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研究生： 范乃妍
Fan, Nai-Yen
論文名稱： 硫酸鈣骨水泥性質研究
Investigation of Properties of Calcium Sulfate Cement
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： 2006
畢業學年度： 94
語文別： 中文
論文頁數： 81
中文關鍵詞： 硫酸鈣骨水泥 、生物可吸收性陶瓷 、生醫材料
外文關鍵詞： calcium sulfate, bone conductivity, biomaterial
相關次數： 點閱：185  下載：4 
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    • 中文摘要
    硫酸鈣在生醫材料領域，已展現優良的生物相容性及骨引導性，但缺點是植入人體後吸收速度會過快。本實驗中將半水硫酸鈣與水溶液反應，欲作抗壓強度測試的試片勢將原本的cement填入不銹鋼模中使其在模中硬化，最後將試片置於模擬人體的生理環境-Hanks’ solution中。一天抗壓強度測試之結果，發現bM的溶液C能使硫酸鈣骨水泥的抗壓強度達36MPa，即使浸泡了三十天之久，仍然有17MPa。
    XRD分析顯示二水硫酸鈣是半水硫酸鈣與水溶液反應後之最終相。SEM觀察結果則發現二水硫酸鈣的針狀結構，其形態表現會隨著反應的硬化劑種類而有所改變；本實驗中，此較高的抗壓強度將對應粗短型的針狀結構。
    改變溶液C的pH值以會影響硫酸鈣的水合反應行為；添加氫氧化鈉在溶液C中會造成反應加快，這個現象亦可解釋為何此時硫酸鈣骨水泥的抗壓強度會大幅衰退，且二水硫酸鈣結晶長度相當長。

    Abstract
    Being the biomaterial, calcium sulfate has shown excellent biocompatibility and bone conductivity but has rapid resorption in the human body. An attempt was made by mixing calcium sulfate hemihydrate and aqueous solutions. Samples for compression test were obtained putting the cement paste into stainless steel moulds where allowed to set, and then they were immersed in Hanks’ solution to simulate a physiological environment. For cement immersed one day, the highest compressive strength, 36MPa, was obtained for the samples mixed with solution C of concentration b while the cement immerse thirty days still had strength, 17MPa.
    X-ray analysis showed that calcium sulfate dihydrate is the final phase when calcium sulfate hemihydrate reacted with aqueous solution. In observation of SEM, the cement that initially was pure calcium sulfate hemihydrate that hydration had been processed mixing with aqueous solution and formed calcium sulfate dihydrate with their needles characteristic. These needle structure morphologies would change when calcium sulfate hemihydrate reacted with different hardening solutions. In this experiment, higher compressive strength would leaded by the short and wide needle structure.
    The behavior of hydration of calcium sulfate would varied by changing pH values. Adding NaOH in solution C to adjust higher pH value fastened the hydration reaction. This phenomenon could explain why compressive strengths of samples in these cases were so poor. Relative to it’s length, calcium sulfate dihydrate crystals were longer.

    總目錄 第一章 總緒論...........................................01 1-1 生醫植入材料分類及發展簡介.......................01 1-2 人體硬組織成分及性質簡介.........................09 1-2-1 人體之骨骼.......................................09 1-2-2 骨骼的創傷癒合...................................10 1-3 生物陶瓷的種類...................................16 1-4 生醫骨科人工植入材料所需具備的條件...............20 1-4-1 骨取代物的生物學要求.............................20 1-4-2 人工骨取代物材料性與製程的要求...................21 1-4-3 骨水泥作為骨缺填充材的材料性質要求...............21 第二章 硫酸鈣簡介.......................................23 2-1 硫酸鈣之結構及相轉換.............................23 2-2 硫酸鈣之水合硬化過程.............................29 2-3 液粉比(liquid-to-powder ratio, L/P)..............30 2-4 硫酸鈣作為骨水泥的優勢...........................31 2-5 硫酸鈣用作生醫植入材的發展回顧...................33 2-6 以硫酸鈣為主的雙相/多相生醫複合材料..............34 2-6-1 CaSO4･ 1/2H2O/ HA composite......................34 2-6-2 CaSO4･ 2H2O/ α-TCP composite....................35 2-6-3 CaSO4/PLLA composite.............................36 2-7 研究目的.........................................42 第三章實 驗原理及步驟.....................................43 3-1 實驗使用藥品.....................................43 3-2 實驗步驟及分析方法...............................43 3-2-1 抗壓強度測試.....................................43 3-2-2 工作及硬化時間的測量.............................43 3-2-3 硬化期間pH值分析.................................44 3-2-4 Hank’s solution pH值量測........................45 3-2-5 X-Ray Diffraction (XRD)分析......................45 3-2-6 Scanning Electron Microscopy(SEM) 表面觀察.......45 第四章 結果與討論.......................................53 4-1 以不同溶液作為硬化劑對硫酸鈣骨水泥性質影響之結果與討 論….............................................53 4-1-1 工作及硬化時間測量結果...........................53 4-1-2 抗壓強度分析.....................................54 4-1-3 SEM微結構觀察....................................55 4-1-4 XRD分析..........................................55 4-2 溶液C濃度改變對硫酸鈣骨水泥性質之影響............62 4-2-1 工作及硬化時間測量結果...........................62 4-2-2 抗壓強度分析.....................................62 4-2-3 SEM微結構觀察....................................63 4-2-4 XRD分析..........................................63 4-3 調整溶液酸鹼度對硫酸鈣骨水泥性質之影響............67 4-3-1 工作及硬化時間測量結果............................67 4-3-2 抗壓強度分析......................................67 4-3-3 SEM微結構觀察.....................................68 4-3-4 XRD分析...........................................68 4-4 硫酸鈣骨水泥短時間及長時間浸泡之結果..............72 4-4-1 抗壓強度分析......................................72 4-4-2 SEM微結構觀察.....................................72 4-4-3 XRD分析...........................................73 結論......................................................77 參考文獻..................................................78 表目錄 表1-1-1 生醫材料的分類與應用.............................06 表1-1-2 有關生醫植入材料的重要發展簡列(Part I)...........07 表1-1-2 有關生醫植入材料的重要發展簡列(Part II)..........08 表1-2-1. 自然骨(bone)的機械性質...........................15 表1-3-2 人體骨骼與常見生醫陶瓷之機械性質比較.............19 表1-3-3 生醫陶瓷各種性質及用途之综合比較.................19 表2-6-1 (a)HA粉末的比表面積 (b)HA粉末的粒徑分布..........38 表3-1-1 實驗所用藥品名稱及來源...........................47 表3-2-1 Hanks' solution 化學成分表.......................49 表4-1-1 酸性溶液的種類及pH值與硫酸鈣工作及硬化時間關係...57 表4-1-2 鹼性溶液的種類及pH值與硫酸鈣工作及硬化時間關係...57 表4-2-1 溶液C濃度變化與硫酸鈣工作及硬化時間關係..........64 表 4-2-2 溶液C濃度變化與硫酸鈣工作及硬化時間關係..........71 表 4-3-1 調整溶液C的酸鹼值對硫酸鈣骨水泥工作及硬化時間之影響 .................................................69 表4-3-2 調整溶液C的酸鹼值對硫酸鈣骨水泥工作及硬化時間之影響 .................................................82 圖目錄 圖1-2-1 人體的骨骼系統...................................12 圖1-2-2 人體骨組織架構...................................13 圖1-2-3 人體骨骼構造，緻密骨皮質骨以及骨基質示意圖.......14 圖1-2-4 骼受創傷後自行癒合之情形與步驟...................16 圖2-1-1 半水硫酸鈣的繞射峰圗.............................25 圖2-1-2 二水硫酸鈣的繞射峰圗.............................25 圖2-1-3 無水硫酸鈣結構...................................26 圗4-1-3 以水溶液(a)為對照組，硫酸鈣骨水泥以(b)鹽酸和(c)溶液 A作硬化劑，浸泡一天的微結構比較..................59 圗4-1-4 以水溶液(a)為對照組，硫酸鈣骨水泥以碳酸鈉(b)和溶液 C(c)作硬化劑，浸泡一天的微結構比較...............60 圖4-1-5 硫酸鈣骨水泥以鹽酸、溶液A碳酸鈉和溶液C作硬化劑， 浸泡一天後與原始粉末及硫酸鈣骨水泥和純水反應浸泡 一天的XRD圖比較..................................61 圖4-2-1 改變溶液C濃度對硫酸鈣骨水泥浸泡Hanks’ solutionㄧ 天抗壓強度結果...................................64 圖4-2-2 以不同濃度的溶液c溶液(a)aM (b)bM (c)cM (d)dM作為 硬化劑，硫酸鈣骨水泥浸泡一天後之結晶形態.........65 圖4-2-3 以純水和不同濃度的溶液C作為硫酸鈣骨水泥的硬化劑 浸泡一天後之XRD分析..............................66 圖4-3-1 調整溶液C酸鹼值對硫酸鈣骨水泥浸泡Hanks’ solution ㄧ天抗壓強度之結果...............................69 圖4-3-2 調整bM的溶液C酸鹼值(a)為未調整(b)pH=φ的硫酸鈣骨水 泥浸泡Hanks’ solution 一天的微結構形態..........70 圖4-3-3 調整溶液C酸鹼值後的硫酸鈣骨水泥浸泡Hanks’solution 一天之XRD分析....................................71 圗4-4-1 以純水、溶液C做為硫酸鈣骨水泥硬化劑的乾壓(dry)及 不同天數之濕壓之抗壓強度結果比較.................74 圗4-4-2 以bM的溶液C作為硫酸鈣骨水泥之硬化劑，浸泡不同天數(a) 一天(b)七天(c)十四天(d)三十天之微結構形態變化....75 圖 4-4-3 以bM的溶液C作為硫酸鈣骨水泥硬化劑，浸泡不同天數XRD分 析比較...........................................76 圖2-1-4 二水硫酸鈣的結構.................................27 圖2-1-5 各相硫酸鈣在不同溫度下之水中溶解度...............28 圖2-1-6 硫酸鈣加熱結晶結構的變化.........................28 圖2-6-1 添加HA的多寡對抗壓強度之影響.....................38 圖2-6-2 cement-B與cement-C 的微結構......................39 圖2-6-3 抗壓強度與CaSO4･ 2H2O/ α-TCP 相對含量之關係.....39 圖2-6-4 CaSO4･2H2O/ α-TCP composite六種試片的XRD........40 圖2-6-5 CSD、CSH、 PLLA 以及CS/PLLA composite 之繞射圖...40 圖2-6-6 CS 含量與接觸角的相對關係........................41 圗3-2-1 實驗流程圖.......................................48 圖3-2-2 抗壓強度測試試片示意圖...........................49 圖3-2-3 硬化時間測量儀器示意圖...........................50 圖3-2-4 雙電極pH meter 示意圖............................50 圖3-2-5 pH meter SP-2200.................................51 圖3-2-6 X光繞射儀之基本原理..............................51 圖3-2-7 SEM 主要構造示意圖...............................52 圖4-1-1 酸性溶液影響硫酸鈣骨水泥抗壓強度結果.............58 圖4-1-2 鹼性溶液影響硫酸鈣骨水泥抗壓強度結果.............58 圗4-1-3 以水溶液(a)為對照組，硫酸鈣骨水泥以(b)鹽酸和(c)溶液 A作硬化劑，浸泡一天的微結構比較..................59 圗4-1-4 以水溶液(a)為對照組，硫酸鈣骨水泥以碳酸鈉(b)和溶液C (c)作硬化劑，浸泡一天的微結構比較................60 圖4-1-5 硫酸鈣骨水泥以鹽酸、溶液A碳酸鈉和溶液C作硬化劑， 浸泡一天後與原始粉末及硫酸鈣骨水泥和純水反應浸泡 一天的XRD圖比較..................................61 圖4-2-1 改變溶液C濃度對硫酸鈣骨水泥浸泡Hanks’ solutionㄧ 天抗壓強度結果...................................64 圖4-2-2 以不同濃度的溶液c溶液(a)aM (b)bM (c)cM (d)dM作為 硬化劑，硫酸鈣骨水泥浸泡一天後之結晶形態.........65 圖4-2-3 以純水和不同濃度的溶液C作為硫酸鈣骨水泥的硬化劑浸泡 一天後之XRD分析..................................66 圖4-3-1 調整溶液C酸鹼值對硫酸鈣骨水泥浸泡Hanks’solution ㄧ 天抗壓強度之結果.................................69 圖4-3-2 調整bM的溶液C酸鹼值(a)為未調整(b)pH=φ的硫酸鈣骨水泥 浸泡Hanks’ solution 一天的微結構形態............70 圖4-3-3 調整溶液C酸鹼值後的硫酸鈣骨水泥浸泡Hanks’solution一 天之XRD分析......................................71 圗4-4-1 以純水、溶液C做為硫酸鈣骨水泥硬化劑的乾壓(dry)及不同 天數之濕壓之抗壓強度結果比較.....................74 圗4-4-2 以bM的溶液C作為硫酸鈣骨水泥之硬化劑，浸泡不同天數(a) 一天(b)七天(c)十四天(d)三十天之微結構形態變化....75 圖 4-4-3 以bM的溶液C作為硫酸鈣骨水泥硬化劑，浸泡不同天數XRD分 析比較...........................................76

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