吳錫侃臺灣大學：材料科學與工程學研究所陳芊卉Chen, Chien-HuiChien-HuiChen2007-11-262018-06-282007-11-262018-06-282006http://ntur.lib.ntu.edu.tw//handle/246246/55202本研究以TiNi形狀記憶合金為基材使用六甲基二矽胺(Hexamethyldisilazane, HMDSN)單體以脈衝式電漿輔助化學沉積法 (PECVD) 沉積非晶質SiC:H薄膜於TiNi合金之上並利用UV 光誘導接枝聚合丙烯醯胺(Acrylamide, AAm)單體，改變薄膜表面官能基，做酵素固定使TiNi合金成為具抗凝血生化特性之生醫材料。薄膜沉積速率快，表面形貌均勻、孔洞少、粗糙度低均在2~4nm之間。並顯著地提升抗腐蝕性，使腐蝕電流密度下降約至少四個數量級。由FTIR所得之吸收光譜，可知Si-C 與C-H等鍵結受破壞，形成Si-H與C=O等鍵結，沉積出高度分支且交錯連結之薄膜。經歷UV 光誘導接枝聚合AAm後，由FTIR光譜可證明成功接枝，表面粗糙度下降至1-2nm，形成新的ㄧ層緻密有機薄膜。接枝後水接觸角由87°下降至36°，與玻璃之相對濕摩擦係數由0.25下降至0.2以下，有利生醫方面之應用。後續經歷固定肝素之處理後，可觀察到聚合鍵結之肝素分子形成之團聚物，且由XPS可偵測出S元素存在為肝素固定之證明。SiC:H organic-like thin films are deposited on TiNi shape memory alloy (SMA) by DC-pulsed plasma enhanced chemical vapor deposition (PECVD) of HMDSN and Ar gas mixtures at room temperature. The organic-like thin films containing peroxides or free radicals can be subsequently grafted with hydrophilic polymer acrylamide (AAm) by UV-induced grafting polymerization. Heparin is immobilized onto grafted-AAm thin films to take TiNi SMA into the anti-thrombin biomaterials. The deposition rate of the plasma-polymerized HMDSN (PPHMDSN) thin film is fast and the root mean square surface roughness is between 2~4 nm. The PPHMDSN thin films not only enhance the corrosion resistance but make the corrosion current density decay four orders. Based on the micro-FTIR spectra, the Si-C and C-H bonds of the original HMDSN monomer are destroyed and new Si-H and C=O bonds are formed. The success of grafting is proved by FTIR. After grafting polymerization of AAm, a new dense organic thin films layer is formed in which the water contact angle decreases from 87° to 36° and the friction coefficient becomes lower. These properties are beneficial to the biomedical applications. According to XPS, the element S can be detected to prove that heparin is covalently immobilized on TiNi SMA.致謝 i 摘要 iii Abstract v 目錄 vii 第一章 前言 1 第二章 文獻回顧 3 2-1 形狀記憶合金簡介 3 2-1-1 形狀記憶效應(SME) 4 2-1-2 擬彈性(PE) 8 2-2 TiNi 基形狀記憶合金 10 2-2-1 TiNi 形狀記憶合金之各相與結晶構造 10 2-2-2 TiNi 形狀記憶合金之力學特性 12 2-2-3 TiNi形狀記憶合金之生物相容性 16 2-3 薄膜製程 19 2-3-1 電漿簡介 19 2-3-2 電漿基本反應 21 2-3-3 電漿表面改質 23 2-3-4 電漿輔助化學氣相沈積(PECVD) 25 2-3-5 直流輝光放電(D. C glow discharge) 27 2-3-6 脈衝式直流電漿輔助化學氣相沈積 (Pulsed-DC PECVD) 30 2-4 生物分子之固定 31 2-4-1 固定理論 31 2-4-2 共價鍵接合機制 33 2-4-3 生物單體-肝素(Heparin)簡介 36 第三章 實驗方法及步驟 53 3-1 薄膜試片之製作 53 3-1-1 TiNi基材之製備 53 3-1-2 鍍膜設備 54 3-1-3 非晶質SiC:H薄膜試片之製備 55 3-1-4 非晶質SiC:H薄膜試片接枝AAm 56 3-1-5 肝素固定 57 3-2 實驗分析 57 3-2-1 薄膜沉積速率之量測 57 3-2-2 水接觸角之量測 58 3-2-3 薄膜化學性質之量測 58 3-2-4 薄膜表面型態之量測 59 3-2-5 電化學分析 60 3-2-6 摩擦係數分析 60 第四章 實驗結果與討論 71 4-1 SiC:H薄膜性質 71 4-1-1 直流脈衝式電漿波形 71 4-1-2 沉積速率 73 4-1-3 FTIR之測試結果 75 4-1-4 抗腐蝕性 79 4-1-5 表面形貌之觀察 81 4-1-6 ESCA (XPS)之測試結果 84 4-2 生物相容性之改善 85 4-2-1 接枝率 86 4-2-2 FTIR之測試結果 87 4-2-3 水接觸角 88 4-2-4 摩擦測試 89 4-2-5 表面形貌 90 4-2-6 固定肝素 91 第五章 結論 119 參考文獻 1237484706 bytesapplication/pdfen-USTiNi形狀記憶合金六甲基二矽胺脈衝式電漿輔助化學沉積法丙烯醯胺(AAm)肝素TiNi shape memory alloyHMDSNDC-Pulsed PECVDAAmHeparinthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/55202/1/ntu-95-R93527071-1.pdf