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標題: | 原子層沉積技術於體外循環管路內壁形成氧化鋁抗血栓薄膜之研究 Anticoaugulation Properties of ALD Process Deposited Al2O3 Films on Inner Wall of Extracorporeal Circulation |
作者: | Li-Chun Wang 王理駿 |
指導教授: | 林新智 |
共同指導教授: | 陳敏璋 |
關鍵字: | 原子層沉積,醫用高分子,體外循環管路,血液相容性,抗血栓, ALD,Medical Polymer,Extracorporeal Circulation,Hemocompatibility,anticoaugulation properties, |
出版年 : | 2016 |
學位: | 博士 |
摘要: | 體外循環管路大量應用於葉克膜及血液透析等等醫療用途中,但血液流經管路時,可能會使血液活化而造成凝血機制的啟動,本研究將以數種原子層沉積技術(Atomic layer deposition, ALD)將體外循環管路內壁形成氧化鋁抗血栓薄膜,探討其薄膜性質及抗血栓特性。加熱式ALD(Thermal mode ALD, T-ALD)及電漿輔助ALD(Plasma mode ALD, PE-ALD)兩種ALD製程將氧化鋁沉積於醫療用聚氯乙烯(Polyvinylchloride, PVC)表面,以未處理的PVC做為對照組,比較表面沉積50, 100, 150, 200 cycle氧化鋁的薄膜特性及抗血栓情形,評估方法包括:顯微觀察、機械性質、表面粗糙度、化學組成、表面官能基、晶體結構等,抗血栓測試包括蛋白質吸附、親疏水性、血液細胞貼附、發炎情形等數種生醫檢測,探討氧化鋁應用於體外循環管路之抗血栓層的可能性。
實驗結果顯示,當PVC表面包覆不同ALD模式所沉積的氧化鋁後,表面形貌、物化特性及抗血栓情形皆有相當大的差異,T-ALD氧化鋁表面會有島狀的形貌產生並隨cycle數增加島狀逐漸擴大覆蓋表面,且因為TMA會去攻擊DEHP中親核(Nucleophilic)的羰基(Carbonyl)或酯基(ether)而形成鋁-氧-烷單元(Aluminum–oxygen–alkyl units),使膜層中出現以臭氧或氧電漿才會出現的官能基,另外膜層中的白蛋白/纖維蛋白原比例較高與血液細胞貼附較少而表現出較佳的抗血栓能力,主要是表面官能基(-CH3, -OH等)、疏水性與等電點的影響而不易形成血栓,並且膜層附著性及抗彎曲的性質較好,適用於體外循環管路;另外PE-ALD氧化鋁不論沉積的cycle數多寡,膜層皆非常均勻,歸因於氧電漿使表面產生均勻的官能基以及置換效果佳,將三甲基鋁的甲基幾乎完全的置換,雖然TMA會與DEHP形成鋁-氧-烷單元,但氧電漿與TMA的反應中也會產生許多鋁-氧-烷的官能基,另外膜層中的白蛋白/纖維蛋白原比例較低與血液細胞貼附較多而表現出較弱的抗血栓能力,主要是表面官能基(-OCH3, -COOH等)、親水性的影響與等電點而有較多的血液細胞貼附,並且膜層附著性及抗彎曲的性質較差,但PE-ALD所沉積出來的氧化鋁仍可適用於需要促進凝血的植體材料表面。 在本實驗中,氧化鋁薄膜因為使用不同的ALD沉積模式而形成不同的物化性質及血液相容性,表現出了ALD的應用多變性,除了應用於半導體產業外,也可根據使用需求調整製程來配合不同的應用,對於生醫產業也會有所貢獻。 Cardiopulmonary bypass tubing (CPB) has been wildly used in hemodialysis, extracorporeal membrane oxygenation (ECMO) treatment, but the coaugulation mechanism will be activated when blood flow passes through foreign material. In this study, atomic layer deposition (ALD) was applied to cover an aluminum oxide (Al2O3) films on the inner wall of the PVC tube to achieve anti-coaugulation properties. Thermal mode ALD (T-ALD, TMA/H2O) and plasma mode ALD (PE-ALD, TMA/O2 plasma) will used to deposit Al2O3 films on PVC surface, and the film properties with deposition of 50, 100, 150, 200 were compared. Several methods have been used to evaluate the properties of ALD films, including the microstructure, mechanical properties, surface roughness, chemical composition, functional group, crystal structure. Meanwhile, the measurements of protein adsorption, hydrophilicity, blood cells adhesion, inflammation were also carried out to evaluate anti-coagulation and applcabity of ALD Al2O3 films. The experimental results show that the physical properties and anti-coaugulation properties have quite much difference between T-ALD and PE-ALD Al2O3 films. T-ALD Al2O3 films exhibit an island structure and their thicknesses increase deposition cycles. TMA will attack the nucleophilic carbonyl or ether groups of DEHP in the PVC to form the aluminum-oxygen-alkyl units, therefore, T-ALD Al2O3 films exist some components that will only synthesized by TMA/O3 or O2 plasma. In addition, ascribe to surface functional group (-CH3, -OH etc.), hydrophobicity and isoelectrical point the films show better anti-coaugulation properties of high albumin/fibrinogen ratio and less blood cells adhesion. Besides, T-ALD Al2O3 films show great adhesion and bending resistance, which can be applied in the CPB. PE-ALD create a uniform Al2O3 films for various ALD cycles, because oxygen plasma has better reactivity that –CH3 in TMA can almost react, oxygen plasma can also produce multiple functional group on polymer substrate. In spite of TMA is likely attacking nucleophilic carbonyl or ether groups of DEHP in the PVC to form aluminum-oxygen-alkyl units, oxygen plasma can still produce this component too. In addition, the surface functional groups (-OCH3, -COOH etc.), hydrophilicity and isoelectrical point cause that films have weaker anti-coaugulation properties of low albumin/fibrinogen ratio and relatively more blood cells adhesion. However, this film also shows the applicability in the field of promoting blood clotting. Although PE-ALD Al2O3 films show poor adhesion and bending resistance, it can be applied in the fields where accelerating the clotting situation is preferred, such as implant. In this research, Al2O3 films can express distinct physical properties and anti-coaugulation properties for difference ALD processes. That findings indicate that ALD process has applicability not only in the semi-conductor industry, but also in the biomedical fields by tuning process parameter. For biomedical industry, ALD shall have a great contribution. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/21062 |
DOI: | 10.6342/NTU201603858 |
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顯示於系所單位: | 材料科學與工程學系 |
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