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研究生: 王益昌
Wang, I-Chang
論文名稱: 磷酸鈣骨水泥結構、性質及 伽瑪射線對性質之影響
Structure、properties and the effect of gamma-ray radiation of calcium phosphate cement
指導教授: 朱建平
Ju, Chien-Ping
陳瑾惠
Chern Lin, Jiin-Huey
學位類別: 博士
Doctor
系所名稱: 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年: 2005
畢業學年度: 93
語文別: 中文
論文頁數: 138
中文關鍵詞: 伽瑪射線消毒穿透式電子顯微鏡磷酸鈣骨水泥
外文關鍵詞: sterilization, gamma-ray, transmission electron microscopy, calcium phosphate cement
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  •   由於鈣磷系骨水泥(CPC)具有優異的生物相容性及引骨性,因此在牙科及外科手術上常用來當作填充修補材料。以四鈣磷酸鹽(TTCP)/ 二鈣磷酸鹽(DCPA)為主要成分的鈣磷系骨水泥的硬化機制一般認為與磷灰石(apatite)的生成有關,為了瞭解反應過程中鬚晶或針狀結晶(whiskers or needle-like crystals)的生成對於硬化機制之影響且避免分析上的困難,本實驗使用單一成分四鈣磷酸鹽粉末為原料,並使用磷酸氫二銨(diammonium hydrogen phosphate,(NH4)2HPO4)鹼性溶液來作為處理鬚晶成長的溶液,在不同的鬚晶前處理時間觀察其微結構的變化。

      實驗結果發現隨著四鈣磷酸鹽表面鬚晶處理時間的增加,鬚晶型態從細小球狀逐漸成長為細長型鬚晶,且鬚晶的長度及寬度亦逐漸增加,因此我們提出在此鈣磷系骨水泥實驗中長度增加速度較寬度快,鬚晶的相則由初期的非晶質結構逐漸轉變成四鈣磷酸鹽晶格結構,最後變成磷灰石的晶格結構。而抗壓強度隨著初期鬚晶的成長(低於10 分鐘處理)而略微增加,但當鬚晶結構開始變成磷灰石相(30 分鐘處理)時,強度亦下降,直到以磷灰石相為主時強度降至最低。

      經過表面處理的四鈣磷酸鹽亦做細胞培養及動物植入實驗以評估其生物相容性。實驗結果顯示該材料無細胞毒性,並於兔子植入後之組織切片觀察結果亦顯示出對植入材周圍的組織無不良影響且有良好的鍵結,顯示表面處理不影響其生物相容性。

      本研究另一方面探討四鈣磷酸鹽/二鈣磷酸鹽鈣磷系骨水泥經不同γ-ray 照射劑量消毒滅菌後,對其機械性質,包括操作時間、硬化時間及抗壓強度的影響。實驗結果發現,當γ-ray 劑量強度到達30 kGy 時,4操作時間及硬化時間均會變長,且抗壓強度為最高,經過氫氧基磷灰石(HA)生成率的計算結果亦發現,四鈣磷酸鹽/二鈣磷酸鹽鈣磷系骨水泥經30 kGy γ-ray 劑量強度消毒滅菌後,其氫氧基磷灰石生成率為最高。SEM 觀察微結構的結果亦顯示出隨著γ-ray 劑量強度的增加,其微結構亦由花瓣型(sharp-edged petal-like morphology)結構(10 kGy)變成圓柱型(globular-like morphology)(30 kGy),到80 kGy 時變成以珊瑚型(dull-edged coralline-like morphology)為主要的結構。

      Due to its superior biocompatibility and osteoconductivity, calcium phosphate cement (CPC) has been suggested for use as a filling material in dental and orthopedic applications. It is generally accepted that the setting mechanism of TTCP/DCPA (dicalcium phosphate anhydrous, CaHPO4) -
    based CPC involves formation of apatite crystals. To eliminate such complications and single out the effect of whisker treatment on TTCP in basic solution, the present study investigates the changes in microstructure and microchemistry during whisker formation on the surface of a monolithic TTCP powder in a basic phosphoric acid solution using TEM technique.

     The results are as whisker-treating time increased, the whiskers continued to grow in length and width. The initial structure of whisker is amorphous and becomes non-stoichiometric TTCP in ten min treated-time.The final crystal structure is apatite. The average 1 d-compressive strength of the CPC remains high (>40 MPa) when the treating time was 10 min or less.
    When the treating time increased to 30 min the compressive strength of the CPC largely declined. When apatite starts to dominate the surface, the strength of the CPC largely declines.

     To assess the biocompatibility of surface-treated TTCP, cytotoxicity and implantation tests were studied. The results of cytotoxicity and histology show that the surface-treated TTCP is not cytotoxicity and can induce the
    growth of the natural bone.

     The purpose of the other study is to investigate the γ-ray effect on the structure and some critical properties, such as working/setting time and compressive strength, of a TTCP/DCPA-based CPC. Experimental results indicate that working/setting time, compressive strength, TTCP-HA
    conversion rate and morphology of the present CPC are all related to the dosage of γ-ray sterilization. The best γ-ray dosage appears to be 30 kGy which leads to slightly longer setting/working time, the highest TTCP-HA
    conversion rate and the highest compressive strength. With increasing γ-ray dosage, the morphology of CPC changed from sharp-edged petal-like morphology (10 kGy) to globular-like morphology (30 kGy) to dull-edged coralline-like morphology (80 kGy).

    中文摘要……………………………………………………………………...3 英文摘要abstract…………………………………………………………….5 致謝……………………………………………………….…………………..7 總目錄………………………………………………………………………...8 圖目錄……………………………………………………………………….11 表目錄……………………………………………………………………….15 第一章總緒論………………………………………………………………16 1-1 生醫植入材料分類及發展簡介……………………………………..16 1-2 人體硬組織成分及性質簡介…………………………………….….26 1-3 骨科植入材料性質…………………………………………………..32 1-4 氫氧基磷灰石性質…………………………………………………..34 1-4-1 氫氧基磷灰石的特性………………………..……………….34 1-4-2 氫氧基磷灰石的晶體結構…………………………………...35 1-4-3 氫氧基磷灰石的環境穩定性………………………………...35 1-4-4 氫氧基磷灰石結構中的離子取代現象……………………...36 1-4-5 生物合成的磷灰石…………………………………………...36 第二章鈣磷系骨水泥的發展與簡介………………………………………44 2-1 鈣磷系列生醫陶瓷分類與發展…………………………………….44 2-2 鈣磷系鹽類的溶解相圖…………………………………………….47 2-3 鈣磷系鹽類水解形成氫氧基磷灰石…………………………….....48 2-4 四鈣磷酸鹽的水解………………………………………………….52 2-5 非晶質磷酸鈣鹽類…………………………………………….55 2-5-1 非晶質磷酸鈣鹽類的基本性質……………………..…55 2-5-2 非晶質磷酸鈣鹽類的結構……………………………..55 2-6 鈣磷系骨水泥的優缺點及應用……………………………….……59 第三章消毒方法的簡介……………………………………………………62 3-1 完全消毒滅菌的定義………………………………………………..62 3-2 消毒滅菌方法的分類與比較………………………………………..63 3-3 消毒方法對生醫植入材性質的影響………………………………..69 第四章穿透式電子顯微鏡在四鈣磷酸鹽粉末表面處理後之微結構 分析…………………………………………………………………72 4-1 前言…………………………………………………………………..72 4-2 實驗方法……………………………………………………………..74 4-2-1 四鈣磷酸鹽原始粉末製備…………………….……………..74 4-2-2 四鈣磷酸鹽表面處理及TEM 試片之製作…………………74 4-2-3 XRD 分析…………………………………………...……….74 4-2-4 抗壓強度的測量……………………………………………...75 4-3 結果與討論…………………………………………………………..78 4-4 結論…………………………………………………………………..81 第五章γ-ray消毒滅菌法對四鈣磷酸鹽/無水二鈣磷酸鹽鈣磷系骨水泥性 質的影響…………………………………………………………..91 5-1 摘要…………………………………………………………………..91 5-2 前言…………………………………………………………………..92 5-3 實驗方法……………………………………………………………..94 5-3-1 鈣磷系骨水泥材料製備……………………………………...94 5-3-2 抗壓強度測試………………………………………………...94 5-3-3 工作及硬化時間的測量……………………………………...95 5-3-4 硬化期間pH 值分析………………………………………....95 5-3-5 XRD 分析…………………………………………………….95 5-3-6 四鈣磷酸鹽-氫氧基磷灰石轉換率的計算………………….96 5-3-7 SEM 表面觀察……………………………………………….96 5-3-8 FTIR 分析…………………………………………………….96 5-4 結果與討論…………………………………………………………..99 5-5 結論…………………………………………………………………103 參考資料…………………………………………………………………...125 作者簡介及論文著作……………………………………………………...137

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