臺灣博碩士論文加值系統

由於鈦具有優異的生物相容性，因此可作為理想的人工義齒基材。目前於鈦表面噴砂後燒附陶瓷，金屬與陶瓷的鍵結強度未臻理想，使得純鈦於牙科臨床應用始終令人擔憂。本研究旨在評估陽極氧化表面處理對商業用純鈦金屬與牙科陶瓷結合性質之影響。研究過程選用商業用純鈦(c.p.Ti)為基材，其表面經矽砂紙研磨後，試片依不同的表面處理方式分成四個組別：未處理(UT組)、陽極氧化處理(AT組)、噴砂處理(ST組)及噴砂後再陽極氧化處理(SAT組)。表面處理後的所有試片，使用掃描式電子顯微鏡(SEM)觀察其表面形貌特徵，以粗度計測量其表面粗糙度，並以X光光電子能譜儀(XPS)分析表面的化學物質。之後再將純鈦專用之超低溫瓷粉燒附於處理後的金屬表面，以能量散射光譜儀(EDS)分析金屬與陶瓷結合界面之元素擴散情形，並以萬能試驗機做三點彎曲測試測量金屬與陶瓷的鍵結強度。三點彎曲試驗後之金屬試片與陶瓷的破斷面以場發射掃描式電子顯微鏡觀察其形貌，使用能量散射光譜儀(EDS)以點方式分析破斷面殘留之元素成分，並以面分析方式對試片表面陶瓷殘留量進行定量分析，比對金屬與陶瓷的鍵結強度。
實驗結果顯示：純鈦金屬經過不同表面處理後，噴砂再陽極氧化處理(SAT組)的表面粗糙度值1.79 µm為最大；噴砂再陽極氧化處理(SAT組)後燒附牙科陶瓷的試片，可測得的金屬與陶瓷鍵結強度47.7 MPa為ISO 9693所規範之最低數值25 MPa 的1.88倍。所有經三點彎曲測試後之純鈦金屬試片的破斷面均發現陶瓷殘留，在陶瓷的破斷面則有鈦金屬殘留，破斷的位置都出現在純鈦金屬與陶瓷的結合界面處且呈現出貼附及黏附混合斷裂型態。最後將本研究之實驗結果實際應用於臨床牙冠(Crown)的製作，以噴砂後再陽極氧化乃純鈦金屬燒附陶瓷最佳化的表面處理方式，此研究結果將可提供日後牙科用鈦金屬研發的參考依據。

With its superior biocompatibility, titanium has become an ideal material for artificial dental application. The bonding strength between metal and porcelain is not enough using current technology, in which porcelain is sintered on the sandblasted titanium surface, which makes the application of pure titanium in dentistry a disconcerting matter. The aim of present study is to assess the effects of anodic oxidation on the bonding properties between commercially pure titanium (c. p. Ti) and dental porcelain. After the surface was grinded with silica sand, the specimens were divided into four groups based on different surface treatment methods: untreated (UT) group, anodic oxidation treatment (AT) group, sandblast treatment (ST) group, and anodic oxidation treatment after sandblasting (SAT) group. Scanning electronic microscope (SEM) was used to observe the surface features and the characteristics of all surface treated specimens. The surface roughness is measured with a surface roughness measuring instrument, and the chemical composition on the surface was analyzed using the X-ray photoelectron spectrometer (XPS). Ultra-low fusing porcelain was then fused on the treated surface of c.p. Ti. Energy dispersive spectrometer (EDS) was used to analyze the element diffusion on the bonding interface between metal and porcelain. The bonding strength between the metal and the porcelain was measured by three-point bending test using a universal testing machine. The features on the fractured section of the metal specimen and the porcelain that endured three-point bending test were observed using a field emission scanning electron microscope. The residual elements on the fractured surface were analyzed with EDS, and quantitative analysis for the amount of porcelain residue remained on the surface of the specimen was conducted using surface analysis method in order to compare the metal and the porcelain bonding strengths. The results showed that: the surface roughness measurement of the SAT group at 1.79 µm, was the greatest among the different surface treated pure titanium specimens. The metal and porcelain bonding strength of the specimen fused with dental porcelain in SAT group was 47.7 MPa, which was 1.88 times greater than 25 MPa specified by ISO 9693. Porcelain residues were found in the fractured surfaces of all pure titanium specimens after measuring the three-point bending test, while titanium residues were found in the fractured surfaces of porcelain. The location of the fractures was found to be in the bonding interface between pure titanium and porcelain, exhibiting mixed fracture pattern of both cohesion and adhesion failures. Finally, the present study has applied the results in the manufacturing of clinical crown, demonstrating that anodic oxidation treatment after sandblasting is the best surface treatment for porcelain fusing to c.p.Ti. The results from the present study may be used as a reference for the research and development of dental titanium in the future.

中文摘要 I
AbstractIII
總目錄 V
圖目錄 IX
表目錄 XIII
第一章 前言 1
1-1 研究動機 1
1-2 研究目的 5
第二章 文獻回顧 7
2-1 生醫材料 7
2-2 牙科用合金 9
2-3 鈦 10
2-4 牙科陶瓷 13
2-5 噴砂 15
2-6 陽極氧化 17
2-7 金屬與陶瓷嵌合 20
2-8傳統陶瓷融合金屬牙冠 22
2-9 電腦輔助設計/製造純鈦基底冠製作技術(CAD/CAM技術) 24
第三章 材料與方法 26
3-1 實驗流程 26
3-2 試片製備及表面處理 27
3-3 陽極氧化表面處理 27
3-3-1 電解液製備 27
3-3-2 陽極氧化處理之參數 27
3-3-3 純鈦表面陽極氧化處理 28
3-4 噴砂處理 29
3-5 材料表面分析 29
3-5-1 形貌觀察 29
3-5-2 晶相分析 29
3-5-3 元素分析 30
3-5-4 粗糙度量測 30
3-5-5 水滴接觸角測試 30
3-6 陶瓷堆築 31
3-7 鍵結強度測試 32
3-8 金屬/陶瓷界面分析 33
3-9 金屬/陶瓷破斷面分析 34
3-10 臨床牙冠製作 34
第四章 結果與討論 37
4-1 晶相分析結果 37
4-2 表面形貌 38
4-3 表面粗糙度量測結果 39
4-4 水滴接觸角量測結果 41
4-5 表面化學成分分析結果 43
4-6 金屬/陶瓷橫截面影像 46
4-7 金屬/陶瓷鍵結強度測試結果 48
4-8 金屬/陶瓷破斷面型態與元素分析結果 49
4-9 破斷面元素定量分析 56
4-10臨床牙冠製作成品 57
第五章 結論 64
參考文獻 65
作者自述 73

[1] 中華民國生物醫學工程學會 2008。生物醫學工程導論。滄海書局。
[2] 蘇明德 2008。科學發展；426期：66-71。
[3] 中村正明，武田昭二，大島浩，藤崎照泰，福間正泰，中川正史。日本全國齒科技工士教育協議會齒科理工學。牙冠牙橋技術學。合記圖書出版社 2010。
[4] R.R. Wang, K.K. Fung. Oxidation behavior of surface-modified titanium for titanium-ceramic restoration. The Journal of Prosthetic Dentistry. 1997; 77:423-434.
[5] H. Kimura, C.J. Horng, M. Okazaki, J. Takahashi. Oxidation effect on porcelain-titanium interface reactions and bond strength. Dental materials Journal. 1990; 9: 91-99.
[6] M. Adachi, J.R. Mackert , E.E. Parry,C.W. Fairhurst. Oxide adherence and porcelain bonding to titanium and Ti-6Al-4V alloy. Journal of Dental Research. 1990; 69: 1230-1235.
[7] H. Yilmaz, C. Dincer. Comparison of the bond compatibility of titanium and an NiCr alloy to dental porcelain. Journal of Dentistry. 1999; 27: 215-222.
[8] S. Atsü, S. Berksum. Bond strength of three porcelain to two forms of titanium using two firing atmospheres. The Journal of Prosthetic Dentistry. 2000; 84: 567-574.
[9] Clemson University Advisory Board for Biomaterials. Definition of the word biomaterial. The 6th Animal International Biomaterial Symposium.
[10] J.B. park, R.S. Lakes. Biomaterials: an introduction. 2nd ed. Plenum press, New York 1992; 2-3
[11] 國立編譯館 2007。生物醫學材料。合記圖書出版社。
[12] O. Robinson, P. Ancientrome: City Planning and Administration London, New York, 1992.
[13] 謝成木 2005 。鈦及鈦合金鑄造。機械工業出版社。
[14] H. Klinkmann, H.W. Schmitt. Hemodialysis and membrane biocompatibility. Contr Nephrol. 1984; 37: 70-77.
[15] 柯賢文 2005。腐蝕及其防治。全華科技圖書股份有限公司。
[16] 黃振賢 1994。機械材料。文經圖書有限公司。
[17] 方立陞 2011。三元 Ti-5Cr-9Mo 於牙科應用之研究。中台科技大學；醫學工程暨材料研究所。
[18] 中村正明，武田昭二，大島浩，藤崎照泰，福間正泰，中川正史。日本全國齒科技工士教育協議會齒科理工學。牙科材料學。合記圖書出版社2010。
[19] J.R. Mackert, E.E. Parry, C.W. Fairhurst. Oxide morphology and adherence on dental alloys designed for porcelain bonding. Oxidation of Metals. 1986; 25: 319-333.
[20] W.A. Brantel, Z. Cai, E. Papazoglou, J.C. Mitchell, S.J. Kerber, G.P. Mann, et al. X-ray diffraction studies of oxidized high-palladium alloys. Dental Materials. 1996; 12: 333-341.
[21] B. Della, R.V. Noort. Ceramic surface preparations for resin bonding. American Journal of Dentistry. 1998; 11(6): 276-280.
[22] I. Nergiz, P. Schmage, W. Herrmann, M. zcan. Effect of alloy type and surface conditioning on roughness and bond strength of metal brackets. American Journal of Orthodontics and Dental facial Orthopedics. 2002; 125(1): 42-50.
[23] B. Della, R. Van Noort. Ceramic surface preparations for resin bonding. American Journal of Dentistry. 1998; 11(6): 276-280.
[24] M.B. Blatz, A. Sadan, M. Kern. Resin-ceramic bonding: a review of the literature. J Prosthet Dent. 2003; 89(3): 268-274.
[25] M.F. Ayad, N.Z. Fahmy, S.F. Rosenstiel. Effect of surface treatment on roughness and bond strength of a heat-pressed ceramic. Journal of Prosthetic Dentistry. 2008; 99(2): 123-130
[26] V. Bacuova, D. Draganovska. Analyses of the quality of blasted surfaces. Materials Science. 2004; 40(1): 125-131.
[27] S. Bouzid, N. Bouaouadja. Effect of impact angle on glass surfaces eroded by sand blasting. Journal of the European Ceramic Society. 2000; 20(4): 481-488.
[28] D.S. Park, M.W. Cho, H. Lee. Effects of the impact angle variations on the erosion rate of glass in powder blas ting process. International Journal of Advanced Manufacturing Technology. 2004; 23(5-6): 444-450.
[29] D.V. De Pellegrin, G.W. Stachowiak. Simulation of three-dimensional abrasive particles. Wear 2005; 258(1-4 SPEC. ISS.): 208-216.
[30] Y.I. Oka, K. Okamura , T. Yoshida. Practical estimation of erosion damage caused by solid particle impact: Part 1:Effects of impact parameters on a predictive equation. Wear 2005; 259(1-6): 95-101.
[31] Y.I Oka, H. Ohnogi, T. Hosokawa, M. Matsumura. The impact angle dependence of erosion damage caused by solid particle impact. Wear. 1997; 203-204: 573-579.
[32] Y.I. Oka, T. Yoshida. Practical estimation of erosion damage caused by solid particle impact: Part 2: Mechanical properties of materials directly associated with erosion damage. Wear 2005; 259(1-6): 102-109.
[33] C. Kajdas. Importance of the triboemission process for tribochemical reaction. Tribology International. 2005; 38(3): 337-353.
[34] T.T Heikkinen, L.V.J. Lassila, J.P. Matinlinna, P.K. Vallittu. Effect of operating air pressure on tribochemical silica-coating. Acta Odontologica Scandinavica. 2007; 65(4): 241-248.
[35] J.A. Hautaniemi, J.T. Juhanoja, H. Herø. Porcelain bonding on Ti: Its dependence on surface roughness, firing time and vacuum level. Surface and Interface Analysis. 1993; 20: 421-426.
[36] M. Könönen, J. Kivilahti. Bonding of low-fusing dental porcelain to commercially pure titanium. Journal of Biomedical Materials Research. 1994; 28: 1027-1035.
[37] T. Dérand, H. Herø. Bond strength of porcelain on cast vs. wrought titanium. European Journal of Oral Sciences. 1992; 100:184-188.
[38] J.L. Gilbert, D.A. Covey, E.P. Lautenschlager. Bond characteristics of porcelain fused to milled titanium. Dental Materials. 1994; 10: 134-140.
[39] O. Miyakawa, K. Watanabe, S. Okawa, M. Kanatani, S. Nakano, M. Kobayashi. Surface contamination of titanium by abrading treatment. Dental Materials Journal. 1996; 15: 11-21.
[40] B.W. Darvell, N. Samman, W.K. Luk, R.K.F. Clark, H. Tideman. Contamination of titanium casting by aluminium oxide blasting. Journal of Dentistry.1995; 23: 319-322.
[41] 胡啟章2002。電化學原理與方法。五南書局。
[42] Bengogh, Stuart, British Patent 223,994, 1923.
[43] F. Keller, M.S. Hunter, D.L. Robinson. Structural features of oxide coatings on aluminum. Journal of the Electrochemical Society. 1953; 100: 411–419.
[44] J.P. O'Sullivan and, G.C. Wood. The Morphology and Mechanism of Formation of Porous Anodic Films on Aluminum. Proceedings of the Royal Society of London. Series A, Mathematical and Physical, 1970.
[45] G.E. Thompson, G.C. Wood. Porous anodic film formation on aluminum. Nature. 1981; 290: 230-232.
[46] G.E. Thompson, G.C. Wood. Corrosion: Aqueous Process and passive films. Treaties on Materials Science and Technology 23. Chap.5, Academic Press Inc. London. 1983; 206.
[47] V.P. Parkhutik, V.I. Shershulsky. Theoretical modelling of porous oxide growth on aluminium. Journal of Physics D: Applied Physics. 1992; 25: 1258-1263.
[48] H. Masuda. K. Fukuda. Ordered metal nanohole arrays made by a two-step replication of honeycomb structures of anodic alumina. Science. 1995; 268: 1466-1468.
[49] A.P. Li, F. Mu¨ ller, A. Birner, K. Nielsch, U. Go¨sele. Hexagonal pore arrays with a 50–420nm interpore distance formed by self-organization in anodic alumina. Journal of Applied Physics. 1988; 84: 6023-6026.
[50] O. Jessensky, F. Mu¨ ller, U. Go¨sele. Self- organized formation of hexagonal pore arrays in anodic alumina. Applied Physics letters. 1988; 72: 1173-1175.
[51] A.P. Li, F. Mu¨ ller, A. Birner, K. Nielsch, U. Go¨sele. Polycrystalline nanopore arrays with hexagonal ordering on aluminum. The Journal of Vacuum Science and Technology A.1999; 17: 1428-1431.
[52] H. Masuda, M. Yotsuya, M. Asano, K. Nishio. Self-repair of ordered pattern of nanometer dimensions based on self-compensation properties of anodic porous alumina. Applied Physics Letters. 2001; 78: 826-828.
[53] N.Q. Zhao, X.X. Jiang, C.S. Shi, J.J. Li, Z.G. Zhao, X.W. Du. Effects of anodizing conditions on anodic alumina structure. Journal of Materials Science. 2007 ; 42: 3878-3882.
[54] V. Zwilling, M. Aucouturier, E. Darque-Ceretti. Anodic oxidation of titanium and TA6V alloy in chromic media：An electrochemical approach. Electrochimica Acta. 1999; 45: 921-9329.
[55] D. Gong, C.A. Grimes, O.K. Varghese, W. Hu, R.S. Singh, Z. Chen, E.C. Dickey. Titanium oxide nanotube arrays prepare by anodic oxidation. Material Research Society. 2001; 16: 3331-3334.
[56] M.G. Troia, G.E. Henriques, M.F. Mesquita, W.S. Fragoso. The effect of surface modifications on titanium to enable titanium-porcelain bonding. Dental Materials. 2008; 24: 28-33.
[57] Y. Tanaka, I. Watanabe, T. Okabe. Cross-sectional TEM analysis of porcelain fused to gold-coated titanium. Dental Materials Journal. 2007; 26: 84-88.
[58] M.K. Lee, Z. Cai, J.A. Griggs, L. Guiatas, D.J. Lee, T. Okabe. SEM/EDS evaluation of porcelain adherence to gold-coated cast titanium. Journal of Biomedical Materials Research. Part B, Applied Biomaterials. 2004; 68: 165-173.
[59] E. Miura, T. Tabaru, J. Liu, Y. Tanaka, T. Shiraish, K. Hisatsune. Effect of gold coating on interfacial reaction between dental porcelain and titanium. Materials Transactions. 2004; 45: 3044-3049.
[60] S. Zinelis, X. Barmpagadaki, V. Vergos, M. Chakmakchi, G. Eliades. Bond strength and interfacial characterization of eight low fusing procelains to cp Ti. Dental Materials. 2010; 26: 264-273.
[61] L.L. Hench, R.J. Splinter, W.C. Allen, T.K. Greenlee. Bonding mechanisms at the interface of ceramic prosthetic materials. Journal of Biomedical Materials Research. 1971; 5: 117-141.
[62] F.J. Knap, G. Ryge. Study of Bond Strength of Dental Porcelain Fused to Metal. Journal of Dental Research. 1966; 45: 1047-1051.
[63] G.R. Markert, R.D. Ringle, E.E. Parry, A.L. Evans, C.W. Fairhurst. The Relationship Between Oxide Adherence and Porcelain-Mental Bonding. Journal of Dental Research. 1988; 67: 474-478.
[64] J.M. Carter, J. Al-Mudafar, S.E. Soresen. Adherence of a nickel-chromium alloy and porcelain. The Journal of Prosthetic Dentistry. 1979; 41: 167-172.
[65] J.E. Bowers, S.G. Vermilyea, W.H. Griswold. Effect of metal conditioners on porcelain-alloy bond strength. The Journal of Prosthetic Dentistry. 1985; 54: 201-203.
[66] 鍾國雄 2007。牙科材料學。合記圖書股份有限公司。
[67] W.F. Ho. A comparison of tensile properties and corrosion behavior of cast Ti-7.5Mo with c.p.Ti, Ti-15Mo and Ti-6Al-4V alloys. Journal of Alloys and Compounds. 2008; 464: 580-583.
[68] J.X. Li, Y.M. Zhang, Y. Han, Y.M. Zhao. Effects of micro-arc oxidation on bond strength of titanium to porcelain. Surface & Coatings Technology. 2010; 204: 1252–1258.
[69] C.W. Peng, T.Y. Ke, L. Brohan, M. Richard-Plouet, J.C. Huang, E. Puzenat, H.T. Chiu, C.Y. Lee. (101)-exposed Anatase TiO2 Nanosheets. Chem. Mater. 2008; 20: 2426-2429.
[70] W.C. Wagner, K. Asgar, W. Bigelow, R.A. Flinn. Effect of interfacial variables on metal-porcelain bonding. Journal of Biomedical Materials Research. 1993; 27(4): 531-537.
[71] Y. Wu, J. Moser, L.M. Jameson, W.F.P. Malone. The effect of oxidation heat treatment on porcelain bond strength in selected base metal alloys. The Journal of Prosthetic Dentistry. 1991; 66(4): 439-444.
[72] N. Suansuwan, M.V. Swain. Adhesion of porcelain to titanium and a titanium alloy. Journal of Dentistry. 2003; 31: 509-518.
[73] T. Dérand, H. Herø.Bond strength of porcelain on cast vs. wrought titanium. European Jouranl of Oral Sciences. 1992; 100(3): 184-188.
[74] A. Acar, ö. Ìnan, S. Halkaci. Effects of airborne-particle abrasion, sodium hydroxide anodization, and electrical discharge machining on porcelain adherence to cast commercially pure titanium. Journal of Biomedical Materials Research Part B: Applied Biomaterials.2007; 82(1): 267-274.
[75] M.G.T. Jr, G.E.P. Henriques, M.A.A. Nóbilo, M.F. Mesqutia. The effect of thermal cycling on the bond strength of low-fusing porcelain to commercially pure titanium and titanium-aluuminium-vanadium alloy. Dental Materials. 2003; 19: 790-796.