臺灣博碩士論文加值系統

目前將具生物生物活性的陶瓷披覆在金屬上的方法廣為大家所研究主要是在解決生物相容性，離子釋放以及穩定的固定在金屬植入材上的問題。但以目前而言，這些問題仍未解決；如披覆膜薄、所需鍍膜時間較長且鍵結強度弱。另外植入材的表面不具有抗菌性，增加植入後細菌感染的機會。
因此在本研究中，將基材316L不銹鋼利用電化學在模擬體液中沉積的方式沉積氫氧基磷灰石(HAp)。適當控制化學參數-電流、溫度和pH 值, 找出最佳披覆在316L不銹鋼上鍍層條件。再以最佳條件用相同的方法於含鋅的電解液中電鍍，期望改質後的表面具有抑制微生物的感染及增生。
首先，在表面改質後的XRD, SEM, EDX結果知，當基材經鹼處理10 M NaOH在溫度60C 時間24小時之後再熱處理至溫度400℃，表面會有鈉鉻的氧化層相出現並穩定於316L不銹鋼上。鈉鉻氧化層的形成將會成為金屬基材與之後沉積的似骨的磷灰石的結合。而在電化學沉積過程中，由沉積在不同條件的XRD, FTIR, SEM, EDX, Potentiodynamic test 及Scratch test結果顯示，在提供10mA電鍍1小時 在80℃時為最佳的鍍膜條件。在此條件下，膜厚可達10~20μm而且均勻。另外鍍膜也具有很好的抗蝕性、抗刮性、所需的鍍膜時間較短。有效的改進sol-gel法的缺點。接著，使用最佳條件在含鋅的電解液中以相同的電鍍方式進行，可電解沉積出含鋅的磷酸鈣化合物。我們可以找出CaZn2(PO4)2*H2O、Zn3(PO4)2*H2O、Zn2P2O7及CaO 等成分在基材上，隨的鋅離子濃度的增加而增加。
由現在的結果暗示鋅與三鈣磷酸鹽結合會增加穩定的ZnTCP結晶結構的產生。這些含鋅的化合物將增加抑制細菌的效果。由agar plant、OD值及SEM 的抑菌活性測試結果，所有的結果顯示當基材在披覆沒有含鋅的HAp及有含鋅的磷酸鈣後分別浸入在含有金黃色葡萄球菌ATCC 29213及綠膿桿菌ATCC 27853的nutrient broth (NB) 的溶液中時，隨著鋅成分的增加，細菌的量會減少由agar plant、OD值及SEM 影像可知。由現今結果知含鋅的磷酸鈣會減少微生物的感染及增生。這似乎是試片表面吸附一些鋅離子，當浸泡在含有金黃色葡萄球菌ATCC 29213及綠膿桿菌ATCC 27853的nutrient broth (NB) 的溶液中時，導致鋅離子的釋放在nutrient broth (NB) 的溶液中，然後引起細菌的細胞壁及細胞膜的破壞，因此當增加鋅離子的濃度時，使表面改質後的316L不銹鋼具有明顯的抑菌性。

Coating bioactive ceramics onto metals was a popular method to resolves the problems of biocompatibility, ion released and fixation of metal implant. But at present, it should not solve the problems; as the coating layer was only a thin film, needed a long-term treatment, and have poor bonding strength. On the other hand, the surface of implant materials should not antibacterial, so that increasing ratio of infect with bacterial.
So in our research, 316L stainless steel was selected as the substrate and electrolytically deposition with hydroxyapatite (HAp) in an aqueous solution of simulated body fluid. By controlling the chemical parameters such as potential, temperature, pH value, find the best deposition condition with calcium phosphate –coated on 316L stainless steel substrate. Used the best deposition condition in the same method, electrolytically deposition with zinc-containing calcium phosphate in an aqueous solution of simulated body fluid that zinc containing. Wish the modified surface reducing the microbial-induced infections and degradations.
At first, the results of XRD, SEM, EDX for modified surface sample, after substrate treated with 10 M NaOH at 60C for 24h and heated to 400℃ temperatures. The sodium chromium oxide would be phased out and fixed on 316L stainless steel. So, a stable layer of sodium chromium oxide formed, which would be an inter-compound to bridge up metallic substrate and later deposited bone-like apatite.
At electrodeposition process, The results of XRD, FTIR, SEM, EDX, Potentiodynamic test, scratch test for deposition at different condition. All of results was showed that the best deposition condition of 10mA for 1hr at 80℃. In the operation conditions, the coating layer was above 10~20 μm and uniform. However, it also have good corrosion-resisting, scratch test and short time was compared with sol-gel method. As follows, used the best deposition condition in the same method, electrolytically deposition with zinc-containing calcium phosphate component. We can find the CaZn2(PO4)2*H2O、Zn3(PO4)2*H2O、Zn2P2O7及CaO were appeared on the surface when the concentration of Zn ion of electrolytic increased. The present results indicate that Zinc incorporated into tricalcium phosphate (TCP) increase the stability of the crystal structure of ZnTCP. Those components of zinc containing will improvement in bacteria responsible effect.
From the antibacterial activity test as shown in agar plant, OD value, and SEM. All of results showed that when the samples of HAp-coated with and without Zn-treatment were immersed into the nutrient broth (NB) solution which containing bacterial for Staphylococcus aureus ATCC 29213 and Pseudomonas aeruginosa ATCC 27853, respectively. The quantity of bacteria decreased with zinc content increased as shown in agar plant, OD value and SEM morphologies. The present results that zinc-containing of calcium phosphate was reducing the microbial-induced infection and degradations. It seem that the surface of sample was absorption some zinc ions. When immersed in nutrient broth (NB) solution which containing Staphylococcus aureus ATCC 29213 and Pseudomonas aeruginosa ATCC 27853, it lead to zinc ions release from nutrient broth (NB) solution, then cause to destroy for the bacterial wall and bacterial membrane. So that it have more antiseptic effect on 316L stainless steel as increasing of zinc concentration.

Chapter 1 Introduction……………………………………………………1
1.1 Introduction……………………………………………….………….1
1.2 Classification and treatment of fracture………………………1
1-2.1 Classification of fractures …………………………………1
1-2.2 General principles of facture treatment……………………2
1-2.3 The development of traditional fixation in broken bone……………………………………………………………………………3
1.3 Some methods for coating bioactive ceramics onto tough metals…………………………………………………………………………4
1.4 Material and method of antiseptic………………………………6
1.5 The aim of study………………………………………………………9
Chapter 2 Basic Theories…………………………………………………15
2.1Biomaterials……………………………………………………………15
2.1.1 Condition for biomaterials……………………………………15
2.1.2 Classification of biomaterials………………………………16
2.2 316L stainless steel ………………………………………………17
2.3 Apatite………………………………………………………………………18
2.4 Substituted apatites………………………………………………20
2.5 Electrochemical deposition………………………………………21
2.6 Implant caused infections…………………………………………23
Chapter 3 Materials and Methods………………………………………35
3.1 Flow chart……………………………………………………………35
3.2 Specimen and surface treatment preparation…………………36
3.3 The electrodeposition of calcium phosphate coating…………37
3.4 Specimen analysis….……………………..…………………………38
3.5 Corrosion test………………………………………………………38
3.6 Scratch-test…………………………………………………………40
3.7 The electrodeposition of Zn-HAp coating………………………40
3.8 Antibacterial activity test………………………………………41
Chapter 4 Result and Discussion………………………………………43
4.1 Analysis surface of substrate after the alkali and heat treatments…………………………………………………………………43
4.1.1 Analysis of XRD………………………………………………43
4.1.2 Analysis of SEM………………………………………………43
4.1.3 Analysis of EDX…………………………………………………44
4.2 Analysis surface of substrate after electrodeposition…………………49
4.2.1 Analysis of XRD…………………………………………………49
4.2.2 Analysis of Micro-FTIR…………………………………………54
4.2.3 Analysis of SEM…………………………………………………59
4.2.4 Analysis of EDX………………………………………………..63
4.3 Analysis surface of substrate after electrodeposition on zn-containing solution …………………………………………………….79
4.3.1 Analysis of XRD…………………………………………………79
4.2.2 Analysis of Micro-FTIR….……………………………………79
4.2.3 Analysis of SEM…………………………………………………80
4.2.3 Analysis of EDX……………………………………………………81
4.4 Antibacterial activity test………………………………………81
4.4.1 The antibacterial activity influence of different zinc
concentration……………………………………………………………81
Chapter 5 Conclusions…………………………………………………95
References…………………………………………………………………96

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