近幾十年以來，鈦基、鐵基及鈷基合金已被廣泛研究並實際應用於生醫方面。然而，上述合金除了含有過量溶出會對人體造成傷害的元素以外，其過高的彈性模數亦會造成應力遮蔽效應，導致對植入體周邊的組織產生不良影響，除此之外，現有之生醫材料之植入體在傷癒後有需要經二次手術將植入體取出的缺點，增加病患的手術相關風險。基於此，新一代生物可降解之材料便逐漸受到重視與研究，在這之中，鎂合金尤受注目，除了因為鎂是身體中不可或缺的大量元素之外，亦具有與骨頭較接近之彈性模數。然而，鎂合金的抗腐蝕性質並不理想，作為生物可降解材料無法達到使周圍組織生長齊全之前便分解殆盡，因此，控制鎂合金的降解速率成為了最迫切的課題。科學家們透過表面處理的技術，在材料表面形成一層保護層來達到控制降解速率的效果，而羥磷灰石因著其優良的生物相容性以及骨整合性，使其適合用於生醫材料之鍍層。在諸多表面鍍層方法之中，電化學沉積法具有製程簡單、沉積溫度低、鍍層成分及厚度可控制之特點，也因此該方法在生醫材料的鍍層方面被廣泛的應用。除此之外，Komarov等人在2007年發表了超音波機械鍍膜技術，該方法乃是利用超音波使腔體內的鋼球震動，並藉此將粉體擊打並鍍至基材上。此一方法在生醫材料領域尚未被應用，且利用該法所得到之鍍層，在抗腐蝕能力方面亦未被研究。故在本研究中，電化學沉積以及超音波機械鍍層技數將被用來在AZ31B鎂合金表面鍍一層羥磷灰石，並且針對其抗腐蝕能力進行評估與研究。
在本研究中，經由XRD、EDS、FT-IR等分析，證實電化學沉積以及超音波機械鍍層均能有效地在AZ31B鎂合金表面鍍上羥磷灰石鍍層。而最需關注的抗腐蝕性質方面，根據電化學阻抗頻譜以及動電位極化法之實驗結果，以電化學沉積以及超音波機械鍍層等兩種技術分別製做的具羥磷灰石鍍層之AZ31B鎂合金在模擬人體體液下，相較於未進行任何表面處理之AZ31B鎂合金均具有較大的極化阻抗值以及較小的腐蝕電流密度。因此，經由實驗結果可以證實羥磷灰石鍍層可抑制鎂合金整體的降解速率，使其在生醫材料領域的實際應用上更向前邁進了一步。

For few decades, Ti-based, Fe-based and Co-based alloys have been widely investigated and applied in biomedical aspect. Yet, such alloys contain elements which will harm human body in high level; also, the Young’s moduli of these alloys are much higher than that of human bone, which will induce stress-shielding effect, causing negative effect to surrounding tissues. Moreover, secondary surgery may be necessary to remove the implant while the tissue is fully healed. To solve these problems, a new embryonic field, biodegradable materials, was under investigated. Among this field, Mg alloys received most attention, which was mainly because Mg exists abundantly in human body; furthermore, Mg alloys possess closer Young’s modulus to that of human bone. However, the obstacle for Mg alloys in biomedical application was its rapid degradation rate, which would lead to complete dissolution earlier than the tissue was sufficiently healed. Hence, the degradation rate control for Mg alloys became a critical issue. Scientists used surface modification methods to fabricate a coating on the material surface, achieving the goal for controlling the degradation rate. Hydroxyapatite (HA) was a suitable composition for biomaterial coating owing to its excellent biocompatibility and osteointegrity. Electrodeposition was a well-developed method featuring simple process, low deposition temperature and controllable for coating thickness and composition. In addition, Komarov et al. announced a new way that can fabricate coating through the mechanical method, the technique was called ultrasonic mechanical coating and armoring (UMCA). However, for this technique, its application on biomaterials was not observed yet; moreover, the corrosion study for the coating made by this technique was barely found. In this study, both electrodeposition and ultrasonic mechanical coating and armoring techniques were applied to form hydroxyapatite coating on AZ31B Mg alloy, respectively. Their corrosion resistance was also investigated and their extent of enhancement was under evaluation.
In this study, through X-ray diffraction (XRD), electron dispersive spectroscopy (EDS) and Fourier-transformed infrared spectroscopy (FT-IR) analyses, it can be confirmed that both electrodeposition and ultrasonic mechanical coating and armoring (UMCA) can successfully fabricate hydroxyapatite coating on AZ31B surface. As for the most concerned corrosion resistance, according to electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (Tafel) results, coated AZ31B showed larger polarization resistance and decreased corrosion current density. Hence, it can be demonstrated the degradation rate of hydroxyapatite coating can be effectively inhibited, which makes Mg biodegradable materials step forward to practical application.

論文審定書 i
致謝 ii
中文摘要 v
Abstract vii
Table of Content ix
List of Figures xii
List of Tables xvii
Chapter 1 Introduction 1
1.1 The development of metallic biomaterials 1
1.2 The development of biodegradable materials 2
1.3 Motivation 3
Chapter 2 Background and Literature Review 6
2.1 Biodegradable materials 6
2.2 Biodegradable metals 6
2.2.1 Fe-based biodegradable materials 7
2.2.2 Zn-based biodegradable materials 8
2.2.3 Mg-based biodegradable materials 9
2.3 Surface modification 12
2.3.1 Physical surface modification 13
2.3.2 Chemical surface modifications 14
2.3.2.1 Miscellaneous chemical surface modification methods 14
2.3.2.2 Electrodeposition 15
2.3.3 Mechanical surface modifications 17
2.3.3.1 Typical mechanical surface modification 17
2.3.3.2 Ultrasonic mechanical coating and armoring (UMCA) 18
2.4 Cathodic reactions for coating CaP 19
2.5 Corrosion 22
2.5.1 Corrosion types 23
2.5.2 Electrochemical measurements 25
2.5.2.1 Electrochemical impedance spectroscopy (EIS) 26
2.5.2.2 Potentiodynamic polarization 29
Chapter 3 Experimental Procedures 31
3.1 Preparation of specimens 32
3.2 Parameters of surface modification methods 32
3.2.1 Cathodic polarization 32
3.2.2 Electrodeposition and alkali post-treatments 33
3.2.3 Ultrasonic mechanical coating and armoring 34
3.3 Phase/composition characterization and morphology investigation 34
3.3.1 X-ray diffractometer (XRD) 34
3.3.2 Scanning electron microscope (SEM) 35
3.3.3 Fourier-transform infrared spectroscopy (FT-IR) 35
3.4 Electrochemical tests 35
Chapter 4 Results and Discussion 37
4.1 Cathodic polarization and electrodeposition 37
4.2 X-ray diffraction (XRD) analysis 37
4.2.1 Electrodeposited AZ31B specimen 38
4.2.2 UMCA treated AZ31B specimen 38
4.3 Morphology observation and composition characterization 39
4.3.1 Electrodeposited AZ31B specimen 39
4.3.2 UMCA treated AZ31B specimen 40
4.4 Functional group characterization through FT-IR 42
4.5 Electrochemical tests 43
Chapter 5 Conclusions 48
References 50
Tables 58-69
Figures 70-129

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