應用電漿技術製備超疏水膜材之研究; Preparation of Superhydrophobic Films by Plasma Technology

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Title:	應用電漿技術製備超疏水膜材之研究;Preparation of Superhydrophobic Films by Plasma Technology
Authors:	楊士賢;Shih-Hsien Yang
Contributors:	化學工程與材料工程研究所
Keywords:	超疏水;能率循環;脈衝電漿;粗糙度;黏著性;有機矽氧烷;大氣電漿;接觸角;傾斜角;超雙疏;duty cycle;adhesion;roughness;pulsed plasma;superhydrophobic;contact angle;superamphiphobic;atmospheric pressure plasma
Date:	2009-07-02
Issue Date:	2009-09-21 12:29:14 (UTC+8)
Publisher:	國立中央大學圖書館
Abstract:	本論文採用具疏水官能基之單體配合不同電漿沉積方式調變操作參數，於單一步驟下快速製備具低表面能的粗糙結構，使膜材具有優異的超疏水特性。並對其物理、化學、機械強度及光學等特性進行有系統的分析及探討，並由結果對電漿沉膜機制進行討論。其重要研究結果如下：首先使用低壓沉積系統及C6F6單體配合脈衝式電漿在單一製程下沉積超疏水薄膜，探討脈衝電漿的能率循環(Duty Cycle, DC)對沉積膜材表面結構及化學特性的影響。結果發現，當電漿能率循環由1逐漸減少到0.1時，膜材結構會由薄膜逐漸的轉變為顆粒狀，大幅的增加了薄膜表面的粗糙度，因此造就了超疏水薄膜。此外，將易剝落的膜材沉積在低極性基材上，可大幅增加與薄膜之黏著性，以增加薄膜的應用性。於低壓下使用三種有機矽氧烷Ethoxytrimethylsilane (EOTMS)、Diethoxydimethylsilane (DEODMS)以及Methyltriethoxysilane (MTEOS)等單體，混入不同流率之氧氣進行沉積反應。實驗結果可得知，當導入氧氣於反應中可在矽晶片上沉積出硬度8H等級的硬質矽膜。另外使用PMMA做為基板時，沉積一層緩衝層(Buffer Layer)並將硬膜厚度增加到1500 nm，硬質膜則具有5B等級黏著度、7H等級硬度以及良好的疏水特性。另外發展自組式大氣電漿(Atmospheric Pressure Plasma, APP)沉積系統進行沉積超疏水薄膜。結果可得知，在HMDSN大氣電漿中混入較高的氧氣比例可得較快的沉積速率，當電漿噴嘴(Nozzle)間距由20 mm逐漸減少至10 mm，膜材結構會由平坦轉變成較為粗糙的表面，因此，可在10 mm的噴嘴間距條件下，製備具水滴接觸角(Contact Angle)超過150°以及傾斜角(Sliding Angle)小於5°的超疏水薄膜。最後由電腦模擬及量測數據的討論，可提出一簡單的成膜機制說明電漿參數對鍍膜成果的影響。利用大氣電漿於導電玻璃及不導電的光學玻璃上進行沉積，實驗結果發現，當以導電玻璃做為基板所引發的電弧(Arc)現象進行鍍膜，可製備具170°的水滴接觸角以及2.2°的傾斜角的薄膜。另外使用導電基板並改變不同載台移動速度進行沉積，可於載台移動速度150 mm/s的條件下，沉積出薄膜具水滴接觸角169.0°、二碘甲烷油滴接觸角146.9°以及高達97.1%之平均可見光絕對穿透率，成功的以極快速的方式製備透明超雙疏薄膜。 In this paper, the superhydrophobic films were prepared rapidly in one step by adjusting various parameters. Besides, the physical, chemical, mechanical strength, and optical properties were analyzed and discussed. The plasma deposition mechanisms were also discussed through above results as following: First, super-hydrophobic films were deposited in one-step simple process by pulsed RF C6F6 plasma, and the influence of duty-cycle (DC) on the surface structure and chemical characteristics of depositing fluorocarbon films were investigated. It was found that with decreasing the DC from 1 to 0.1, the rough structure of the film which had a lot of particles was obtained. Besides, this composite structure with low surface energy resulted in exhibiting the desirable super-hydrophobic surface property. Finally, the fluorocarbon films were prepared on cotton substrate and the adhesion on the substrate was strong. Second, the silicon wafer and plastic substrate have been coated silica films by Plasma enhanced chemical vapor deposition (PECVD). The films were deposited by introducing Ethoxytrimethylsilane (EOTMS), Diethoxydimethylsilane (DEODMS) and Methyltriethoxysilane (MTEOS) into the RF bell jar reactor fed with different oxygen flow rate. When adding oxygen into PECVD reactor, SiOx films with hardness 8H were deposited on hard silicon wafer. On the other hand, the SiOx film with 5B degree adhesion, 7H degree hardness, and hydrophobic characteristic could be obtained when a buffer layer was coated between the 1500nm-thick of SiOx film and the PMMA substrate. Third, the chemical properties and surface morphology of superhydrophobic (SH) films deposited by self-assembled RF atmospheric-pressure plasma jet (APPJ) deposition system was investigated. The O2/HMDSN (hexamethyldisilazane) and Ar serve as the deposition precursor and ionization gas, respectively. Consequently, the smooth surface was transformed into a rough surface with many particles when the nozzle-to-sample distance was decreased from 20 mm to 10 mm. The SH films (contact angle over 150° and sliding angle below 5°) were obtained when the nozzle-to-sample distance was 10 mm. A simplified deposition mechanism is proposed to explain the effect of process parameters on the films that are formed. Finally, the film was coated on the conductive and the non-conducting glass by APPJ system. It was found that the Arc condition would be produced on the conductive glass, and the superhydrophobic films ( contact angle: 170o, sliding angle: 2.2o ) could be prepared using the HMDSN monomer by Arc-APPJ. Besides, the absolute optical transmittance of the film increased with increasing the speed of stage. Finally, the transparent superamphiphobic film (WCA: 169o, OWA: 146.9o and Tavg: 97.1%) could be prepared rapidly in optimum condition (150 mm/s) by Arc-APPJ.
Appears in Collections:	[National Central University Department of Chemical & Materials Engineering] Electronic Thesis & Dissertation

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