臺灣博碩士論文加值系統

鎂合金具有輕量化、彈性係數與人體硬組織相近、優良的生物相容性及生物可降解性、降解後的離子釋出不會對人體造成毒性等特性，使其被視為新一代的硬組織取代場合之醫用金屬植入材料。本研究即採用AZ91D鎂合金作為基材並進行AZ91D之表面改質處理，其目的除了藉由水熱法進行AZ91D之表面處理被覆具有誘導骨骼生長之多孔性生物活性鍍層以調控其腐蝕速率之外，更可利用多孔性鍍層做為載體緩釋藥物，達到兼具多功能之生物可降解鎂合金植入材料。實驗將AZ91D試片浸置於以磷酸氫鈣/氫氧化鈣/六氟磷酸為原料所調配，含Ca、P、F元素並具Ca/P莫爾比為1.67之混合溶液中，利用水熱法之壓力釜裝置將其加熱至175ºC、持溫1.5小時之飽和蒸氣壓環境下，在AZ91D基材表面合成被覆氟離子取代型氫氧基磷灰石(FHA)鍍層，另亦以水熱法在AZ91D表面製備氫氧化鎂(Mg(OH)2)鍍層作為對照組，接著利用旋轉塗佈法在FHA與Mg(OH)2鍍層表面被覆聚乙二醇(PEG)，並進行水熱合成FHA、Mg(OH)2鍍層及經PEG塗佈之複合鍍層微觀組織、表面粗糙度分析、親疏水性測試、鍍層附著力試驗、極化曲線測試和浸泡實驗分析。微觀組織解析結果顯示FHA鍍層表面為具有針狀結構團簇成球堆積之特徵且富含孔隙，Mg(OH)2鍍層表面則呈現片狀結構堆疊之多孔隙組織，FHA與Mg(OH)2鍍層經PEG被覆後，發現其鍍層表面孔隙皆受到PEG滲入現象，並致使被覆PEG鍍層之表面粗糙度降低，而PEG的披覆仍可保留FHA/Mg(OH)2鍍層的親水性，在模擬體液(SBF)環境進行電化學腐蝕實驗之分析結果顯示PEG-FHA與PEG-Mg(OH)2鍍層在SBF溶液較未經表面處理之AZ91D及水熱製成FHA、Mg(OH)2鍍層有較低腐蝕電流密度與腐蝕速率，顯示經PEG包覆有助於FHA與 Mg(OH)2鍍層在降解緩釋的過程中減緩了腐蝕速率。而浸泡實驗記錄受腐蝕減少的重量，證明FHA/Mg(OH)2鍍層對於AZ91D鎂合金能大幅增強其抗腐蝕能力，而經過PEG披覆過後改變鍍層周圍浸泡溶液的黏稠度，進而達到降低腐蝕速率的目的。

Magnesium-based (Mg-based) alloys have several biomedical advantages including light-weight, the elastic modulus close to human bones and other hard tissues, good biocompatiblity, excellent biodegradability and non-toxicity of release Mg-ions to the human body after degradation. Mg alloys can be thought of a new generation biomedical metallic implant materials fot the hard tissue replacements. AZ91D Mg alloy is selected as the substrate for the subsequently surface treatments in this study. The purpose of surface treatment for AZ91D is to control its corrosion rate and introduce new bone growth with the deposition of a porous bioactive surface coating. In addition, the porous bioactive coating can be applied as a drug release carrier to release drugs slowly and the AZ91D with porous bioactive surface coating will be achieved as a multifunction biodegradable metallic implant material. In this study, AZ91D Mg alloy substrate is immersed in a CaHPO4/Ca(OH)2/HPF6 reagent solution with Ca, P, F elements and a Ca/P molar ratio of 1.67. The hydrothermal process for synthesizing F-substituted hydroxyapatite (FHA) on AZ91D is performed at 175°C, held for 1.5 hr in an autoclave with an ambient saturated steam pressure environment. Besides, Mg(OH)2 surface layer, which is used as a control, was also synthesized onAZ91D by the hydrothermal treatement. Subsequently, the polyethylene glycol (PEG) is deposited onto the hydrothermal FHA and Mg(OH)2 surface layers by the spin-coating process. Microstructure observations, surface roughness measurements, contact angle tests and adhesion tests of FHA, Mg(OH)2 surface layers and PEG modified composite coatings are then examined in this study. Experimental results show that a specific needle-like crystalline aggregated porous structure is observed on the surface of the hydrothermal FHA coating, whereas a hexagonal flake-like crystallites porous structure is observed on the Mg(OH)2 coating. The decrease of surface roughness of the composite coating is resulted from the reduction of surface porosity of FHA and Mg(OH)2 after depositing the PEG top coat. Electrochemical corrosion analysis results show that spin-coated PEG-FHA and PEG-Mg(OH)2 composite coatings represents lower corrosion current density and corrosion rate within simulated body fluid (SBF) than uncoated AZ91D substrate and hydrothermal FHA and Mg(OH)2 coatings. It can be recognized that the degradation and corrosion rate of hydrothermal FHA and Mg(OH)2 coatings are apparently reduced after the deposition of PEG top coating.

摘要.....i
Abstract.....ii
誌謝.....iv
總目錄.....v
表目錄.....vii
圖目錄.....viii
第一章 前 言.....1
第二章 文獻回顧.....2
2.1 生醫材料.....2
2.1.1 金屬生醫材料.....2
2.1.2 陶瓷生醫材料.....3
2.1.3 可降解高分子生醫材料.....4
2.2 生物可降解鎂合金.....5
2.3 氫氧基磷灰石與氟離子取代型氫氧基磷灰石.....7
2.4 水熱法.....8
2.5 表面親疏水性.....9
2.6 電化學原理.....10
2.6.1 動電位極化曲線.....10
第三章 實驗內容與方法.....19
3.1 鎂合金基材前處理.....19
3.2 水熱法鍍層之製備.....19
3.3 旋轉塗佈披覆PEG鍍層處理.....20
3.4 表面粗糙度分析.....20
3.5 表面親疏水性分析.....21
3.6 X-ray繞射組成分析.....21
3.7 電子顯微鏡微觀組織分析.....21
3.8 鍍層附著力強度測試.....21
3.8.1 拉伸試驗.....21
3.8.2 百格試驗.....22
3.9 抗腐蝕特性分析.....22
3.9.1 配製Kokubo's SBF 模擬體液.....22
3.9.2 動態電位極化曲線.....22
3.9.3 模擬體液浸泡實驗.....23
第四章 實驗結果與討論.....37
4.1 PEG修飾之複合鍍層微觀組織分析.....37
4.1.1 鍍層形貌與鍍層厚度.....37
4.1.2 鍍層表面粗糙度.....41
4.1.3 鍍層表面微觀組織.....42
4.1.4 EDS元素分佈分析.....46
4.2 X-ray繞射組成分析(XRD).....51
4.3 鍍層附著力分析.....54
4.2.1 百格測試.....54
4.2.2 剪切力拉伸試驗.....56
4.4 鍍層與複合鍍層表面親疏水性.....61
4.5 電化學腐蝕分析.....63
4.5.1 FHA鍍層電位極化曲線分析.....63
4.5.2 Mg(OH)2鍍層極化曲線分析.....65
4.6 模擬體液浸泡實驗.....69
4.7 FHA、Mg(OH)2利用PEG披覆經模擬體液浸泡後微觀組織.....77
第五章 結論.....79
參考文獻 .....81

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