臺灣博碩士論文加值系統

中文摘要
高分子材料因其性能不斷的突飛猛進，許多具有良好光學、機械性質的塑膠材料紛紛被開發出來，在不斷的追求輕量化及安全性的趨勢下，目前正在許多應用上取代傳統的玻璃材質，成為下一代光學產品的材料。然而因為塑膠材質本身就有不耐刮的特性，所以目前在其應用上都會鍍上一層硬膜以增加其抗磨耗性，不過附著力的問題一直是在高分子材料表面鍍上硬膜的很大瓶頸，而除了抗磨耗的功用外，若我們可以控制此硬膜的親/疏水性，則其應用的範圍將會更加廣泛。因此本研究擬在光學塑膠上鍍上一層可控制親/疏水性且附著力良好的保護硬膜。
本研究採用電漿化學氣相沈積法在PC、PMMA上鍍膜，因為PECVD在製程上具有良好的彈性，可藉由簡單的操作參數調整即可大範圍的改變薄膜的性質，所以已被廣泛的應用在製備各種薄膜。且在此研究中，我們主要是以有機矽烷化物（HMDSO、MTMS）來沈積薄膜，因為以此為原料所沈積的薄膜具有良好的光學及機械性能，並且可藉由鍍膜條件的調整，使薄膜的組成結構由趨近於氧化矽的親水結構，變化至趨近於類鑽碳的疏水結構。
實驗結果發現由純HMDSO所成長的薄膜具有良好的疏水性，由IR及ESCA的分析我們發現HMDSO膜內有不少的甲基殘留，這些甲基即可能是薄膜呈疏水性的原因。而在親水性薄膜方面，我們發現以氧氣加入HMDSO及MTMS中所鍍的薄膜具有不錯的親水效果，由IR及ESCA的分析發現，這是因為加入大量氧氣之後，氧氣會將有機矽烷類結構中的甲基侵蝕掉，使鍍出的薄膜變成類似玻璃、石英的親水結構。另外，我們還發現可以利用高分子結晶區、非結晶區的分佈特性，以電漿做適當的前處理，使高分子表面形成凹凸不平的結構後，再鍍上一層薄膜，如此基板表面的親/疏水性都可以大幅度的提高。
關於薄膜的附著力方面，在我們的實驗範圍之內，鍍在PC基板上的薄膜，其附著力都相當良好，在我們測試範圍內都未發生剝落的情形；而在PMMA基板上，薄膜的附著力則是和鍍膜的組成有很大的關連，其中以加氧薄膜的附著力最差，因此我們先以附著力較好的鍍膜組成，先鍍上一層中間層之後在將加氧的薄膜鍍在此薄膜上，如此對此加氧薄膜的附著力的確獲得了初步的改善效果。

Abstract
The quality of optic plastics has been greatly improved recently. Due to its light weight and high toughness, plastics is gradually replacing glass in many optical application. However, optic plastics suffers a major problem in scratch-resistance. Therefore, a hard coating on the relatively soft plastics surface is required. This study is aimed at depositing on the optic plastics an adherent hard coating with controllable surface properties, like hydrophillicity and hydrophobicity.
Plasma enhanced chemical vapor deposition (PECVD) has been employed to deposit hard films on polycarbonte (PC) and polymethylmethacrylate (PMMA) substrates using hexamethyldisiloxane (HMDSO) and methyltrimethoxysilane (MTMS) as reactants. Our results show that the films deposited using HMDSO are highly hrdrophobic. IR ad ESCA show that methyl groups reside in the deposited films, accounting for the hydrophobicity of the films. By flowing O2 with HMDSO, the films become hydrophillic. IR and ESCA show that methyl groups are etched away from the film and the film structure become close to that of SiO2, accounting for the hydrophillicity of the films. Beside, both the hydrophobicity and hydrophillicity of the films can be greatly enhanced by increasing surface roughness of polymer substrates. By utilizing the heterogeneous nature of polymer surface, plasma etching using O2 or O2/HMDSO is quite effective in creating a rough surface.
All the films deposited on PC substrates exhibit good adhesion, with no film detachment under all peeling test conditions. However, the adhesion on PMMA is strongly dependent on the film structure.
The adhesion becomes very poor while adding O2 in the HMDSO. An interfacil layer deposited by using HMDSO only, before depositing the top hydrophillic layer by using HMDSO/O2 mixture, improves the film adhesion, but is yet not satisfactory.

總目錄
中文摘要………………………………………………………………… …Ⅰ
英文摘要…………………………………………………………………….Ⅱ
誌謝………………………………………………………………………….Ⅲ
總目錄……………………………………………………………………….Ⅳ
表目錄……………………………………………………………………….Ⅵ
圖目錄………………………………………………………………………Ⅶ
第一章 緒論...................................................................................................1
1-1 前言............................................................................................................1
1-2 研究動機、背景......................................................................................3
1-2-1 開發親/疏水膜的動機.......................................................................3
1-2-2 在塑膠上鍍膜的難處........................................................................4
1-2-3 使用電漿鍍膜的優點........................................................................7
第二章 理論基礎............................................................................................9
2-1 電漿的基本原理.......................................................................................9
2-2 電漿對表面的效應.................................................................................15
2-2-1 物理效應.............................................................................................15
2-2-2 化學效應.............................................................................................18
2-2-3 電漿和高分子表面的作用...............................................................20
2-3 電漿中的化學反應..................................................................................25
2-3-1 電漿反應的特色.................................................................................25
2-3-2 氣相中的化學反應.............................................................................27
2-3-3 電漿化學氣相沈積法........................................................................28
2-3-4 電漿聚合..............................................................................................30
2-4 老化............................................................................................................33
2-5 濕潤現象及接觸角..................................................................................35
2-5-1 表面自由能和接觸角的關係...........................................................36
2-5-2 表面粗糙度及不均勻性對接觸角的影響......................................42
第三章 實驗方法與步驟...............................................................................47
3-1 實驗流程....................................................................................................47
3-2 系統設備....................................................................................................48
3-2-1 進料系統...............................................................................................48
3-2-2 反應器...................................................................................................49
3-2-3 電源供應器..........................................................................................49
3-3 實驗藥品、材料.......................................................................................50
3-3-1 基板材料...............................................................................................50
3-3-2 實驗藥品及氣體...................................................................................51
3-4 實驗步驟.....................................................................................................52
3-4-1 基板前處理............................................................................................52
3-4-2 實驗步驟................................................................................................52
3-5 分析與鑑定.................................................................................................53
3-5-1 靜態接觸角............................................................................................53
3-5-2 附著力測試............................................................................................53
3-5-3 光學及電子顯微鏡...............................................................................54
3-5-4 IR、ESCA、EDX、UV-Visible...........................................................54
第四章 結果與討論.........................................................................................55
4-1 系統演進.....................................................................................................55
4-2 親水性薄膜.................................................................................................58
4-2-1 表面化學組成的影響..........................................................................58
4-2-2 表面型態和粗糙度的影響..................................................................65
4-2-3 耐久性.....................................................................................................71
4-3 疏水性薄膜.................................................................................................73
4-3-1 表面化學組成的影響...........................................................................73
4-3-2 表面型態及粗糙度的影響..................................................................80
4-3-3 耐久性......................................................................................................91
4-4 附著力的改善..............................................................................................92
4-4-1 不同鍍膜成分的比較............................................................................92
4-4-2 基板偏壓及膜厚對薄膜附著力的影響..............................................95
4-4-3 中間層.....................................................................................................101
4-5 薄膜的光學性質.........................................................................................102
第五章 結論.......................................................................................................105
參考文獻.............................................................................................................106
附錄.......................................................................................................................112
自述.......................................................................................................................114

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