report, Int J Oral Maxillofac Implants, 16:193–200, 2001.
18.K. Conner, R. Sabatini, B. Mealey, V. Takacks, M. Mills, D. Cochran, Guided bone regeneration around titanium plasma-sprayed, acid-etched and hydroxyapatite-coated implants in the canine model, J Periodontol, 74:658–68, 2003.
19.S. Hansson, M. Norton, The relation between surface roughness and interfacial shear strength for bone-anchored implants, A mathematical model, J Biomech,32:829–36, 1999.
20.田福助, 電化學-理論與應用, 新科技書局, 2004.
21.S. Ramya, R. P. George, R. V. Subba Rao, R. K. Dayal, Detection of algae and bacterial biofilms formed on titanium surfaces using micro-Raman analysis, Applied Surface Science, 2010.
22.J. Yang, S. Mei ,Jose M. F. Ferreira, P. Norby, S. Quaresma, Fabrication of rutile rod-like particle by hydrothermal method:an insight into HNO3 peptization, 2005.
23.H. W. Kim, H. S. Kim, H. G. Na, J. C. Yang, D. Y. Kim, Growth, structural, Raman, and photoluminescence properties of rutile TiO2 nanowires synthesized by the simple thermal treatment, Journal of Alloys and Compounds 504 pp. 217–223, 2010.
24.S. Ma‥ndl , G.Thorwarth, M. Schreck, B. Stritzker, B. Rauschenbach, Raman study of titanium oxide layers produced with plasma immersion ion implantation, Surface and Coatings Technology 125 pp.84–88, 2000.
25.T. Bezrodna, T. Gavrilko, G. Puchkovska, V. Shimanovska, J. Baran ,M. Marchewka, Spectroscopic study of TiO2 (rutile) benzophenone heterogeneous systems, Journal of Molecular Structure 614 pp.315–324, 2002.
26.R. J. Betsch, H. L. Park, and W. B. White, Raman spectra of stoichiometric and defect rutile, Mat. Res. Bull., Vol.26, pp.613-622, 1991.
27.J.F. Mammone, S.K. Sharma, Raman study of rutile (TiO2) at high pressures,Solid State Communications, Vol. 34, pp.799-802,1980.
28.J. Kunze, A. Seyeux, P. Schmuki, Anodic TiO2 layer conversion: fluoride-induced rutile formation at room temperature, Electrochemical and Solid-State Letters 11,2K11-K13,2008.
29.T. L. Villarreal , J. M. Pérez, R. Gómez, Adsorption studies on titanium dioxide by means of Raman spectroscopy, C. R. Chimie 9 806-816, 2006.
30.J. M. Wu , B. Huang, Y. H. Zeng, Low-temperature deposition of anatase thin films on titanium substrates and their abilities to photodegrade Rhodamine B in water, Thin Solid Films 497 292-298, 2006.