具鵝毛仿生結構之電活性抗菌防蝕塗層之製備、鑑定及應用研究

本論文研究主軸結合了「鈍性氧化層」、「阻氣性」和「疏水性」共三個概念，製備具仿生結構之電活性聚苯胺/生質碳材複合塗層，分別進行「抗菌」及「防腐蝕」性質的差異測試。第一部分以「化學氧化聚合法」製備電活性聚苯胺 (Electroactive Polyaniline, PANI)，並且以傅立葉紅外光譜儀 (Fourier Transform Infrared Spectroscopy, FTIR)、核磁共振光譜儀 (Nuclear Magnetic Resonance, NMR) 佐證其化學結構。以凝膠滲透色譜儀 (Gel Permeation Chromatography, GPC) 得知其分子量，以循環伏特安培儀 (Cyclic Voltammetry, CV) 測試氧化還原能力，電催化能使其產生緻密鈍性氧化層，由化學分析電子光譜 (Electron Spectroscopy for Chemical Analysis, ESCA) 證實鈍性氧化層生成。第二部分使用高溫爐製備疏水性碳化椰子殼 (Hydrophobic Coconut Carbon, HCC)，以原位聚合法 (In-situ) 和苯胺進行化學氧化聚合時加入不同重量百分比之碳化椰子殼，透過 FTIR 探討結構，穿透式電子顯微鏡 (Transmission Electron Microscopy, TEM) 探討分散性，並且經由氣體滲透率分析儀 (Gas Permeation Analyzer, GPA) 證實當添加量為 1wt-%HCC (PANI-1) 既可均勻分散其阻氣效果提升高達 66%， CV 驗證趨勢電位下降，氧化還原電流明顯增加最多達 7 倍，接觸角 (Contact Angle, CA) 得疏水性微幅提升10°。第三部分以聚二甲基矽氧烷 (Polydimethylsiloxane, PDMS) 奈米壓印技術仿製「天然鵝毛」表面結構，製備仿生 PDMS 負模板，將 PANI 及PANI-1 進行轉印，成功製備仿生聚苯胺塗層 BPANI 及 BPANI-1，以掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 觀察表面結構，以水滴接觸角 (CA) 證實有效創造顯著疏（排）水效果，平坦PANI 約73° 而BPANII-1 達144.49°，疏（排）水提升高達 1 倍。最後，結合第一部分電活性聚苯胺、第二部分疏水阻氣碳化椰子殼及第三部分仿生疏（排）水表面結構，分別進行抗菌及防腐蝕測試。抑制生物膜測試以「大腸桿菌」 (Escherichia coli) 、「綠膿桿菌」(Pseudomonas aeruginosa) 和「金黃色葡萄球菌」 (Staphylococcus aureus) 進行 1、7和14天時間變因實驗，使用微量盤分光光度計 (Microplate Reader) 定量，比較 PANI、PANI-1、BPANI和BPANI-1四種膜材，「天然鵝毛」仿生結構所衍生的抗菌效率優於導入疏水碳化椰子殼的抗菌效率(BPANI  PANI-1)。「天然鵝毛」仿生結構結合導入疏水碳化椰子殼(BPANI-1) 具有最佳的抗菌效果，其中針對「大腸桿菌」抗菌效率高達76.45%。另一方面，防腐蝕測試透過「塔伏試驗」 (Tafel test) 以及電化學阻抗分析儀 (Electrochemical impedance spectroscopy, EIS) ，本研究結果顯示：「天然鵝毛」仿生結構所衍生的防腐蝕效能優於導入疏水碳化椰子殼的防腐蝕效能(BPANI  PANI-1)。「天然鵝毛」仿生結構結合導入疏水碳化椰子殼(BPANI-1) 具有最佳的防腐蝕效能，其保護效率高達99.99%。

關鍵字

仿生；疏水；電活性；聚苯胺；阻氣；抑制生物膜；防腐蝕

並列摘要

The main axis of this thesis incorporates three concepts "densely passive metal oxide layers", "gas barrier" and "hydrophobicity". On the synthesis of composite coatings of electroactive polyaniline(PANI)/bio-carbon, a biomimetic surface was prepared upon the composites. Differential tests for "anti-biofilm" and "anticorrosion" properties for the biomimetic composite coatings were carried out, respectively. In the first part, electroactive polyaniline (PANI) was prepared by "chemical oxidation polymerization", and its chemical structure of PANI was confirmed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Molecular weight of PANI was obtained by gel permeation chromatography (GPC), and corresponding redox capability was tested by cyclic voltammetry (CV). Electron spectroscopy for chemical analysis (ESCA) confirmed the formation of passive oxide layers. The second part of this dissertation uses a high temperature tubular furnace to prepare hydrophobic coconut carbon (HCC). Different weight percentage of HCC were added to aniline monomer, followed by performing the In-Situ chemical oxidization polymerization. HCC and its PANI-based composites were characterized by FT-IR. Transmission electron microscopy (TEM) was used to investigate the dispersion of HCC in PANI matrix, and it confirmed that 1wt-% of HCC can evenly disperse in PANI (denoted by PANI-1) and therefore increased the O2 gas barrier effect of 66%, as evidenced by the studies of gas permeability analyzer (GPA). Moreover, the CV showed that the potential of PANI-1 was decreased and the redox current of PANI-1 was increased significantly up to 7 times as-compared to that of PANI. Contact angle (CA) of PANI-1, as-compared to that of PANI, was found to be slightly increased ~ 10°. The third part of this dissertation is to prepare the surface structure of "natural goose feather" by nano-casting technique with polydimethyl-siloxane (PDMS) as a negative template. After treatment, PANI coating with biomimetic surface structure of goose feather were prepared successfully and denoted by BPANI, which was observed by scanning electron microscope (SEM). The CA of water droplets on flat PANI and BPANI was found to be 73° and 144.49°, respectively. It indicated that the hydrophobicity of BPANI with bio-mimetic structure was increased significantly as-compared to that of PANI with smooth surface structure. Finally, BPANI-1 combined with the PANI, the HCC, and the biomimetic surface structure was prepared and applied in the inhibition of biofilm and anti-corrosion tests, respectively. Three bacteria, Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus, was used to perform the inhibition of biofilm tests for the experiments of 1, 7 and 14 days. Microplate reader was used to quantify and compare four membrane materials of PANI, PANI-1, BPANI and BPANI-1. The antibacterial efficiency showed that PANI with biomimetic structure of "natural goose feather" was found to be better than the PANI incorporating 1 wt-% of HCC. The PANI with both biomimetic structure and incorporating 1 wt-% of HCC (denoted by BPANI-1) was found to show the best inhibition of biofilm effect, especially for Escherichia coli was as high as 76.45%. On the other hand, anti-corrosion performance of as-prepared coatings was carried out by Tafel plots and electrochemical impedance spectroscopy (EIS). The anticorrosion results of this study also showed that PANI with biomimetic structure was better than that the PANI incorporating 1 wt-% of HCC. The PANI with both biomimetic structure and incorporating 1 wt-% of HCC (denoted by BPANI-1) was found to show the best anti-corrosion performance, and its protection efficiency was as high as 99.99%.

並列關鍵字

biomimetic ； hydrophobic ； electroactive ； polyaniline ； gas barrier ； inhibition of biofilm ； anticorrosion

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