仿生超疏水材料與電活性高分子材料的製備、鑑定及其防蝕與感測性質研究

Preparation, Characterization and Anti-corrosion as well as Sensing Properties of Biomimetic 3D-nanopatterning Super-hydrophobic Polymeric Materials and Electroactive Materials

彭志偉(Chih-Wei Peng)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/博士(2012年)

https://doi.org/10.6840/cycu201200595

摘要

本論文以不同的合成技術製備一系列的仿生超疏水材料與電活性高分子材料，並進行結構的鑑定及物理性質的分析。本研究主要分為二個部份：
第一部分為聚苯胺超疏水防蝕塗料，首先利用複印的方式複製新鮮千年芋(Xanthosoma sagittifolium)的表面結構，得到仿生聚二甲基矽氧烷(PDMS)模板，將化學氧化聚合之聚苯胺聚溶液塗佈於冷軋鋼(CRS)上，再以壓印的方式將PDMS模板，成功轉印以製備出仿生聚苯胺超疏水表面，透過原子力顯微鏡(AFM)與掃描式電子顯微鏡 (SEM)鑑定，發現表面有許多微米尺度的乳突，以及許多奈米尺度的皺褶，與轉印後的聚苯胺表面結構相符，證實成功複製千年芋表面微結構，且具仿生微結構之聚苯胺塗層表面的接觸角 (Contact Angle)從90∘(不具微結構之聚苯胺表面)大幅上升至156∘，接觸角明顯提升66∘，最後利用電化學儀器對具仿生結構之聚苯胺塗料進行防腐蝕測試，得知其在防蝕能力上相較於無微結構之聚苯胺有大幅的提升。
此外，透過UV光固化的方式，成功製備出光固化型仿生超疏水環氧樹脂塗料，同樣透過AFM與SEM鑑定，證實利用UV光固化的方式，所轉印之表面結構與植物表面之微結構相符，光固化型超疏水環氧樹脂塗層接觸角(Contact Angle)為151∘與平滑環氧樹脂塗層(88∘)比較亦提升了近63∘，最後以電化學防腐蝕測試證實，具仿生結構之超疏水環氧樹脂塗料具有的排水性，於防蝕測試結果有大幅的提升，在防蝕應用上具有重大潛力。
第二部份為電活性二氧化矽接枝苯胺五聚體電紡絲製備與物性探討，研究中以利用氧化偶合一步法合成苯胺五聚體(Aniline Pentamer)，並選用矽烷偶聯劑(3-Isocyanatopropyltriethoxysilane)進行電活性矽烷的合成，再以電紡絲技術製備出電活性二氧化矽纖維(Electroactive Silica Fibers，ESF)，利用傅立葉轉換紅外線光譜儀(FTIR)、質譜儀 (Mass) 、氫核磁共振譜（1H-NMR spectroscopy）鑑定材料之化學結構，以掃描式電子顯微鏡(SEM)鑑定材料之表面形態，最後以循環伏特電位儀 (CV)將此複材應用於偵測抗壞血酸 (Ascorbic acid, AA)之生物感測器。

關鍵字

電活性 ； 環氧樹脂 ； 電紡絲 ； 感測器 ； 聚苯胺 ； 防腐蝕 ； 超疏水

並列摘要

In this research, a series of biomimetic 3D-nanopatterning super-hydrophobic polymeric materials and electroactive materials were prepared by different technologies. This essay is divided into two parts.
In the first part, anticorrosion coating materials were prepared by replicating fresh plant leaves. Superhydrophobic polyaniline coating applied for corrosion protection was prepared and coated on the surface of cold rolled steel (CRS) using a nanocasting technique from the surface structure of fresh Xanthosoma sagittifolium leaves. First, the transparent PDMS template was replicated from the surface structure of fresh Xanthosoma sagittifolium. Subsequently, the coating was fabricated on the CRS electrode using a nanocasting technique with a transparent PDMS template and a polyaniline solution as the ink. The CRS electrode coated with super-hydrophobic surface (SHS) of polyaniline was found to exhibit a water contact angle (CA) of 156∘, which was significantly higher than the smooth polyaniline coated on the CRS by spin coating (CA = 90∘). The SHS polyaniline coating material not only shows superior water repellent properties but also electroactive properties. It should be noted that the CRS coated with SHS polyaniline was found to exhibit remarkably enhanced corrosion protection on the basis of a series of electrochemical corrosion measurements performed under saline conditions.
Further, UV-curing nanocasting technique was also used to develop advanced anticorrosive coatings with bio-mimetic xanthosoma sagittifolium leaf-like, non-fluorinated, super-hydrophobic polymeric Surfaces. Epoxy-acrylate coatings with biomimetic structures can be prepared by performing the UV-radiation process upon casting UV-curable precursor with photo-initiator onto cold-rolled steel (CRS) electrode under PDMS template. Surface morphology of as-synthesized epoxy-acrylate coatings obtained from this UV-curing nanocasting technique was found to show lots of micro-scaled mastoids, each decorated with many nano-scaled wrinkles was investigated systematically by scanning electron microscopy (SEM) and atomic force microscopy (AFM). It should be noted that the water contact angle (CA) of coating with bio-mimetic natural leaf surface was ~ 151°, which was found to significantly higher than that of corresponding polymer with smooth surface (i.e., CA = 88°). Significantly increase of contact angle indicated that this bio-mimetic morphology exhibited effectively water-repelling properties, implying that it may be the potential candidate as advanced anticorrosive coating materials, which can be identified by series of electrochemical corrosion measurements.
The second part, the electroactive silica fibers (ESF) based on conjugated segments of aniline pentamer (AP) were successfully prepared and characterized. First, aniline pentamers were prepared by chemical oxidative coupling reaction, followed by reacting with silane coupling agent (3 –isocyanato propyl triethoxy silane). The electrospining solution was prepared by electroactive silane and tetraethoxysilane (TEOS) through acid-catalyzed sol-gel reaction. The as-prepared electroactive silica fibers were then characterized through Fourier transform infrared spectroscopy (FTIR), liquid chromatography mass spectrometry (LC-mass), 1H-nuclear magnetic resonance (1H-NMR). The morphology of electroactive silica fibers were investigated by scanning electron microscope (SEM). Finally, the composite used to detect ascorbic acid (AA) of the biosensor by electrochemical cyclic voltammetric (CV).

並列關鍵字

epoxy ； electroactive ； electrospun ； sensor ； anti-corrosion ； superhydrophobic surfaces ； polyaniline

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