臺灣博碩士論文加值系統

氫氧基磷灰石鍍層己經使用在承載負荷的硬組織植體應用上。本研究利用電漿噴鍍技術製造功能性HA/Ti漸層在Ti6Al4V基材上，以改善鍍層-基材界面特性。這種漸層方式是採用底層為Ti鍵結層，表層為HA層，中間則是HA/Ti混合層，混合層是以改變Ti和HA粉末的輸入速率和粉量，將Ti含量隨著厚度增加而減少。在本論文中，將探討HA/Ti漸層及其經過後續熱處理，對其抗腐蝕性、塗層-基材之界面穩定性、與鍵結強度有何影響。實驗的結果指出功能性漸層的表面化學性質和形態跟純HA鍍層相似。但漸層的鍵結強度則較優於HA單層。疲勞循環測試發現HA鍍層鍵結強度顯著下降23%，然而在一百萬次的循環載荷下的HA/Ti漸層並沒有明顯的強度減少。適當的熱處理讓漸層的非晶質磷酸鈣結晶化。在模擬體液下電化學測量的結果也指出在疲勞測試後，漸層比單獨HA鍍層有較好的性質。經熱處理後抗腐蝕性提高。經600oC熱處理，不但能夠增加結晶性和降低鍍層缺陷，而且增加鍵結強度，噴鍍後熱處理可提升HA/Ti漸層品質。

Hydroxyapatite coating have been used as load-bearing implant
applications. The aim of this work is to deposit functionally graded HA/Ti
layers using plasma spray to improve the coating-substrate interface
properties. In addition to the Ti bondcoat and the top HA biolayer, the
alternating layers were created by means of changing the feeding rate and
input powder of Ti and HA. The stability of the graded coatings such as
corrosion resistance and fatigue, and bonding strength of the potential
graded coatings without and with post-deposition heat treatment were
examined. Results showed that surface chemistry and morphology of the
graded coatings were similar to those of monolithic HA coatings. The
bonding strength values of the as-sprayed graded coating were much
superior to those of monolithic HA coatings. The cyclic fatigue did have a
statistically significant effect on bond strength of monolithic HA coatings,
with a decrease of 23%. However, the graded coatings were able to survive 1
million cycles of loading in air without significantly reduced bond strength.
The in vitro electrochemical measurement results also indicated that the
graded coatings had a more beneficial and desired behavior than monolithic
HA coatings after fatigue. An appropriate heat treatment resulted in
recrystallization of amorphous calcium phosphate of as-sprayed coatings.
The enhancement of the resistance to corrosion took place after heat
treatment. Consequently, we concluded that the heat treatment at 600℃,
endowing with increased crystallinity and the reduced defects as well as
enhanced bond strength, may be a suitable post-deposition treatment method
to promote the characteristics of graded HA/Ti coatings.

總目錄
致謝.............................................................................................................I
中文摘要................................................................................................... II
Abstract ...................................................................................................III
總目錄......................................................................................................IV
表目錄......................................................................................................VI
圖目錄.................................................................................................... VII
第一章 文獻回顧......................................................................................1
1-1 生醫骨科材料.................................................................... 1
1-2 鈦金屬................................................................................ 2
1-3 氫氧基磷灰石的基本性質................................................. 5
1-3-1 氫氧基磷灰石的合成............................................... 5
1-3-2 氫氧基磷灰石在室溫下水溶液中的穩定性........... 7
1-4 人工牙根............................................................................ 8
1-4-1 人工牙根表面之探討............................................... 9
1-4-2 人工牙根之表面技術............................................. 10
1-4-3 電漿噴塗技術......................................................... 13
1-4-4 電漿噴塗陶瓷塗層之性質..................................... 15
1-4-5 影響塗層性質的電漿噴塗參數............................. 15
1-5 電漿噴鍍氫氧基磷灰石鍍層........................................... 16
1-5-1 氫氧基磷灰石於高溫下之穩定性......................... 16
1-5-2 氫氧基磷灰石之生物親合性................................. 17
第二章 實驗步驟....................................................................................18
2-1 電漿噴塗塗層製程.......................................................... 18
2-2 電漿噴度後熱處理.......................................................... 19
2-3 相組成和顯微結構分析................................................... 19
2-4 噴塗層鍵結強度測定和疲勞測試................................... 20
2-5 電化學測試...................................................................... 20
2-6 統計學分析...................................................................... 20
第三章 結果與討論................................................................................22
3-1 電漿噴鍍後之成份組成分析........................................... 22
3-2 顯微結構.......................................................................... 26
3-3 疲勞測試和熱處理之鍵結強度....................................... 28
3-4 電化學測試...................................................................... 30
V
第四章 結論............................................................................................35
第五章 參考文獻....................................................................................36
VI
表目錄
圖一、 商業HA 粉末及HA 鍍層、HA/Ti 漸層表面之X 光繞射結果
(H：apatite；A：α-TCP；B：β-TCP：C：CaO)......................23
圖二、商業HA 粉末及HA 鍍層、HA/Ti 漸層表面之複利葉紅外線
光譜結果..........................................................................................23
圖三、電漿噴塗後(a)及其分別於400℃(b)、500℃(c)、600℃(d)及700
℃(e)下進行後續熱處理，塗層表面之X 光繞射結果 (H：
apatite；A：α-TCP；B：β-TCP；C：CaO)..............................25
圖四、電漿噴塗後(a)及其分別於400℃(b)、500℃(c)、600℃(d)及700
℃(e)下進行後續熱處理，塗層表面之複利葉紅外線光譜結果...25
圖五、(a)漸層噴鍍截面SEM 微結構圖及(b)漸層噴鍍縱向Ti、Ca 與
P 之元素分析結果...........................................................................26
圖六、漸層噴鍍(a)及其分別於400℃(b)、500℃(c)、600℃(d)及700
℃(e)下進行後續熱處理，噴塗層截面SEM 微結構圖................27
圖七、漸層噴鍍及其分別於400℃、500℃、600℃及700℃下進行後
續熱處理，噴塗層與基材之結合強度...........................................29
圖八、HA 鍍層在疲勞測試(a)前、(b)後及HA/Ti 鍍層在疲勞(c)前、
(d)後開路電位圖.............................................................................31
圖九、HA 鍍層在疲勞測試(a)前、(b)後及HA/Ti 鍍層在疲勞(c)前、
(d)後典型極化曲線圖......................................................................31
圖十、漸層鍍層(a)、及其分別於400℃、500℃、600℃及700℃下進
行後續熱處理，在除氧之Hank’s balanced salt solution 下所得開
路電位圖..........................................................................................33
圖十一、漸層鍍層(a)、及其分別於400℃、500℃、600℃及700℃下
進行後續熱處理，所得典型極化曲線圖.......................................34
VII

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