臺灣博碩士論文加值系統

本研究即在研究包埋鑄造法(Investment Cast)鑄造後製程中之化學銑製程序與鑄件之表面性質研究。 所用之包埋材料對鑄造鈦合金鑄件性質之影響，研究之包埋材料共有兩種：一為氧化鋯(Zirconia)，另一為鋯砂(Zircon)，結果發現以高溫穩定性較佳之Zirconia包埋材料所製成之鑄件具有較佳之表面性質，表面依鑄件厚度不同存有250-800μm厚之α相層。 鈦合金鑄件表層之α相層以化學蝕銑方式來去除，蝕銑溶液採用氫氟酸與硝酸為主之混合酸液，試以不同比例之氫氟酸與硝酸量分別來進行蝕銑工作，觀察其蝕銑速率與蝕銑後之表面，並測量蝕銑中所吸收的氫含量，以獲得較佳之蝕銑液成分比。 另外，以不同蝕銑操作條件，如溫度變化、攪拌及界面活性劑之添加等，取得較佳之蝕銑參數條件，以改善鑄件之表層性質，並提供應用至鈦合金鑄造之後製程加工作業。 最後，以直流極化掃描來研究鈦合金於氫氟酸-硝酸溶液之反應機構，了解氫氟酸與硝酸在反應中之作用，結果發現，所測得之電化學反應與浸漬於相同氫氟酸-硝酸混液內之化學溶解反應相符合，氫氟酸中添加硝酸溶液時，其反應速率會增加，當硝酸含量達一臨界值時，腐蝕電位會提高，使鈦合金較為鈍態。 將鈦合金浸漬於硫酸、磷酸、鹽酸及硝酸溶液中，研究鈦合金於極化過程中之表面性質，發現鈦合金具有良好之耐蝕性，在上述酸液中皆會生成氧化膜，其中以硫酸溶液之電荷轉移量最大，可推算其生成之膜厚最大，而隨硫酸濃度增加，其氧化膜厚度亦增厚。 而鈦合金置於含Cl-之鹽酸溶液時，外加電壓至 +5.85 V時，其會有腐蝕現象產生。

摘要 i
表目錄 iv
圖目錄 v
第一章 前言 1
第二章 文獻回顧 3
2.1 純鈦及鈦合金 3
2.1.1 純鈦之基本性質 3
2.1.1.1 鈦之物理性質 4
2.1.1.2 鈦之化學性質 4
2.1.2 鈦合金之基本性質 4
2.1.2.1 添加合金元素對鈦性質之影響 4
2.1.2.2 Ti-6Al-4V合金之特性 6
2.2 鈦合金鑄造簡介 8
2.2.1 鈦合金之鑄造技術 8
2.2.2 鈦合金鑄件之微結構與機械性質 11
2.2.3 鑄模材料與鑄件表面之反應 13
2.3 化學銑製 16
2.3.1 化學蝕銑簡介 16
2.3.2 鈦合金之化學蝕銑 16
2.3.3 氫破壞 17
2.4 鈦合金之耐蝕性質 19
第三章 理論背景 20
3.1 腐蝕與鈍化過程 20
3.2 氫對鈦合金之影響及擴散機制 21
第四章 實驗方法 26
4.1 鈦合金鑄造成型 26
4.2 鑄件斷面組成及元素分析 26
4.3 硬度測試 27
4.4 試片前處理 27
4.5 化學蝕銑 32
4.6 吸氫量測定 32
4.7 電化學試驗 32
第五章 實驗結果與討論 35
5.1 鈦合金之鑄造與鑄件分析 35
5.1.1 鈦合金鑄件鑄造 35
5.1.2 鑄件之微結構觀察 41
5.1.3 鑄件之機械性質 43
5.2鈦合金鑄件表層之氧化層蝕銑 52
5.2.1 蝕銑後之表面狀態 52
5.2.2 蝕銑中之問題與探討 70
5.2.2.1 鑄造體表面微裂縫問題 70
5.2.2.2 熱裂 76
5.2.2.3 鑄件形狀問題 80
5.2.2.4 蝕銑溫度之影響問題 81
5.2.2.5 添加界面活性劑對蝕銑之影響 81
5.2.2.6 化學蝕銑對操作人員與環境之影響 81
5.2.3 吸氫問題 82
5.3 鈦合金鑄件於氫氟酸-硝酸混液中之腐蝕行為 91
5.4 鈦合金之表面性質 110
第六章 結 論 125
參考文獻 126

1.Okazaki Yoshimitsu, Kyo Kenji, Ito Yoshimasa, and Tateishi
Tetsuya, “Corrosion Resistance and Mechanical Properties of
New Titanium Alloys for Centrifugally Cast Dental Implants,”
Materials Transactions, JIM, Vol. 38, No. 2, pp. 163-170,
1997.
2.Froes F.H., “The Eight World Titanium Conference,” Journal
of Metals, No. 7, pp. 59, 1996.
3.Ida K., Togaya T., and Suzuld M., ”Mechanical Properties of
Pure Titanium and Titanium Alloys,” J. Jpn Dent Mater, Vol.
27, pp. 777-782, 1989.
4.Eylon D., and Frores F.H., “Titanium Net-Shape
Technologies,” Journal of Metals, No. 6, pp. 36-41,1984.
5.Myers J.R., Bomberger H.B., and Froes F.H., “Corrosion
Behavior and Use of Titanium and Its Alloys,” Journal of
Metals, No. 10, pp. 50-60, 1984.
6.Niinomi Mitsuo, “Recent Titanium R&D for Biomedical
Applications in Japan,” Journal of Metals, No. 6, pp. 32-34,
1999.
7.Semiatin S.L., Seetharaman V., and Weiss I., “The
Thermomechanical Processing of Alpha/Beta Titanium Alloys,”
Journal of Metals, No. 6, pp. 33, 1997.
8.Eylon D., Froes F.H., and Gardiner R.W., “Developments in
Titanium Alloy Casting Technology,” Journal of Metals, No.
2, pp. 35-47, 1983.
9.Wegmann G., Albrecht Joachim, Liitering Gerd, Folkers Klaus-
Dieter, and Liesner Christian, ”Microstructure and
Mechanical Properties of Titanium Casting,” Z. Metallkd.,
Vol. 88, pp. 764-773, 1997.
10.Ivasishin O.M., and Markovsky P.E., ”Enhancing the
Mechanical Properties of Titanium Alloys with Rapid Heat
Treatment,” Journal of Metals, N. 7, 1996.
11.賴耿陽編著，金屬鈦理論及應用，復漢出版社，民79年。
12.李滄曉、倪國裕等編著，航太鑄件鑄造技術，中山科學研究院材發中
心與中華民國鑄造學會編印，民80年。
13.Poulsen E. R., and Hall J. A., “Extractive Metallurgy of
Titanium: A Review of the State of the Art and Evolving
Production Techniques,” Journal of Metals, No. 7, pp. 60,
1983.
14.Okavbe Toru, Ohkubo Chikahiro, Wataanabe Ikuya, Okuno Osamu,
and Takada Yukyo, ”The Present Status of Dental Titanium
Casting,” Journal of Metals, No. 9, pp. 24-29, 1998.
15.Newman J.R., “Titanium Castings,” Metals Hand books (9th
edition, ASM, Publication), Vol. 3, pp. 407-417.
16.Luchsmger E., Meyer J.M., and Susz C.P., “Titamum Casting
Alloys for Dental Application,” J Dent Res, Vol. 63 (spec
iss): 540, 1984.
17.Luchsinger E., Meyer J.M., and Susz C.P., “Casting of
Titanium Alloys,” J Dent Res, Vol. 70 (spec iss), pp. 1595,
1985.
18.Larsen Don, and Colvin Greg, ”Vacuum-Die Casting Titanium
for Aerospace and Commercial Components,” Journal of
Metals, No. 6, pp. 26-27, 1999.
19.Watanabe I., Watkins J.H., Nakajima H., Atsuta M., and Okabe
T., “Effect of Pressure Difference on the Quality of
Titanium Casting,” J. Dent. Res., Vol. 76, pp. 773-779,
1997.
20.Adachi M., Mackert J.R., Parry E.E., and Fairhurst C.W.,
“Oxide Adherence and Porcelain Bonding to Titanium and Ti-
6AI-4V Alloy,” J Dent Res, Vol. 69(6): 1230-1235,1990.
21.Almquist P., Chan D.C.N., Blackman R., and Margins D.A., ”
The Effects of Sprue Number and Position on Titanium Crown
Margins,” J Dent Res, Vol. 70 (spec iss), pp. 1758, 1991.
22.Arango J., Stein R.S., and Millstein P.L., “Castability and
Marginal Fit of Pure Titanium Castings,” J Dent Res, Vol.
70 (spec iss), pp. 2187, 1991.
23.Baez R.J., Nonaka T., and Blackman R., “Ti Castability and
Surface Characteristics with Three Phosphate Bonded
Investments,” J Dent Res, Vol. 70 (spec iss), pp. 1757,
1991.
24.Bomberger H.B., and Froes F. H., “The Melting of
Titanium,” Journal of Metals, Vol. 12, pp. 39, 1984.
25.Bessing C., and Bergman M., “Metallographic
Characterization of Four Alternative Alloys Intended for
Fixed Prostheses,” Acta Odontal Scand, Vol. 44, pp.101-112,
1986.
26.Bessing C., and Bergman M., “The Castability of Unalloyed
Titanium in Three Different Casting Machines,” Swed Dent J,
Vol. 16: 109-113, 1992.
27.Bessing C., “ Evaluation of the Castability of Four
Different Alternative Alloys by Measuring the Marginal
Sharpness,“ Acta. Odontol Scand, Vol. 44, pp.165-172, 1986.
28.Hiackman R., Barghi N., and Tran C., “Dimensional Changes
in Casting Titanium Removable Partial Denture Frameworks,”
J Prosthet Dent, Vol. 65, pp. 309-315, 1991.
29.Blackman R., Baez R., and Barghi N., “Marginal Accuracy and
Geometry of Cast Titanium copings,” J Prosthet Dent, Vol.
67, pp. 435-440, 1992.
30.Chai T.l., and Stein R.S., ”Porosity and Accuracy of
Multiple Unit Titanium Castings,” J Prosthet Dent, Vol. 73,
pp. 534-541, 1995.
31.Cooney J.P., Doyle T.M., and Caputo A.A., ”Surface
Smoothness and Marginal Fit with Phosphate-Bonded
Investments,” J Prosthet Dent, Vol. 41, pp. 411-417, 1979.
32.Donovan T., and Prince J., “An Analysis of Margin
Configurations for Metal-Ceramic Crowns,” J Prosthet Dent,
Vol. 53, pp. 153-157, 1985.
33.Doundoulakis J.H., “Surface Analysis of Titanium after
Sterilization: Role in Implant-Tissue Interface and
Bioadhesion,” J Dent Res, Vol. 58, pp. 417-478, 1987.
34.Greener E.H., Moser J.B., Opp J., Szurgot K., and Marker
B.C., “Properties of Centrifugally Cast Commercial Ti and
Ti-6AI-4V,” J Dent Res, Vol. 65 (spec iss), No. 317,1986.
35.Hamanaka H., Doi H., Yoneyama T., and Okuno, “Dental
Casting of Titanium and Ni-Ti Alloys by a New Casting
Machine,” J Dent Res, Vol. 68, pp. 1929-1533,1989.
36.Hero H., Syverud M., Waarii M., and Jorgensen R.B., “
Casting of Ti Restoration: Dimensional Fit and Porosity,” J
Dent Res, No. 70 (spec iss), pp.1763, 1991.
37.Hero H., and Waarii M., “Mold Filling and Porosity in
Casting of Titanium,” Dent Mater, Vol. 9, pp. 15-18, 1993.
38.Hero H., Syverud M., Waarii M., and Kleven E., ”Dimensional
Fit of Cast Titanium Restorations,” Journal of Materials
Science, Vol. 4, pp. 210-212, 1993.
39.Holmes J.R., Bayne S.C., Holland G.A., and Sulik W.D., ”
Considerations in Measurement of Marginal Fit,” J Prosthet
Dent, Vol. 64, pp. 405-408, 1989.
40.Hong J.M, Razzoog M.E., and Lang B.R., ”The Effect of
Recasting on the Oxidation Layer of a Palladium-Silver
Porcelain Alloy,” J Prosthet Dent, Vol. 59, pp. 420-425,
1988.
41.Hung C.J., Okazaki M., Takahashi J., and Kimura H.,
“Thermal Oxidation Effect on Porcelain-Titanium
Restoration,” Kaohsiung J Med Sci, No. 5, pp.522-528, 1989.
42.Hruska A.R., and Borelli P., “Quality Criteria for Pure
Titanium Casting, Intraoral Welding, and a Device to Aid in
Making Uncontaminated Castings,” J Prosthet Dent, Vol. 66,
pp. 561-565, 1991.
43.Ida K., Tani Y., Tsutsumi S., and Togaya T, “Clinical
Application of Pure Titanium Crowns,” Dent Mater J, Vol. 4,
pp. 191-195, 1985.
44.Ida K., Takeuchi M., Togaya T., and Tsutsumi S., ” Studies
on the Dental Casting of Titanium Alloy. Part 1. Casting of
Pure Titanium,” J Jpn Res Soc Dent Mater Appi, Vol. 37, pp.
45-52, 1980.
45.Kononen M., Rintanen J., Waltimo A., and Kempainen P.,
“Titanium Frame-Work Removable Partial Denture Used for
Patient Allergic to Other Metals: A Clinical Report and
Literature Review,” J. Prosthet Dent., Vol. 73, pp. 4-7,
1995.
46.Kay G.W., Jablonski D.A., and Dogon I.L., “Factors
Affecting the Seating and Fit of Complete Crowns: A Computer
Simulator Simulation Study,” J Prosthet Dent, Vol. 55, pp.
13-18, 1986.
47.Kelly J.R., Davis S.H., and Campbell S.D., “Nondestructive,
Three-Dimensional Fit Mapping of Fixed Prostheses,” J.
Prosthet Dent., Vol. 61, pp. 368-373, 1989.
48.Leong D., Chai J., Lautenschlager E.P., Gilbert J.,
“Marginal Fit of Machine Milled Titanium and Cast Titanium
Single Crowns,” Int. J. Prosthodont, Vol. 7, pp. 440-447,
1994.
49.Lofstrom L.H., and Barakat M.N., “Scanning Electron
Microscopic Evaluation of Clinically Cemented Cast Gold
Restorations,” J. Prosthet Dent., Vol. 61, pp. 644-669,
1989.
50.Miyakawa O., Watanabe K., Okawa S., Nakano S., Kobayashi M.,
and Shiokawa N., “Layered Structure of Cast Titanium
Surface,” Dent Mater J, Vol. 8, pp. 175-185, 1989.
51.Miyakawa O., Watanabe K., Okawa S., Nakano S., Kobayashi M.,
and Shiokawa N., “Skin Holes of Titanium Casting,” Dent Mater J, Vol. 12, pp. 171-181,1993.
52.Mori T., Jean-Louis M., Yabugami M., and Togaya T., “The
Effect of Investment Type on the Fit of Cast Titanium
Crowns,” Aust Dent J, Vol. 39, pp. 348-352, 1994.
53.Omar R., “Scanning Electric Microscopy of the Marginal Fit
of Ceramometal Restorations with Facially Butted Porcelain
Margins,” J Prosthet Dent, Vol. 58, pp. 13-18, 1987.
54.Papadopulos T., and Axelsson M., “Influence of Heating Rate
in Thermal Expansion of Dental Phosphate-Bonded Investment
Material,” Scand J Dent Res, Vol. 98, pp. 60-65, 1990.
55.Parr G.R., Gardner L.K., and Toth R.W., “Titanium: The
Mystery Metal of Implant Dentistry. Dental materials
Aspects,” J Prosthet Dent, Vol. 54, pp. 410-414, 1985.
56.Peregrina A.M., and Rieger M.R., “Evaluating Six Sprue
Designs Used in Making High-Palladium Alloy Castings,” J
Prosthet Dent, Vol. 56, pp. 192-196, 1986.
57.Peregrina A.M., and Schorr B.L., “Comparison of the Effects
of Three Sprue Designs on the Internal Porosity in Crowns
Cast with a Silver-Free High-Palladium Alloys,” J Prosthet
Dent, Vol. 64, pp. 162-166, 1990.
58.Rensburg F.V., and Strafing H., “Evaluation of the Marginal
Integrity of Ceramometal Restorations: Part II,” J Prosthet
Dent, Vol. 52, pp. 210-214, 1984.
59.Richter-Snapp K., Aquilino S.A., Avare C.W., and Turner
K.A., “Change in Marginal Fit as Related to Margin Design, A
Alloy Type, and Porcelain Proximity in Porcelain-Fused-to-
Metal Restorations,” J Prosthet Dent, Vol. 60, No. 418-424,
1988.
60.Roggensack M., Walter M.H., and Boning K.W., “Studies on
Laser-Welded and Plasma-Welded Titanium,” Dent Mater, Vol.
9, pp. 104-107, 1993.
61.Sarrett D.C., Richeson J.S, and Smith G.E, “Scanning
Electron Microscopy Evaluation of Four Finishing Techniques
on Margins of Gold Castings,” J Prosthet Dent, Vol. 50, pp.
784-792, 1983.
62.Schwartz I.S., “A Review of Methods and Techniques to
Improve the Fit of Cast Restorations,” J Prosthet Dent,
Vol. 56, pp. 279-283, 1986.
63.Sorensen J.A., “A Standardized Method for Determination of
Crown Margin Fidelity,” J Prosthet Dent, Vol. 64, pp. 18-
24, 1990.
64.Sunnerkrantz P.A., Syverud M., and Hero H., “Effect of
Casting Atmosphere on the Quality of Ti-Crowns,” J Dent
Res, Vol. 98, pp. 286-272, 1990.
65.Taira M., Moser J.B., and Greener E.H., “Face Coats for
Dental Casting Titanium Alloys,” J Dent Res, Vol. 64 (spec
iss), pp. 317, 1985.
66.Taira M., Moser J.B., and Greener E.H., “Study of Ti Alloys
for Dental Castings,” Dent Mater, Vol. 5, pp. 45-50, 1989.
67.Wang R.R., and Boyle A.M., “A Simple Method for Inspection
of Porosity in Titanium Castings,” J Prosthet Dent, Vol.
70, pp. 275-276, 1993.
68.Wang R.R, and Welsch G.E, “Joining Titanium Materials with
Tungsten Insert Gas Welding, Laser Welding and Infrared
Brazing,” J ProsthetDent, Vol. 74, pp. 521-530, 1995.
69.Wang R.R., and Fenton A., “Titanium for Prosthodontic
Applications: A Review of the Literature,” Quintessence
Int, Vol. 27, pp. 401-407, 1996.
70.Waterstart R.M., and Giuseppetti A.A., “Casting Apparatus
and Investment Mold Material for Metal at Very High
Temperatures,” J Dent Res, Vol. 64(spec iss), pp. 317, 1985.
71.Suzuki Ken-Ichiro, Nishikawa Koji, and Watakabe Siro,
“Stability of Yttria for Titanium Alloy Precision Casting
Mold,” Materials Transctions, JIM, Vol. 38, No.1, pp. 54-
62, 1997.
72.Suzuki Ken-Ichiro, “The High-Quality Precision Casting of
Titanium Alloys,” Journal of Metals, No. 9, pp. 20,1998.
73.Takahashi J., Kimura H., Lautenschlager E.P., Chern Lin
J.H., Moser J.B., and Greener E.H., “Casting Pure Titanium
into Commercial Phosphate-bonded SiO2 Investment Molds,” J.
Dent. Res., Vol. 69, pp. 1800-1805, 1990.
74.Suzuki Ken-Ichiro, Nishikawa Koji, and Watakabe Siro, “Mold
Filling and Solidification during Centrifugal Precision
Casting of Ti-6Al-4V Alloys,” Materials Transactions, JIM,
Vol. 37, No.12, pp. 1793-1801, 1996.
75.Taira M., Moser J.B., and Greener E.H., “Studies of Ti
Alloys for Dental Casting,“ Dental Materials, No. 1, pp. 45-
50, 1989.
76.Watanabe I.,. Watkin J.H, Nakajima H., Atsuta M., and Okabe
T., “Effect of Pressure Difference on the Quality of
Titanium Casting,” J. Dent. Res., Vol. 76, No.3, pp.773-
779, 1997.
77.Herø H., Syverud M., and Waarli M., “Mold Filling and
Porosity in Castings of Titanium,” Dent. Mater., Vol. 9,
pp. 15-18, 1993.
78.Sittig C., Textor M., and Spencer N.D., “Surface
Characterization of Implant Materials C.P. Ti, Ti-6Al-7Nb
and Ti-6Al-4V with Different Pretreatments,” Journal of
Materials Science in Medicine, Vol. 10, pp. 35-46, 1999.
79.Harris W. T., Chemical Milling, Oxford Press, 1976.
80.Dini J.W., “Fundamentals of Chemical Milling,” American
Machinist, No. 7, pp. 113-128, 1984.
81.Kreml J.M., Pierpont G.C., and Liebel J.M., “Chemical
Removal of Metals from the Surface of Titanium and Titanium
Alloys,” British Patent 1304043, January, 1973.
82.Sittig C., Textor M., Spencer N.D., Wielandand M., and
Vallotton P.-H., ”Surface Characterization of Implant
Materials C.P. Ti, Ti-6Al-7Nb and Ti-6Al-4V with different
pretreatments,” Journal of Materials Science: Materals in
Medicine, Vol. 10, pp.35-46, 1999.
83.Roni J.C., “Titanium Chemical Milling Etchant,” US Patent
3,844,859, Oct 29, 1974.
84.Bijlmer P.F.A., “Plicking Titanium in Hydrofluoric-Nitric
Acid,” Metal Finishing, Vol. 68, No. 11, pp. 64, 1970.
85.Straumanis M.E., and Chen P.C., “The Mechanism and Rate of
Dissolution of Titanium in Hydrofluoric Acid,” Journal of
the Electrochemical Society, Vol. 98, No. 6, pp. 234-240,
1951.
86.Sutter E. M. M., and Goetz-Grandmont G. J., “The Behaviour
of Titanium in Nitric-Hydrofluoric Acid Solutions,”
Corrosion Sci., Vol. 30, pp. 461-476, 1990.
87.Wilhelmsen Werner, “The Influence of Hydrofluoric Acid and
Fluoride Ion on the Corrosion and Passive Behaviour of
Titanium,” Electrochimica Acta, Vol. 32, No. 10, pp. 1469-
1474, 1987.
88.Le Goff P., and Ducros R., Surface Science, Vol. 21, pp. 136-
152, 1970.
89.Sato N., and Okamoto G., “Electrochemical Passivation of
Metals,” in Comprehensive Treatise of Electrochemistry (eds
Bockris J. O’M., Conway B. E., Yeager E., and White R. E.),
Vol. 4, Plenum press, New York, 1981.
90.Abdel Rahim M.A., “Variation of the Dielectric Constant of A
Anodic Oxide Films on Titanium with Oxygen Evolution,” J.
of Applied Electrochem., Vol. 25, pp. 881-885, 1995.
91.Macagno V., and Schultze J.W., “The Growth and Properties
of Thin Oxide Layers on Tantalum Electrodes,” J.
Electroanal. Chem., Vol. 180, pp. 157-170, 1984.
92.Ronald J. Solar, Solomon Pollack R., and Korostoff Edward,
“In Vitro Corrosion Testing of Titanium Surgical Implant
Alloys: An Approach to Understanding Titanium Release from
Implants,” J. Biomed. Mater. Res., Vol. 13, pp. 217-250,
1979.
93.Patrito E.M., Torresi R.M., Leiva E.P.M., and Macagno V. A.,
“Potentiodynamic and AC Impedance Investigation of Anodic
Zirconium Oxide Films,” J. Electrochem. Soc., Vol. 137, No.
2. 1990.
94.Barels Chr., Schultze J.W., Stimming U., and Habib M.A.,
“The Electrochemical Behaviour of Hafnium,” Electrochim.
Acta, Vol. 27, No. 1, pp. 129-140, 1982.
95.Torresi R.M., Cámara O.R., and De Pauli C. P., ”Influence o
of the Hydrogen Evolution Reaction on the Anodic Titanium
Oxide Film Properties,” Electrochim. Acta, Vol. 32, pp.
1357-1363, 1987.
96.De Becdelievre A.M., Fleche D., and De Becdeliever J.,
“Effect of Nitrogen Ion Implantation on the Electrochemical
Behaviour of Ti6Al4V in Sulphuric Medium,” Electrochim.
Acta, Vol. 33, No. 8, pp. 1067-1072, 1988.