摘 要
在骨外科手術上金屬是經常被使用的人造材料。但是放置在生理環境下時，金屬離子會自然釋出，對身體局部區域和整個系統組織造成傷害。鈦金屬和其合金，在空氣中表面會自發性地產生一層由Anatase相或Rutile相組成的TiO2鈍化膜，所以離子釋出比其他金屬少。過去的文獻報導，將試片經過硝酸鈍化處理過後，在空氣中400℃持溫45分鐘，對防止離子釋出的效果非常好，其表面鈍化膜TiO2是較緊密的組態Rutile結構，因此被認為是防止離子釋出的因素。
然而離子釋出的改善也有可能是因為在高溫使得表面氧化膜厚度的增加造成。因此，本研究探討經硝酸鈍化處理試片，其相變化及厚度單獨改變，以及相變化與厚度同時改變對離子釋出的影響。實驗分二部分進行。第一部分的實驗中，利用穿透式電子顯微鏡（TEM）來觀察Ti-6Al-4V合金經400℃及700℃真空中以及25至400℃空氣中熱處理試片，表面鈍化膜的相變態，並以X光光電子光譜量測TiO2鈍化膜之厚度。第二部分為測試經真空中熱處理兩組分別為Rutile及Anatase相之試片的離子釋出情況；以及在空氣中各種溫度熱處理，使相同的Rutile相鈍化膜變厚，探討厚度對離子釋出的影響。
在本研究的實驗變數範圍內，顯示Rutile相TiO2鈍化膜是抑制Ti-6Al-4V合金金屬離子釋出的主要因素；增加鈍化膜厚度，對抑制金屬離子的釋出有次要的貢獻。同時控制TiO2鈍化膜之相組成及增加鈍化膜厚度將對於Ti-6Al-4V合金金屬離子的釋出產生加成效果。

Abstract
In orthopaedic surgeries, metals are often used, however, when placed in a physiological environment, metal ions are released with potentially harmful local and systematic effects. In application, a tenacious oxide film of TiO2 , formed spontaneously either as anatase or rutile phase on the surface of titanium and its alloys, will be conducive to the reduction of ion release. Previous study reported that a heat treatment at 400℃for 45 min of the nitric acid passivated Ti-6Al-4V alloy significantly reduced the ion release, however, the factor contributing to the improvement were uncertain.
The present research aimed to study the individual and combined effects of phase and thickness of TiO2 oxide film on the ion release of the Ti-6Al-4V alloy. In part I of the experiments, TEM was used to examine the phase of oxide film of the 33﹪nitric acid passivated material vacuum heat treated at 400℃and 700℃, or air heat treated from 25℃to 400℃. Also, XPS method was employed to measure the thickness of the oxide film. In part II of the experiments, ion release of the differently treated materials was measured by ICP analysis. Within the experimental range studied, the study indicated that the rutile phase of TiO2 on the surface of passivated Ti-6Al-4V plays a major role, while the thickness of oxide is secondary, in contributing to the repress ion of ion release in a physiological environment. Simultaneous controls of phase and thickness of TiO2 oxide will additively contribute to the reduction of ion release.

目錄
中文摘要************************..I
英文摘要************************.II
目錄**************************III
表目錄*************************VII
圖目錄*************..**..******.***IX
第一章 前言*********************..*..1
第二章 理論與文獻回顧****************.*..4
2-1 Anatase-Rutile相變化***************.*4
2-1-1以熱力學角度探討 Anatase-Rutile相變化****.*4
2-1-2壓力對Anatase-Rutile相變化的影響**..*****5
2-1-3 Anatase-Rutile相變化的動力學及機制******...6
2-2 本實驗的理論架構*****************..8
第三章 實驗內容與方法*****************.10
3-1 TiO2氧化膜相變態研究************..**..11
3-1-1 TEM前驅試片硝酸鈍化處理..******..***11
3-1-2 TEM前驅試片熱處理..******.******..12
3-1-3 TEM試片製作及觀察*************.14
3-2 表面TiO2氧化膜厚度量測研究.**..*********15
3-2-1膜厚研究試片硝酸鈍化處理**...*******..15
3-2-2膜厚研究試片熱處理*************..16
3-2-3 XPS分析*************..*****17
3-3 離子釋出實驗*******************17
3-3-1離子釋出實驗試片硝酸鈍化處理********..18
3-3-2離子釋出實驗試片熱處理***********..18
3-3-3浸泡模擬體液****************..19
3-3-4測試離子釋出****************..19
第四章 實驗結果********************..21
4-1 TiO2薄膜之相變態研究***************21
4-1-1硝酸鈍化處理TEM試片****.*******..21
4-1-2真空中熱處理試片**************.21
4-1-3空氣中熱處理試片**************.22
4-2 TiO2薄膜之膜厚研究****************25
4-3 離子釋出實驗*******************25
4-3-1表面氧化膜TiO2相組成對離子釋出的影響**..*..25
4-3-2表面氧化膜TiO2厚度對離子釋出的影響**..**..26
4-3-3表面氧化膜TiO2相組成及厚度同時改變對離子釋出的影響.********************.26
第五章 討論**********************..27
5-1 A25試片中為何不存在Anatase相**********..27
5-2 表面氧化膜中的TiO、Ti2O3 Suboxides*.******. .27
5-3 實驗架構的修正*****************..31
5-4 V400為Anatase相的原因*************..30
5-4-1 熱力學的解釋**************..*32
5-4-2 本論文的觀點***************..33
5-5 離子釋出********************..55
5-5-1 TiO、Ti2O3化合物對離子釋出的影響*****38
5-5-2 表面氧化膜TiO2Rutile相的結晶性對離子釋出的影響******.**************..39
第六章 結論**********************..40
參考文獻************************..41

參考文獻
〔1〕 G. Meachim, D. F. Williams, "Changes in non-osseous tissue adjacent to titanium implants.", J. Biomed. Mater. Res, Vol. 7, pp. 555-572, 1973.
〔2〕 P. Ducheyne, G. Williams, M. Martens, J. Helsen, "In-vivo metal ion release from porous titanium fiber material." J. Biomed. Mater. Res, Vol. 18, pp. 293-308, 1984.
〔3〕 J. L. Woodman, J. J. Jacibs, J. O. Galante, R. M. Urban, "Metal ion release from titanium based prosthetic segmental replacements of long bones in baboons: a long term study." J. Orthop. Res, I, pp. 421-430, 1984;.
〔4〕 D. N. S. Kerr, M. K. Ward. In: Sigel, Sigel A, eds., "Aluminium and its Role in Biology." Metal Ions in Biological Systems, New York and Basle: Dekker, Vol. 24, pp. 217, 1988.
〔5〕 H. Geber, S. M. Perren, In. M. Davis, ed. Evaluation of Biomaterials, Chichester, England: Wiley, pp. 307-314, 1980.
〔6〕 B. Kasemo and J. Lausmaa, "Surface science aspects on inorganic biomaterials." CRC Crit. Rev. Biocomp, Vol. 2, pp. 335-380 1986.
〔7〕 R. C. Weast, D. R. Lide, M. J. Astle, and W. H. Beyer, eds. CRC Handbook of Chemistry and Physics, 70th edition, CRC Press, Boca Raton, Florida, 1990.
〔8〕 G. Radegran, J. Lausmaa, L. Mattsson, U. Rolander, and B. Kasemo, "Preparation of ultra-thin oxide windows on titanium for TEM analysis." J. Electron Microscopy Technique, Vol. 9, PP. 99-106, 1991.
〔9〕 A. Wisbey, P. J. Gregson and L. M. Peter and M. Tuke, "Effect of surface treatment on the dissolution of titanium-based implant materials." Biomaterials, Vol. 12, July, 1991.
〔10〕 M. Browne and P. J Gregson, "Surface modification of titanium alloy implants." Biomaterials, Vol. 15, No. 11, 1994.
〔11〕 E. A. B. Effah, P. D. Bianco, and P. Ducheyne, "Crystal structure of the surface oxide layer on titanium and its changes arising from immersion" Journal of Biomedical Materials Research, Vol. 29, PP. 73-80, 1995.
〔12〕 Robert D. Shannon and Joseph A. Pask, "Kinetics of the Anatase-Rutile Transformation." Journal of The American Ceramic Society ,Vol. 48, No. 8, pp. 391-398, 1965 .
〔13〕 David R. Gaskell, Introduction to Metallurgical Thermodynamics, Second Edition, pp. 165-167 .
〔14〕 Yet-Ming Chiang, Dunbar Birnie III, W. David. Kingery, Physical Ceramics： Principles for Ceramic Science and Engineering, pp. 108-109, pp. 116, pp. 16, pp. 144, pp. 155.
〔15〕 E. S. Bumps, H. D. Kessler, and M. Hansen, Trans. Am. Soc. Metals, 45, 1013, 1954.
〔16〕 R. C. De Vries and Rustum Roy, Am. Ceram. Soc. Bull, Vol. 33,〔12 〕, pp. 370-372, 1954.
〔17〕 Krishnankutty-Nair P. Kumar, Scripta Metallurgica et Materialia, Vol.32, No. 6, pp. 873-877, 1995.
〔18〕 Neal R. Armstrong and Rod K. Quinn, Surface Science, Vol. 67, pp. 451-468, 1977.
〔19〕 Jukka Lausmaa, Bengt Kasemo, Applied Surface Science, Vol. 44, pp. 133-146, 1990.
〔20〕 C. D. Wagner, Faraday Discussions Chem. Soc, Vol. 60, pp. 291-298, 1975.
〔21〕 L. Porte, M. Demosthenous and Tran Minh Duc, J. Less Common Met, Vol. 56, pp. 183, 1977.
〔22〕 A. C. Fraker and A. W. Ruff, JR, Corrosion Science, Vol. 11, pp. 763-765, 1971.
〔23〕 J. W. Hickman and E. A. Gulbransen, Analytical Chemistry, Vol. 20, No. 2, February, pp. 158-165, 1948.
〔24〕 Denny A. Jones, Principles and Prevention of Corrosion, pp. 414.
〔25〕 W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics, Second Edition, pp. 897.
〔26〕 Relva C. Buchnan, Ceramic Materials for Electrons：Processing, Properties, and Applications, Second Edition, pp. 380.
〔27〕 Tzer-Ming Lee, Edward. Chang, Surface Characteristics and Biological Responses of Vacuum-Diffusion-Brazed Ti-6Al-4V, Department of Materials Science and Engineering National Cheng Kung University June, 1998, pp. 69.