臺灣博碩士論文加值系統

改善氫氧基磷灰石(HAp)在不可降解的植入材上的機械強度及附著力來增進生醫相容性一直都是本實驗室這幾年研究的重點，然而它們永久留於體內仍有風險的問題。純鐵則有可能成為生物可降解植入材，因為它具被腐蝕性且它的腐蝕產物亞鐵離子正是血紅素所需要的元素。在本研究中使用純鐵基材置入於pH值為14.2，濃度1 M的氫氧化鈉(NaOH)溶液中進行鈍化，之後置入硝酸氧鋯ZrO(NO3)2溶液中進行電化學沉積氧化鋯(ZrO2)，最後再置入NH4H2PO4和Ca(NO3)2•4H2O的混合溶液中沉積氫氧磷灰石(HAp)，形成ZrO2/HAp之複合鍍層，經由退火方式使鍍層能與基材形成更穩定的鍵結，透過掃描電子顯微鏡(SEM)、X光繞射分析(X-ray Diffraction，XRD)以及動態極化測試等材料檢測，結果呈現已披覆ZrO2/HAp鍍層基材比未處理基材在Hank''s solution溶液中的腐蝕電流密度低，已從0.1 mA/cm2降至0.021 mA/cm2顯示ZrO2/HAp複合鍍層可有效的提升抗腐蝕能力，控制腐蝕速率而使它有機會成為可降解的生醫植入材。

致謝.............. i
摘要.............. ii
ABSTRACT.......... iii
總目錄............ iv
表目錄............ vii
圖目錄............ viii
第1章 前言.......................... 1
第2章 文獻回顧...................... 3
2-1 生醫材料之簡介.................. 3
2-1-1 生醫材料的定義................ 3
2-1-2 生醫材料所具備的性質與要求.... 3
2-1-3 生醫材料分類.................. 5
2-2 氫氧基磷灰石(HYDROXYAPTITE)..... 8
2-2-1 氫氧基磷灰石之基本性質........ 8
2-2-2 氫氧基磷灰石之合成............ 11
2-3 高溫氧化........................ 12
2-3-1 高溫氧化...................... 12
2-3-2 氧化熱力學.................... 12
2-3-3 純鐵(Fe)的高溫氧化............ 15
2-4 氧化鋯之性質.................... 17
2-5 電化學沉積(ELECTROCHEMICAL DEPOSITION)... 18
2-6 電解沉積氧化鋯之反應機構................. 19
2-7 電解沉積氫氧基磷灰石(HAP)之反應機構...... 20
2-8 極化(POLARIZATION)....................... 20
2-8-1 活性極化(Activation polarization)...... 22
2-8-2 濃度極化(Concentration polarization)... 23
2-8-3 電阻極化(Resistance polarization)...... 24
2-9 鈍化(Passivation)........................ 25
2-9-1 金屬鈍化的意義......................... 25
2-9-2 金屬鈍化的機制原理..................... 25

第3章 實驗步驟與方法......................... 27
3-1 試片的準備與前處理....................... 27
3-2 電解液之調配............................. 30
3-2-1 硝酸鋯電解液之調配..................... 30
3-2-2 氫氧基磷灰石電解液之調配............... 30
3-3 陰極極化................................. 30
3-4 電化學沉積............................... 31
3-4-1 最佳沉積電流密度....................... 31
3-4-2 最佳沉積時間........................... 31
3-5 陰乾與燒結............................... 31
3-6 SEM/EDS鍍層之表面型態觀察及化學成份分析.. 32
3-7 X光繞射(XRD)分析......................... 32
第4章 結果與討論............................. 35
4-1 陰極極化................................. 35
4-1-1 硝酸鋯水溶液之陰極極化實驗............. 35
4-1-2 磷酸鈣電解液之陰極極化實驗............. 37
4-2 電解沉積製程之參數探討....................38
4-2-1 選擇最佳沉積電流........................38
4-2-2 選擇最佳之沉積時間..................... 41
4-3 陰乾與燒結參數設定對薄膜的影響........... 41
4-4 燒結後之X光繞射分析...................... 42
4-5 動態極化測試............................. 43
第5章 結論................................... 50
參考文獻..................................... 51

1. H. Li, Y. Zheng, L. Qin, "Progress of biodegradable metals", Prog. Nat. Sci.Mater
Int. 24 414–422(2014).
2. Y.F. Zheng, X.N. Gu, F. Witte, "Biodegradable metals", Mater. Sci. Eng. R 77
1–34(2014).
3. H. Hermawan, "Biodegradable Metals: From Concept to Applications", Springer,
Heidelberg,Germany, 2012.
4. X.N. Gu, Y.F. Zheng, Y. Cheng, S.P. Zhong, T.F. Xi, "In vitro corrosion and
biocompatibility of binary magnesium alloys", Biomaterials 30(2009) 484.
5. S.L. Yang, Z.H. Wu, W. Yang, M.B. Yang, “Thermal and mechanical properties of chemical crosslinked polylactide (PLA)”, Polym. Test. 27 (2008)957.
6. K.Y. Cai, K.D. Yao, Z.M. Yang, X.Q. Li, “Surface modification of three-dimensional poly(d, l-lactic acid) scaffolds with baicalin”, A histological study, Acta Biomater. 3 (2007)597.
7. S.F. Zhu, N. Huang, L. Xu, Y. Zhang, H.Q. Liu, H. Sun, Y.X. Leng,
"Biocompatibility of pure iron: In vitro assessment of degradation kinetics and
cytotoxicity on endothelial cells", Mater. Sci. Eng. C 29 (2009) 1589.
8. C.W. Siah, D. Trinder, J.K. Olynyk, "Iron overload", Clin.Chim.Acta 358
(2005)24.
9. R.Waksman, R. Pakala, R. Baffour, R. Seabron, D. Hellinga, F.O. Tio,
" Short-term effects of biocorrodible iron stents in porcine coronary arteries",
J. Interv. Cardiol. 21 (2008) 15.
10. M. Peuster, C. Hesse, T. Schloo, C. Fink, P. Beerbaum, C. Von Schnakenburg,
"Long-term biocompatibility of a corrodible peripheral iron stent in the porcine
descending aorta", Biomaterials 27 (2006) 4955.
11. 鈴木弘茂,"精密陶瓷的最新技術",工業技術研究院出版,P.159-171(1984).
12. Bulter,C.A.,Jones,L.C.1998.Initial stability of porous coated total hip femoral components: a mechanical study of micromovement.Journal of Orthopaedic Research 13,pp.549-560.
13. L.L.Hench,"Bioceramics:From Concept to Clinic,"J.Am.Ceram.Soc.,74﹝7﹞(1991)1487-1510.
14. K.A.Khora,*,C.S.Yipa,P.Cheangb,"Post-spray hot isostatic pressing of plasma sprayed Ti-6Al-4V/hydroxyapatite composite coatings",Journal of Materials Processing Technology 71 P.280-287(1997).
15. F.Brossa,A.Cigada,R.Chiesa,L.Paracchini,and C.Consonni,"Adhesion properties of plasma sprayed hydroxyapatite coatings for orthopaedic prostheses,"Biomedical Materials Engineering,3,127-136(1993).
16. Allen J.Bard and Larry R.Faulkner,"Electrochemical Methods",(1980).
17. Denny A.Jones,"Principles and Prevention of Corrosion",Maxwell Macmillan International Edition,(1992).
18. A. Ravaglioli and A. Krajewski, "Bioceramics,"Chap.1,. Chapman&Hall, 1992.
19.耿藝文 and 王盈錦, "生醫材料之現況與展望,".生物業.2,23-28(1991).
20.D.F.Williams,and R.Roaf,Implants in Surgery. W.B.SaundersCompany, London.p.149-64,(1973).
21.蘇建榮,針對不同表面處理之鈦合金骨螺絲作生物親和性的評估,國立成功大學醫學工程研究所碩士論文(2002).
22.汪建民主編,"陶瓷技術手冊(下)".中華民國產業科技發展協會p.1027(1994).
23.林奇民,"The Study of Electrolytic Deposition of Al2O3-HA Bioceramic on
Pure Titanium",國立中興大學 材料工程研究所碩士論文(2000).
24.Ronald.Mc Rae 原著,江招慶 編譯, "實用骨科治療學",藝軒圖書出版社，53(1991).
25.Chien-Jung Su,"Evaluation of Biocompatibility on Various Surface-
Processed Titanium Screws:Animal Model".A Thesis Submitted to the institute of Biomedical Engineering National Cheng Kung University，p3(2002).
26.J.B.Park,"Biomaterials Science and Engineering",Plenum Press,New York and London,(1985).
27.F.C.M.Driessens,"Formation and Stability of Calcium Phosphate in realtion to the phase composition of the mineral in calcified tissues",in "Bioceramics of calcium phosphate,p1-6(1983).
28.J.W.Wang, W.J.Shih, and M.H.Hon.,"Preparation and characterization of Chitosan/poly(acrylic acid)nanoparticles",JOM,v56,n11,November, 2004, p.237(EI:0.591).
29.C.C. Berndt,G.N.Haddad,A.J.D.Farmer,and K.A.Gross,"Thermal Spraying for Bioceramic Applications",Mater.Forum,14 P.161-173(1990).
30.Lorry L.Hench and June Wilson,"An Introduction to Biomaterials", p.139~198.
31.B.D.Ratner,A.S.Hoffman,F.J.Schoen and J.E.Lemons,"Biomaterials Science-An Introduction to Materials in Medicine",Academic Press,San Diego.London.Boston.New York.Sydney.Tokyo.Toronto,P.37-50(1996).
32.I.Zhitomirsky,L.Gal-Or and A.Kohn,"Electrodeposition of ceramic films from non-aqueous and mixed solutions",Journal of Materials Science,30,5307-5312(1995).
33.王寶琪,"電漿熔射氫氧基磷灰石披覆於鈦鋁釩合金基材塗層之塗層特性與生物反應研究",國立成功大學材料科學及工程研究所博士論文,p.29(1994).
34.王朝正,"高溫腐蝕"工程,第七十五卷第三期,p.97-110(2002).
35.N.Birks and G.H.Meier,in"Introduction to High Temperature Oxidation of Metals",Edward Arnold,London,p.17(1983).
36.A.S.khanna,"High Temperature Oxidation and Corrosion",ASM International,p.84-85(2002).
37.李美栓,"金屬的高溫腐蝕",Edward Arnold,London,p.17(1983).
38.賴志育,"The study of Electrolytic Alumina Toughened Zirconias and ZirconiaToughened Alumina Ceramic Coatings on Co-Cr-Mo Alloy",國立中興大學材料工程學研究所碩士論文.
39.Wenjea Tseng,"Microstructural Development on an ZrO2(Y2O3) Surface", Journal of Materials Science Letters,17,p.285-288(1997).
40.R.Winand,"Electrocrystallization:Fundamental Considerations and Application to High Current Density Continuous Steel Sheet Plating", Journal of Applied Electrochemistry,21,P.377-385(1991).
41.胡啟章,"電化學原理及方法",五南圖書出版有限公司,P.6-10(2002).
42.C.C.Chang and S.K.Yen,Proceeding of 1998 Annual Conference of the Chinese Society for Ceramic Socience,P.52(1998).
43.L.Gal-Or,I Silberman and R.Chaim,Journal of the Electrochemical Society Vol.138,P.1939-1972(1991).
44.S.K.Yen and C.M.Lin,"Cathoodic reactions of electrolytic hydroxyapatite coatings on pure titanium",Materials Chemical and Physics,77,70-76,(2002).
45.S.K.Yen,"Characterization electrolytic ZrO2 coating on AISI 316L stainless steel",J.Electrochem.Soc.,146,1392-1397(1999).
46.鮮祺振,"腐蝕控制",徐氏基金會出版(1998).
47.田福助,"電化學理論與應用",新科技書局出版(2014).
48.格里弟 博士編著,"電極動力學",徐氏基金會出版,P.35(1996).
49.金屬表面處理藥劑資訊網.
50.http://www.twwiki.com/wiki/鈍化.
51.許樹恩,吳泰伯 編著,"X光繞射原理與材料結構分析",中國材料科學學會,(1996).
52.S.K.Yen,"Mechanism of electrolytic ZrO2 coating on commerical pure tianium",Institute of Materials Engineer,National Chung Hsing University,Material Chemistry and Physics 63 P.256-262(2000).
53.林素萍,"電解沉積ZrO2/HA生醫陶瓷薄膜於Ti-6Al-4V合金上之研究",國立中興大學 材料工程學研究所碩士論文(2001).