臺灣博碩士論文加值系統

本研究以sol-gel法和化學共沉法來製備氫氧基磷灰石(HA)厚膜；sol-gel法中前趨物是以含四個結晶水的硝酸鈣Ca(NO3)2．4H2O溶於甲醇、乙醇和RO水不同的溶劑中，和三乙基磷酸酯反應生成HA gel，在以旋鍍的方式塗佈於基材表面。而化學共沉法是以氫氧化鈣Ca(OH)2溶解於醋酸(CH3COOH)中，在不同的pH值環境中和磷酸水溶液反應共沉塗佈於基材上。
在sol-gel法方面以不同溶劑經熟化後所配製出的gel有不同的pH值。而在化學共沉法方面，在pH值為4~5時會產生Ca PO3(OH)．2H2O的相，在pH值為6~8時會產生氫氧基磷灰石。
由gel的DTA和TGA熱分析中顯示HA約在600℃後產生，在不同溫度熱處理下的XRD分析中，可以清楚的看出在350℃、400℃熱處理下只有非晶質的相產生，在600℃下則有HA的結晶相產生。
經過旋鍍塗佈後以不同的升溫速率下熱處理，在SEM的顯微組織中可發現較低的旋鍍轉速下可得較大的HA膜厚，且熱處理的溫度提高時，膜的表面會有孔隙狀的結構產生，在600℃熱處理下的HA厚膜表面孔隙直徑約為2.5μm，在700℃下熱處理孔隙直徑上升至5~10μm。此外，降低熱處理的昇溫速率可以減少孔隙狀結構的產生。而由化學沉積法所形成HA厚膜的表面微觀組織，未經煆燒的基材表面在pH值4~6時為片狀結構，在pH值7~8時為粉末顆粒狀結構所構成。經煆燒後隨著pH值得上升，HA厚膜也越平滑；在兩種不同方式的鍍膜下可發現以化學沉積法所得之HA厚膜較sol-gel法來的平滑。
在林格氏液中的sol-gel HA厚膜隨著浸泡時間的增加，膜重也有逐漸的增加。經SEM表面微觀組織的觀察中可發現HA膜表面有析出物的產生造成重量的上升。

In this syudy, Hydroxyapatite (HA, Ca10(PO4)6(OH)2 ) thick films were prepared from sol-gel and coprecipitation method. In the sol-gel method, HA thick films were prepared from the precursors Ca(NO3)2, PO(C2H5O)3, and various solvents including methanol, ethanol, and H2O. The gel was coated on the substrate by spinning coating. For the coprecipitation method, the initial solution of Ca2+ and PO43- were obtained from Ca(OH)2+ CH3COOH and H3PO4+H2O. These two solutions were adjusted at the same pH value before mixing to let the precipitates coated on the substrate.
In the sol-gel method, the gel have different pH value with different solvent after aging. In the coprecipitation method, the major phase was HA when its precursor solution’s pH=6~8, and Ca PO3(OH)．2H2O for pH=4~5.
By DTA and TGA analysis, the gel-coated specimens started to form the hydroxyapatite crystallines at T=~600oC upon heating. From the corresponding X-ray diffraction patterns, there are only amorphous at T=300 and 400℃. But hydroxyapatite crystallines were be found at T=600℃.
By SEM surface morphologies of heat-treated HA thick film after spin-coating, lower coating speed can increase film’s width. A porous surface appeared at high-temperature, the pole size is 2.5μm at 600℃ and 5~10μm at 700℃. However, a lower raising temperature can decrease the porous surface structure. For the coprecipitation method, before calcinations the surface of substrate is plate structure at pH=4~6, and pellet structure at pH=7~8. After calcinations, the HA thick film showed a smooth surface. Between two coating methods, the coprecipitation method formed a smoother surface than sol-gel method.
In Ring’s injection, the weight of sol-gel method HA thick film was increased by days. From SEM surface morphologies, there were educt on the surface of HA thick film, it increased the weight of HA thick film.

中文摘要…………………………………………………………………….……Ⅰ
英文摘要………………………………………………………………………….Ⅲ
誌謝……………………………………………………………………….....……Ⅴ
總目錄……………………………………………………………….……..…..…Ⅵ
圖目錄………………………………………………………………………..…...Ⅷ
表目錄…………………………………………………………………………..…X
第一章 緒論………………………………..………………………………….…1
1-1 研究背景………………...………..……………………………………1
1-2 生醫材料之簡介………………………………………………………...1
1-2-1 生醫材料之定義與發展………………………………..…………..1
1-2-2 生醫陶瓷材料的發展與種類…………………..…………………..4
1-3 研究方向
第二章 理論背景與前人研究…………………………………………………10
2-1 氫氧基磷灰石之特性………………………………………………….10
2-1-1 氫氧基磷灰石之生物活性………………………………………………10
2-1-2 氫氧基磷灰石之基本性質與結構………………………….…….12
2-1-3 氫氧基磷灰石之合成與高溫性質………………….…………….16
2-2 Sol-Gel法製製程簡介…..……………………………….………………….21
第三章 實驗方法………………..…………………………………….………..24
3-1 實驗藥品與儀器……………………………………………………….24
3-1-1 實驗藥品…………………….…………………………………….24
3-1-2 實驗儀器……………….………………………………………….25
3-2 實驗流程……………………………………………………...………..27
3-2-1 以sol-gel法製備氫氧基磷灰石之流程………………………….27
3-2-2 化學共沉法………………………………………………………..30
第四章 結果與討論…………………………..……………………..………….32
4-1 Sol-gel法前趨物之配製…………….…………………….………….32
4-2 熟化和乾燥後sol-gel之DTA與TGA分析…………………………34
4-3 X-光繞射光譜(XRD)……………………….……………………...…39
4-4 SEM微觀組織觀察…………………………………………..………42
4-5 模擬體液觀察…………………………………………….……………48
4-6 以化學共沉法沉積氫氧基磷灰石…………………………………….50
4-6-1 X-光繞射光譜(XRD)……………………….……………………..50
4-6-2 SEM微觀組織觀察………………….……………………….……52
第五章 結論………………………………….…………………………………56
參考文獻………………………………………………………………….………57

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