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研究生： 黃柏偉
Huang, Bo-Wei
論文名稱： 多孔性硫酸鈣之結構與機械性質研究
Investigation of the Structure and Properties of Porous Calcium Sulfate
指導教授： 陳瑾惠
Chern Lin, Jiin-Huey
朱建平
Ju, Chien-Ping
學位類別： 碩士
Master
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： 2007
畢業學年度： 95
語文別： 中文
論文頁數： 130
中文關鍵詞： 多孔性 、硫酸鈣
外文關鍵詞： calcium sulfate, porosity
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    • 人造支架用在治療骨缺陷和骨損壞已經有超過100年的歷史，直到今天它們仍然是治療大體積骨缺陷的有效方法。做為其他用途的骨取代物仍有很大的開發潛力。
    巴黎石膏是一種半水硫酸鈣的生物可吸收性陶瓷，它不貴而且消毒和製作都十分容易。
    在本研究中製作了一系列的硫酸鈣支架，並探討其性質。硫酸鈣支架以溶劑鑄造鹽洗法，並且以氯化鉀混合硫酸鈣，藉由改變硫酸鈣和氯化鉀的比例控制支架的孔隙度。支架浸泡在不同溶液中也可以改變其孔隙度和強度。

    Synthetic scaffold has been used in the treatment of bone defects and fractures for over 100 years. They remain a critical tool in the treatment of large-volume bone defects, and they role as potential substitues for bone graft.
    Plaster of Paris is a hemihydrate of calcium sulfate bioabsorbable ceramic. It is inexpensive, can be sterilized and prepared easily.
    In this study, a series of calcium sulfate scaffolds were prepared and characterized. Calcium sulfate scaffolds were prepared by solvent casting/particulate leaching method and calcium sulfate was mixed with potassium chloride. By changing calcium sulfate/ potassium chloride ratio the porosity of scaffold can be control. Scaffolds immerse in a series of can change their compressive strength and porosity.

    目錄 摘要 I ABSTRACT II 誌謝 III 目錄 IV 表目錄 IX 圖目錄 X 第一章 前言 1 1-1 研究背景 1 1-2 生醫材料的定義 2 1-3 生醫材料的分類 3 1-3-1 金屬材料（metal） 3 1-3-2 陶瓷材料(ceramic) 4 1-3-3 高分子材料(polymer) 4 1-3-4 複合材料(composite) 5 1-4 人體骨骼組織及性質簡介 10 1-4-1 人體骨骼的構造 10 1-4-2 細胞與功能 11 1-4-3 骨骼的成分 12 1-4-4 鈣和磷的代謝 13 1-4-5 骨骼創傷與修復 14 1-4-6 骨折癒合的分期 14 1-5 骨組織工程的概念 20 1-6 研究目的 20 第二章 文獻回顧 21 2-1 人工骨取代物 21 2-1-1 骨取代物的歷史 21 2-1-2 植入材料所需具備的條件 22 2-1-3 骨取代物的生物學要求 23 2-2 生醫陶瓷的種類 24 2-2-1 生物可吸收性陶瓷 24 2-2-2 生物活性陶瓷 24 2-2-3 生物惰性陶瓷 25 2-3 生物支架 27 2-4 多孔性陶瓷對生物活性的影響 27 2-4-1 多孔性陶瓷的基本性質 27 2-4-2 支架的滲透性 28 2-4-3 支架力學 30 2-4-4 生物反應的分類 32 2-4-5 化學反應對生物活性的影響 33 2-4-6 生醫陶瓷可吸收性的來源 34 2-4-7 不可吸收性生醫陶瓷 35 2-5 支架製備方法及優缺點比較 39 2-6 醫療用硫酸鈣發展歷史 43 2-7 硫酸鈣的基本性質 45 2-7-1 α型和β型半水硫酸鈣 45 2-7-2 加速劑對硫酸鈣結晶的影響 53 2-7-3 延遲劑對硫酸鈣結晶的影響 53 2-7-4 半水化合物進行水合反應成石膏的表面型態 54 2-7-5 石膏泥漿硬化的機械性質 54 第三章 實驗步驟與方法 58 3-1 實驗步驟 58 3-1-1 多孔性支架的製作與測試 58 3-1-2 浸泡實驗 58 3-2 實驗步驟與分析原理 61 3-2-1 抗壓強度測試 61 3-2-2 掃描式電子顯微鏡（SEM）分析 62 3-2-3 XRD繞射分析 64 3-2-4 孔隙度測試 67 3-2-5 毒性測試 67 第四章 結果與討論 69 4-1 不同清洗S0條件之比較 69 4-1-1 清洗S0之實驗參數 69 4-1-2 浸泡Hanks’ solution清洗S0之抗壓強度變化 69 4-1-3 浸泡S1清洗S0之抗壓強度 71 4-1-4 浸泡S1清洗S0之XRD分析 71 4-1-5 浸泡S1清洗S0後之SEM微觀結構觀察 72 4-1-6 浸泡S1清洗S0後之EDS分析 72 4-2 添加不同比例S0與壓力對清洗後支架性質的影響 82 4-2-1 添加不同比例S0與壓力對抗壓強度的影響 82 4-2-2 添加不同比例S0與壓力對孔隙度的影響 82 4-2-3 添加不同比例S0與壓力清洗後支架之SEM微結構觀察 82 4-3 浸泡不同溶液之性質變化 88 4-3-1 浸泡t1℃濃度t1℃濃度C1M~C3MS2及S3T1對抗壓強度之影響 88 4-3-2 浸泡t1℃濃度C1M~C3MS2及S3T1之XRD分析 88 4-3-3 浸泡t1℃濃度C1M~C3MS2及S3T1SEM微觀結構觀察 88 4-3-4 浸泡t1℃濃度C4M~C6MS2及S3T1~T7對抗壓強度之影響 89 4-3-5 浸泡t1℃濃度C4M~C6MS2及S3XRD分析 89 4-3-6 浸泡t1℃C6M S2T1~T7SEM微觀結構觀察 90 4-4 支架降解測試 106 4-4-1 浸泡t1℃S1時間對抗壓強度變化 106 4-4-2 浸泡t1℃S1XRD分析 106 4-4-3 浸泡t1℃S1SEM微觀結構 106 4-4-4 浸泡t2℃細胞培養液T1~T7對抗壓強度變化 106 4-4-5 浸泡t2℃細胞培養液T1~T7之XRD分析 107 4-4-6 浸泡t2℃細胞培養液T1~T7之SEM微觀結構 107 4-4-7 浸泡t1℃S1及Hanks’ solutionT1~T3之抗壓強度變化 107 4-4-8 浸泡t1℃S1及Hanks’ solution T1~T3之XRD分析 107 4-4-9 浸泡t1℃S1及Hanks’ solutionT1~T3之SEM微觀結構 108 4-5 細胞毒性測試 122 第五章 結論 124 參考文獻 125 表目錄 表 1-3 1生醫材料的分類與應用。 7 表 1-3 2有關生醫植入材料的重要發展簡列(Part I)。 8 表 1-3 3有關生醫植入材料的重要發展簡列(Part II)。 9 表 1-4 1自然骨(bone)的機械性質。 19 表 2-2 1 人體骨骼與常見生醫陶瓷之機械性質比較。 26 表 2-2 2生醫陶瓷各種性質及用途之综合比較。 26 表 2-4 1常用的生醫陶瓷骨取代物材料 36 表 2-4 2組織反應分類 37 表 2-6 1 α和β型半水硫酸鈣性質 48 圖目錄 圖 1-4 1人體的骨骼系 16 圖 1-4 2人體骨骼構造，緻密骨皮質骨以及骨基質示意圖。 17 圖 1-4 3骨骼受創傷後自行癒合之情形與步驟。 18 圖 2-4 1 HA多孔性陶瓷結構示意圖: 38 圖 2-6 1 不同型態的硫酸鈣CaSO4xH2O 49 圖 2-6 2兩種不同的半水硫酸鈣SEM照片 50 圖 2-6 3α型和β型半水硫酸鈣的水合反應溫度對時間的關係 51 圖 2-6 4α型和β型半水硫酸鈣水合反應中電阻對時間的變化 52 圖 3-1 1實驗流程圖part I，製作多孔性支架 59 圖 3-1 2實驗流程圖part II，浸泡實驗 60 圖 3-3 1掃描式電子顯微鏡作用示意圖 63 圖 3-3 2X-RAY 繞射分析儀示意圖 66 圖 4-1 1添加50%、60% S0，施加P1Kgf製成之試片浸泡在t1℃Hanks’ solutionT1至T3天之抗壓強度變化 73 圖 4-1 2添加p1%、p2% S0，施加P1Kgf製成之試片浸泡在t2℃Hanks’ solution之抗壓強度變化 74 圖 4-1 3添加p1%、p2% S0，施加P2Kgf製成之試片浸泡在t1℃Hanks’ solution之抗壓強度變化 75 圖 4-1 4添加p1%、p2% S0，施加P2Kgf製成之試片浸泡在t2℃Hanks’ solution之抗壓強度變化 76 圖 4-1 5浸泡S1及Hanks’ solution清洗S0之抗壓強度變化 77 圖 4-1 6添加p1% S0以S1清洗T1~T4之XRD 78 圖 4-1 7添加p1% S0浸泡t1℃S1T3之SEM照片 79 圖 4-1 8添加p1% S0浸泡t1℃S1T2之SEM照片 80 圖 4-1 9浸泡t1℃S1T2~T3天清洗S0之EDS分析結果 81 圖 4-2 1添加不同S0比例對抗壓強度的影響 84 圖 4-2 2添加不同S0比例對孔隙度的影響 85 圖 4-2 3施加P2Kgf壓力下添加不同S0比例以去S1清洗T3後之SEM照片 86 圖 4-2 4施加P1Kgf壓力下添加不同S0比例以S1清洗T3後之SEM照片 87 圖 4-3 1浸泡t1℃濃度C1M~C3MS2及S3T1之抗壓強度變化 91 圖 4-3 2浸泡37℃濃度C1M~C3MS2S3T1之抗壓強度變化 92 圖 4-3 3浸泡t1℃濃度C1M~C3MS2及S3T1之XRD分析，對照組二水硫酸鈣 93 圖 4-3 4浸泡t1℃濃度C1M~C3MS2T1之SEM圖 94 圖 4-3 5浸泡t1℃濃度C4M~C6MS3T1~T7之抗壓強度變化 95 圖 4-3 6浸泡t1℃濃度C4MS2之T1~T7抗壓強度變化 96 圖 4-3 7浸泡t1℃C4S2T1~T7 SEM圖 98 圖 4-3 8浸泡t1℃C5M~C6MS2之抗壓強度變化 99 圖 4-3 9浸泡t1℃C6MS2之孔隙度變化 99 圖 4-3 10浸泡t1℃C5MS2之XRD分析 100 圖 4-3 11浸泡t1℃C6M S2之XRD分析 100 圖 4-3 12浸泡t1℃C6MS2SEM圖 102 圖 4-3 13浸泡t1℃C6MS2T7~T10之抗壓強度變化 103 圖 4-3 14浸泡t1℃C6MS2T7~T10之XRD分析 104 圖 4-3 15浸泡t1℃C6MS2T8 ~ T10之SEM照片 105 圖 4-4 1浸泡t1℃S1時間對抗壓強度變化 109 圖 4-4 2浸泡t1℃S1清洗S2不同時間之XRD分析 110 圖 4-4 3浸泡t1℃S1清洗S2之SEM照片 111 圖 4-4 4浸泡S1清洗S2T3之EDS分析結果 112 圖 4-4 5浸泡t2℃細胞培養液T1~T7之抗壓強度變化 113 圖 4-4 6浸泡t2℃細胞培養液T1~T7之XRD分析 114 圖 4-4 7浸泡t2℃細胞培養液T1~T3之SEM照片 115 圖 4-4 8浸泡t2℃細胞培養液T4~T7之SEM照片 116 圖 4-4 9浸泡t1℃S1及Hanks’ solution T1~T3之抗壓強度變化 117 圖 4-4 10浸泡t1℃S1及Hanks’ solution T1~T3之孔隙度變化 118 圖 4-4 11浸泡t1℃S1及Hanks’ solution T1~T3清洗S2之XRD分析 119 圖 4-4 12浸泡t1℃去S1T1~T3之SEM照片 120 圖 4-4 13浸泡t1℃Hanks’ solution T1~T3清洗S2之SEM照片 121 圖 4-5 1多孔性硫酸鈣細胞毒性測試 123

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