本論文旨在藉由甲烷/氧氣混合氣體之射頻式(RF)圓管低壓甲烷(CH4)/氧氣(O2)混合氣體電漿進行聚丙烯薄膜(Polypropylene, PP)之表面改質研究，期望改善聚丙烯薄膜之表面疏水及低表面能之特性。
實驗分為兩大部分，第一部份為探討聚丙烯薄膜於直接電漿區(plasma region)及後輝光放電區(afterglow region)兩種電漿改質位置下，表面親疏水特性變化之差異；第二部份為探討當聚丙烯薄膜放置於直接電漿區及兩種不同電極位置之進氣端區等三種改質狀態。
由本論文研究之結果得知，聚丙烯薄膜於遙距式電漿區會因自由基、部分帶電粒子及離子擴散至表面而使之獲得些微表面改質效果；而隨著電極之位置遠離進氣端，會減少自由基、帶電粒子及離子擴散至進氣端之機率，使得聚丙烯薄膜表面改質之效果降低。此外，於電極中心進行低壓甲烷/氧氣混合氣體電漿改質聚丙烯薄膜則為最有效改善聚丙烯薄膜表面之疏水特性及聚丙烯薄膜低表面能之缺點，水滴接觸角最低可達10°、及表面自由能可至77.5 mJ/m2。

This thesis focuses on exploration of low-pressure methane (CH4)/oxygen (O2) mixing gas plasma surface modification which occurring in luminous gas phase and non-luminous gas phase. Polypropylene (PP) membranes were set at different positions away from glow region of RF CH4/O2 mixture gas plasma with respect to their suitability for surface modification. The photoemission plasma species in RF CH4/O2 mixture gas plasma was identified by Optical Emission Spectroscopy (OES). As a result, the OES data and contact angle value evidently indicated that in CH4/O2 glow discharge. It was found that RF CH4/O2 mixture gas plasma is very effective in the surface hydrophilicity enhancement in luminous gas phase. In this study, the optical emission analysis indicates that the possible contribution of RF CH4/O2 mixture gas plasma is mainly occurred at the combination of electron-impact-dissociation and ionization. Research effort was also given to the surface analysis of RF CH4/O2 mixture gas plasma modified PP membranes. Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS), Confocal Laser Scanning Microscopy (CLSM), and Scanning Electron Microscopy (SEM) were used to detect the correlation between surface property change and luminous effect. In summary, direct CH4/O2 mixed gas plasma treatment is relatively effective to enhance the surface hydrophilicity and surface free energy of PP membrane.

摘要 I
Abstract II
致謝 III
總目錄 V
表目錄 IX
圖目錄 X
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 3
第二章 文獻回顧 6
2.1 基本電漿介紹 6
2.1.1 電漿之生成及基本反應 6
2.1.2 低壓電漿之介紹與應用 13
2.1.3 電漿表面改質之文獻整理 16
2.2 聚丙烯膜簡介 22
第三章 實驗方法與儀器原理 23
3.1實驗目的 23
3.2實驗步驟 25
3.2.1 實驗系統 25
3.2.2實驗前處理 29
3.2.3實驗流程 30
3.3 實驗分析及分析儀器之原理介紹 31
第四章 實驗結果與討論 45
4.1 利用低壓甲烷/氧氣混合氣體電漿進行聚丙烯薄膜之表面改質 47
4.1.1直接電漿區與電漿暗區改質效果之比較 47
4.1.1.1 輝光放電現象 49
4.1.1.2親疏水性分析 52
4.1.1.3 表面自由能 (Surface free energy) 57
4.1.1.4 光放射光譜儀分析 (OES) 61
4.1.1.5傅立葉轉換紅外線光譜儀之分析 (FTIR) 70
4.1.1.6 X射線光電子能譜儀之分析 (XPS) 76
4.1.1.7 表面分析 81
4.1.2 探討改變電極位置對放置於進氣端之聚丙烯薄膜之影響 90
4.1.2.1 輝光放電現象 92
4.1.2.2 親疏水性分析 96
4.1.2.3 表面自由能 101
4.1.2.4光放射光譜儀分析 106
4.1.2.5 傅立葉轉換紅外線光譜儀分析 115
4.1.2.6 聚丙烯薄膜之表面分析 123
第五章 結論 131
參考文獻 132
附錄 A 比較四種不同之混合氣體電漿於聚丙烯(PP)薄膜表面進行電漿改質之結果 140
附錄 B八氟環丁烷(C4F8)於圓管式低壓反應器進行硝酸纖維素(NC)膜表面之電漿沉積研究 145

1.M. Ito, K. Ro, N. Tomikawa, H. Uyama, “Plasma Treatment of Polymer Films by Several Techniques”, J. Photopolym. Sci. Technol., 10, 129-134 (1997).
2.B. Bae, B. H. Chun, D. Kim, “Surface characterization of microporous polypropylene membranes modified by plasma treatment”, Polymer, 42, 7879-7885 (2001).
3.J. X. Tang, N. Y. He, M. J. Tan, Q. G. Hea, H. Chen, “A novel substrate for in situ synthesis of oligonucleotide:plasma-treated polypropylene microporous membrane”, Colloids Surf., A, 242, 53-60 (2004).
4.O. J. Kwon, S. W. Myung, C. S. Lee, H. S. Choi, “Comparison of the surface characteristics of polypropylene films treated by Ar and mixed gas (Ar/O2) atmospheric pressure plasma”, J. Colloid Interface Sci., 295, 409-416 (2006).
5.M. S. Kang, B. Chun, S. S. Kim, “Surface modification of Polypropylene Membrane by Low-Temperature Plasma Treatment”, J. Appl. Polym. Sci., 81, 1555-1566 (2001).
6.D. Kim, M. A. Scibioh, S. Kwak, I. H. Oh, H. Y. Ha, “Nano-silica layered composite membranes prepared by PECVD for direct methanol fuel cells”, Electrochem. Commun., 6, 1069-1074 (2004).
7.F. Bretagnola, M. Tatouliana, F. Arefi-Khonsaria, G. Lorangb, J. Amouroux, “Surface modification of polyethylene powder by nitrogen and ammonia low pressure plasma in a fluidized bed reactor”, React. Funct. Polym., 61, 221-232 (2004).
8.I. Prasertsung, R. Mongkolnavin, S. Damrongsakkul, C. S. Wong, “Surface modification of dehydrothermal crosslinked gelatin film using a 50 Hz oxygen glow discharge”, Surf. Coat. Technol., 205, S133-S138 (2010).
9.N. Gomathi, S. Neogi, “Surface modification of polypropylene using argon plasma: Statistical optimization of the process variables”, Appl. Surf. Sci., 255, 7590-7600 (2009).
10.E. Vassallo, A. Cremona, F. Ghezzi, D. Ricci, “Characterization by optical emission spectroscopy of an oxygen plasma used for improving PET wettability”, Vacuum, 84, 902-906 (2010).
11.Z. Kregar, M. Biscan, S. Milosevic, A. Vesel, “Monitoring Oxygen Plasma Treatment of Polypropylene With Optical Emission Spectroscopy”, IEEE Trans. Plasma Sci., 39, 1239-1246 (2011).
12.洪昭南，電漿反應器，化工技術，第3期 124-135 (1995).
13.劉志宏，利用實驗設計法與電漿診斷技術探討電漿沉積氟碳膜製程之研究，中原大學化學工程學系博士論文。
14.http://www.plasma-us.com/16-6-20302227393865128479.html
15.U. Cvelbar, B. Markoli, I. Poberaj, A. Zalar, L. Kosec, S. Spaic, “Formation of functional groups on graphite during oxygen plasma treatment”, Appl. Surf. Sci., 253, 1861-1865 (2006).
16.D. Garcia, O. Fenollar, R. Lopez, R. Sanchis, R. Balart, “Durability of the Wettability Properties of a Polypropylene Film with a Low-Pressure CH4–O2 Plasma Treatment”, J. Appl. Polym. Sci., 110, 1201–1207 (2008).
17.D. Garcia, L. Sanchez, O. Fenollar, R. Lopez, R. Balart, “Modification of polypropylene surface by CH4-O2 low-pressure plasma to improve wettability”, J. Mater. Sci., 43, 3466-3473 (2008).
18.K. Narushima, N. Matsuda, C. Mizutani, N. Yamashita, N. Inagaki, K. Iio, Y. Isono, M. R. Islam, “Possibility of Solid-State Graft Copolymerization on Poly(ethylene terephthalate) Filmsby Plasma Irradiation and Effects of Surface Modification”, Jpn. J. Appl. Phys., 46, 4252-4259 (2007).
19.Y. W. Parka, N. Inagaki, “Surface modification of Poly(vinylidene fluoride) film by remote Ar, H2, and O2 plasmas”, Polymer, 44, 1569-1575 (2003).
20.M. Ataeefar, S. Moradian, M. Mirabedini, M. Ebrahimi, S. Asiaban, “Surface Properties of Low Density Polyethylene upon Low-Temperature Plasma Treatment with Various Gases”, Plasma Chem. Plasma Process., 28, 377-390 (2008).
21.A. Vesel, “Modification of polystyrene with a highly reactive cold oxygen plasm”, Surf. Coat. Technol., 205, 490-497 (2010).
22.K. J. Clay, S. P. Speakman, G. A. J. Amaratunga, S. R. P. Silva, “Characterization of a-C:H:N deposition from CH4/N2 rf plasmas using optical emission spectroscopy”, Jpn. J. Appl. Phys., 79(9), 7227-7233 (1996).
23.N. Tomozeiu, K. J. Clay, W. I. Milne, “Optical Studies of a-C:H films deposited from CH4, CH4/He, CH4/Ar and CH4/N2 rf plasmas”, J. Optoelectron. Adv. Mater., 2, 43-52 (2000).
24.D. Liu, J. Zhou, E. R. Fisher, “Correlation of gas-phase composition with film properties in the plasma-enhanced chemical vapor deposition of hydrogenated amorphous carbon nitride films”, J. Appl. Phys., 101, (2007).
25.B. Jaleha, P. Parvin, P. Wanichapichart, A. P. Saffar, A. Reyhani, “Induced super hydrophilicity due to surface modification of polypropylene membrane treated by O2 plasma”, Appl. Surf. Sci., 257, 1655-1659 (2010).
26.S. H. Mortazavi, M. Ghoranneviss, A. H. Sari, “Effect of Low Pressure Nitrogen-Oxygen (N2/O2) Plasma Treatment on Surface Properties of Polypropylene Films”, J. Fusion Energy, 30, 48-52 (2011).
27.E. Gonzalez II, R. F. Hicks, “Surface Analysis of Polymers Treated by Remote Atmospheric Pressure Plasma”, Langmuir, 26, 3710-3719 (2010).
28.廖駿偉、蕭祝螽、陳蔚宗，OES技術於電漿製程監測之應用，工業材料雜誌，第213期 171-176 (2004)。
29.http://zh.wikipedia.org/wiki/X%E5%B0%84%E7%BA%BF%E5%85%89%E7%94%B5%E5%AD%90%E8%83%BD%E8%B0%B1
30.http://www-o.ntust.edu.tw/~ch/ESCA2002/ESCA2008.html
31.K. J. Clay, S. P. Speakman, G. A. J. Amaratunga, S. R. P. Silva, “Characterization of a-C:H:N deposition from CH4/N2 rf plasmas using optical emission spectroscopy”, J. Appl. Phys., 79, 7227-7233 (1996) .
32.E. A. H. Timmermans, J. Jonkers, A. Rodero, M. C. Quintero, A. Sola, A. Gamero, D. C. Schram, J. A. M. Van Der Mullen, “Behavior of molecules in microwave-induecd plasmas studied by optical emission spectroscopy. 2: Plasma at reduced pressure”, Spectrochinica Acta Part B, 54, 1085-1098 (1999).
33.N. M. Horii, K. Okimura, A. Shibata, “Investigation of SiO2 deposition processes with mass spectrometry and optical emission spectroscopy in plasma enhanced chemical vapor deposition using tetraethoxysilane”, Thin Solid Films, 343-344, 148-151 (1999).
34.J. Luque, W. Juchmann, E. A. Brinkman, J. B. Jeffries, “Excited state density distributions of H, C, C2, and CH by spatially resolved optical emission in a diamond depositing dc-arcjet reactor”, J. Vac. Sci. Technol. A, 16, 397-408 (1998).
35.F. Claeyssens, M. N. R. Ashfold, E. Sofoulakis, C. G. Ristoscu, D. Anglos, C. Fotakis, “Plume emission accompanying 248 nm laser ablation of graphite in vacuum: Effects of pulse duration”, J. Appl. Phys., 91, 6162 (2002).
36.B. O. Cho, S. Lao, L. Sha, J. P. Chang, “Spectroscopic study of plasma using zirconium tetra-tert-butoxide for the plasma enhanced chemical vapor deposition of zirconium oxide”, J. Vac. Sci. Technol. A, 19, 2751 (2001).
37.C. Huang, C. Y. Tsai, and R. S. Juang, “Surface Modification and Characterization of an H2/O2 Plasma-Treated Polypropylene Membrane”, J. Appl. Polym. Sci., 124, E108-E115 (2012).
38.C. Y. Tsai, R. S. Juang, and C. Huang, “Surface Modification of Polypropylene Membrane by RF Methane/Oxygen Mixture Plasma Treatment”, Jpn. J. Appl. Phys., 50, 08KA02 (2011).
39.Y. Lv, X. Yu, S. T. Tu, J. Yan, E. Dahlquist, “Wetting of polypropylene hollow fiber membrane contactors”, J. Membr. Sci., 362, 444-452 (2010).
40.K. Wang, W. Wang, D. Yang, Y. Huo, D. Wang, “Surface modification of polypropylene non-woven fabric using atmospheric nitrogen dielectric barrier discharge plasma”, Appl. Surf. Sci., 256, 6859-6864 (2010).
41.R. Lopez, R. Sanchis, D. Garcia, O. Fenollar, R. Balart, “Surface Characterization of Hydrophilic Coating Obtained by Low-Pressure CH4-O2 Plasma Treatment on a Polypropylene Film”, J. Appl. Polym. Sci., 111, 2992-2997 (2009).
42.K. N. Pandiyaraj, V. Selvarajan, R. R. Deshmukh, C. Gao, ”Modification of surface properties of polypropylene (PP) film using DC glow discharge air plasma”, Appl. Surf. Sci., 255(7), 3965-3971 (2009).
43.S. Zanini, M. Muller, C. Riccardi, M. Orlandi, “Polyethyene glycol grafting on polypropylene membrane for anti-fouling properties”, Plasma Chem. Plasma Process., 27(4), 446-457 (2007).
44.L. M. H. Groenewoud, G. H. M. Engbers, and J. Feijen, “Plasma Polymerization of Thiophene Derivatives”, Langmuir, 19, 1368-1374 (2003).
45.K. Narushima, M. Fukuoka, H. Kawai, N. Inagaki, Y. Isono, M. R. Islam, “Amination and Oxidation Reactions on Polyethylene Surfaces by Ammonia Plasma Treatment”, Jpn. J. Appl. Phys., 46, 7855-7857 (2007).
46.M. Ghoranneviss, S. Shahidi, J. Wiener, “Surface Modification of Poly Vinyl Chloride (PVC) Using Low Pressure Argon and Oxygen Plasma”, Plasma Sci. Technol., 12, (2010).
47.P. Slepicka, A. Vasina, Z. Kolska, T. Luxbacher, P. Malinsky, A. Mackova, V. Svorcik, “Argon plasma irradiation of polypropylene”, Nucl. Instrum. Methods Phys. Res., Sect. B, 268, 2111-2114 (2010).
48.Y. W. Parka, N. Inagaki, “Surface modification of Poly(vinylidene fluoride) film by remote Ar, H2, and O2 plasmas”, Polymer, 44, 1569-1575 (2003).
49.M. Drabik, J. Hanus, J. Kousal, A. Choukourov, H. Biederman, D. Slavinska, A. Mackova, J. Pesicka, “Composite TiOx/Hydrocarbon Plasma Polymer Films Prepared by Magnetron Sputtering of TiO2 and Poly(propylene)”, Plasma Processes Polym, 4, 654-663 (2007).
50.J. Tyczkowski, J. Zielinski, A. Kopa, I. Krawczyk, B. Wozniak, “Comparison Between Non-equilibrium Atmospheric-Pressure and Low-Pressure Plasma Treatments of Poly(styrene–butadiene–styrene) Elastomers”, Plasma Processes Polym., 6, S419-S424 (2009).
51.M. H. Chiang, K. C. Liao, I. M. Lin, C. C. Lu, H. Y. Huang, C. L. Kuo, J. S. Wu, “Modification of Hydrophilic Property of Polypropylene Films by a Parallel-Plate Nitrogen-Based Dielectric Barrier Discharge Jet”, IEEE Trans. Plasma Sci., 38, 1489-1498 (2010).
52.M. Xu, J. Qiu, Y. Lin, X. Shi, H. Chen, Tan Xiao, “Surface biocompatible modification of polypropylene by entrapment of polypropylene-block-poly(vinylpyrrolidone)”, Colloids Surf., B, 80, 200-205 (2010).
53.M. L. Steen, L. Hymas, E. D. Havey, N. E. Capps, D. G. Castner, E. R. Fisher, “Low temperature plasma treatment of asymmetric polysulfone membranes for permanent hydrophilic surface modification”, J. Membr. Sci., 188, 97-114 (2001).
54.M. L. Steen, A. C. Jordan, E. R. Fisher, “Hydrophilic modification of polymeric membranes by low temperature H2O plasma treatment”, J. Membr. Sci., 204, 341-357 (2002).
55.Y. W. Park, N. Inagaki, “A New Approach for Selective Surface Modification of Fluoropolymers by Remote Plasmas”, J. Appl. Polym. Sci., 93, 1012-1020 (2004).
56.D. Vujosevic, M. Mozetic, U. Cvelbar, N. Krstulovic, S. Milosevic, “Optical emission spectroscopy characterization of oxygen plasma during degradation of Escherichia coli”, J. Appl. Phys., 101, (2007).
57.S. C. Cho, Y. C. Hong, H. S. Uhm, “Hydrophobic coating of carbon nanotubes by CH4 glow plasma at low pressure, and their resulting wettability”, J. Mater. Chem., 17, 232-237 (2007).
58.F. Awaja, S. Zhang, N. James, D. R. McKenzie, “Enhanced Autohesive Bonding of Polyetheretherketone (PEEK) for Biomedical Applications Using a Methane/Oxygen Plasma Treatment”, Plasma Processes Polym., 7, 1010-1021 (2010).
59.http://www.keyence.com.tw/products/microscope/microscope/vkx100_200/vkx100_200.php?id=55f7304a64e030319f18db63446af92d.
60.欣創達科技有限公司，接觸角量測儀使用手冊。
61.吳信誼，低溫大氣電漿製備類二氧化矽薄膜，元智大學化學工程與材料科學學系碩士論文。
62.蔡景元，以低壓電漿表面改質技術應用於醋酸纖維薄膜與聚丙烯薄膜表面研究，元智大學化學工程與材料科學學系碩士論文。
63.http://www-o.ntust.edu.tw/~ch/ESCA2002/ESCA2008.html
64.http://en.wikipedia.org/wiki/File:Nitrocellulose-2D-skeletal.png