臺灣博碩士論文加值系統

本研究是利用化學溶液反應法在不同Ca2+、PO43-及OH-濃度下，探討氫氧基磷灰石或磷酸鈣鹽類在不同基板生成機構。基板包括Ca3(PO4)2、Al2O3及ZrO2等燒結複合材料。化學溶液反應過程是以1M磷酸水溶液，在溫度為25?80℃及pH＝0.7~11條件下，對基板做不同時間的化學反應處理。在pH=2.5時,而Ca2+來源是藉由氫氧化鈣於磷酸水溶液來增加時,基板上的披覆物是CaHPO4?2H2O (Dicalcium phosphate dihydrate , DCPD)為主。這個披覆物再經過在2.5 M NaOH溶液鹼性處理後會轉變為氫氧基磷灰石(HA)。由實驗結果發現:在高pH值溶液中，HA較易形成，而且披覆物的型態是由片狀轉換成網狀。至於在氧化鋁/三鈣磷酸鹽和氧化鋯/三鈣磷酸鹽複合基板，而當三鈣磷酸鹽與氧化鋁或氧化鋯體積比為7:3時，在鹼性溶液處理時，DCPD較易轉換為HA。

A chemical reaction method was used to study the formation mechanisms of hydroxyapatite or calcium phosphate salts on the surface of different ceramic substrates, through controlling different concentrations of Ca2+、PO43- and OH- in the aqueous solution. In this study, sintered Ca3-(PO4)2, Al2O3 and ZrO2 ceramic composites were fabricated to be plate-like substrates for this particular chemical coating process. In the chemical coating or reacting process, different ceramic substrates were dipped in the 1 M H3PO4 aqueous solution at T=25~80℃ and pH=0.7~11, to observe phase existence and microstructure of surface coating. Surface coating was formed to be CaHPO4?2H2O (DCPD) after the Ca3(PO4)2 substrate was dipped in the 1 M H3PO4 aqueous solution at pH=2.5 under a sufficient Ca2+ source from Ca(OH)2 . The surface coating of DCPD was further treated in the alkaline solution, 2.5 M NaOH and it was further transformed into hydroxyapatite. From experimental results, HA was formed easily at a higher pH value. As the pH value increased, the surface morphology of these coatings were changed into the network structure from the initial plate structure. In the Al2O3/Ca3(PO4)2 and ZrO2/Ca3(PO4)2 composite substrates, HA was much easier to form in the alkaline solution when the volume ratio of Ca3(PO4)3/Al2O3 or Ca3- (PO4)2/ ZrO2 was 7/3.

中文摘要i
英文摘要ii
誌謝iv
總目錄v
圖目錄vi
表目錄xi
第一章 序論1
第二章 理論背景3
2-1 生醫陶瓷簡介3
2-1-1 生醫材料的簡介3
2-1-2 生醫材料的定義3
2-1-3 生醫材料之基本要求3
2-1-4 生醫材料的分類4
2-1-5 生醫陶瓷之市場需求及種類6
2-2 各類生醫陶瓷特性8
2-2-1 氧化鋁8
2-2-2 氧化鋯9
2-2-3 孔隙性陶瓷11
2-2-4 複合材料12
2-2-5 氫氧基磷灰石13
2-3 生醫陶瓷的應用20
2-4 氫氧基磷灰石的合成方法23
2-4-1 氫氧基磷灰石的製備方法23
2-4-2 氫氧基磷灰石覆層之特性23
2-5 鈣磷系鹽類的溶解度26
2-5-1 溶解度基本定義26
2-5-2 鈣磷系鹽類的化學溶液反應27
2-6 基板製作31
2-6-1 燒結性質31
2-6-2 基板來源和製作32
2-7 電化學沉積32
2-7-1 磷酸水溶液32
2-7-2 無電電鍍32
2-7-3 電化學沉積沉積的性質33
2-7-4 NaOH 處理之探討35
第三章 實驗方法36
3-1 實驗藥品與儀器36
3-1-1 實驗藥品36
3-1-2 實驗儀器37
3-2 實驗步驟38
3-2-1 實驗流程39
3-2-2 試片製作與前處理40
3-2-3 溶液之調配40
3-2-4 浸鍍時間及條件40
3-2-5 NaOH處理40
3-3 鍍層分析41
3-3-1 XRD 41
3-3-2 SEM/EDS 41
3-3-3 IR 42
3-3-4 DTA/TGA 42
第四章 結果與討論43
4-1 粉末和基板的性質43
4-2 不同基板在化學溶液中浸泡前後pH值改變48
4-3 不同pH值改變對基板表面披覆物相組成的影響50
4-4 pH值改變對基板表面披覆物型態的影響55
4-5 鈣離子濃度及pH值對表面披覆層的影響62
4-6 NaOH處理對基板表面披覆物的影響66
4-7 FTIR及RAIR光譜分析78
第五章 結論80
參考文獻82
圖目錄
圖2-1-5-1 生醫陶瓷於臨床上的應用圖7
圖2-2-5-1 氫氧基磷灰石中各離子的位置18
圖2-2-5-2 CaO-P2O5在無水蒸汽系統之相平衡圖19
圖2-2-5-3 CaO-P2O5在水蒸汽壓500mm-Hg系統下之相平衡圖19
圖2-5-2-1 磷酸鈣鹽類在Ca(OH)2-H3PO4-H2O系統中溶解曲線圖29
圖2-7-3-1 不同的磷酸鈣溶解相圖35
圖3-1-1 實驗流程圖39
圖4-1-1 起始粉末β-三鈣磷酸鹽的DTA與TGA之圖43
圖4-1-2 不同基板體積收縮率44
圖4-1-3 各種基板的X光繞射光譜圖45
圖4-1-4 不同成份基板表面SEM微觀組織47
圖4-2-1 不同基板隨著時間pH值之改變圖49
圖4-3-1 HA基板浸泡不同pH值溶液之XRD圖50
圖4-3-2 Ca3P基板浸泡不同pH值溶液之XRD圖51
圖4-3-3 Al2O3/Ca3P複合基板經1 M H3PO4水溶液處理前後基板表面之XRD圖52
圖4-3-4 ZrO2 /Ca3P複合基板經1 M H3PO4水溶液處理前後基板表面之XRD圖53
圖4-3-5 不同基板浸泡在80℃ 的1M H3PO4的水溶液處理基板表面之XRD圖54
圖4-4-1 在1M H3PO4的水溶液，浸泡不同時間HA基板表面型態的改變之SEM圖55
圖4-4-2 HA基板浸泡不同pH值溶液的表面型態之SEM圖56
圖4-4-3 Ca3P基板浸泡不同pH值溶液的表面型態之SEM圖58
圖4-4-4 Al2O3/Ca3P及ZrO2/Ca3P基板浸泡在1M H3PO4水溶液在25℃和80℃處理1hr後,基板表面的微觀組織59
圖4-4-5 不同基板在浸泡時間為1 h表面堆積物之SEM圖60
圖4-4-6 β-三鈣磷酸鹽粉末溶在1 M H3PO4水溶液之SEM圖61
圖4-4-7 不同基板浸泡在1M H3PO4水溶液80℃之SEM圖61
圖4-5-1 添加Ca離子提高pH值在Ca3P基板之XRD圖63
圖4-5-2 添加Ca離子提高pH值在glass基板之XRD圖63
圖4-5-3 在不同基板的表面型態之SEM圖64
圖4-5-4 當pH=2.5，亦即Ca2+　在溶液濃度增加時，Ca3P基板表面之XRD圖65
圖4-5-5 在pH=2.5時，Ca3P基板表面之SEM微觀組織65
圖4-6-1 Ca3P基板鹼性處理前後之XRD圖66
圖4-6-2 Ca3P基板鹼性處理前後之SEM圖68
圖4-6-3 Al2O3/Ca3P基板鹼性處理前後之XRD圖69
圖4-6-4 ZrO2/Ca3P基板鹼性處理前後之XRD圖69
圖4-6-5 Al2O3/Ca3P基板鹼性處理前後之SEM圖70
圖4-6-6 ZrO2/Ca3P基板鹼性處理前後之SEM圖72
圖4-6-7 ZrO2/Ca3P基板鹼性處理後之SEM圖和EDS圖73
圖4-6-8 Ca3P/Al2O3基板與鹼性處理前後之XRD圖75
圖4-6-9 Ca3P/ZrO2基板與鹼性處理前後之XRD圖75
圖4-6-10 Ca3P/Al2O3基板與鹼性處理前後之SEM圖76
圖4-6-11 Ca3P/ZrO2基板與鹼性處理前後之SEM圖77
圖4-7-1 HA粉末之FTIR光譜圖78
圖4-7-2 Ca3P基板之RAIR光譜圖79
圖4-7-3 複合基板之RAIR光譜圖79
表目錄
表2-1-1 生醫材料分類表5
表2-2-2 氧化鋁與Y-PSZ與性質11
表2-2-5-1 氫氧基磷灰石的物理與化學性質14
表2-2-5-2 人體骨骼和氫氧基磷灰石成分組成的比較15
表2-2-5-3 人體骨骼和氫氧基磷灰石機械性質的比較15
表2-3-1 氫氧基磷灰石的應用表22
表2-4-2-1 不同氫氧基磷灰石的覆層技術25
表2-5-2-1 各種磷酸鈣系鹽類名稱及其簡稱和化學式及Ca/P比28
表2-7-1 不同磷酸根離子穩定之pH 值範圍33
表3-3-1 XRD卡號41
表4-1-1 基板試片代號及名稱與其相組成表45

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