本研究利用較具環保性且鐵片不需複雜的前處理過程的單寧酸(Tannic acid)能與鐵金屬形成穩定鐵之錯化合物的特性，將其應用在鐵金屬表面之防蝕塗佈上，底漆(Base coat)以自由基硬化型環氧樹脂(UV-Epoxy)添加鋅粉和三羥甲基丙烷三丙烯酸酯(Trimethylolpropane triacrylate, TMPTA) ，以不同比例混合後，使用旋轉塗佈(Spin-coating)塗佈在金屬表面上後，以照射紫外光來產生自由基使混摻的化合物產生交聯，其不僅是鋅金屬與單寧酸產生穩定錯化合物鍵結，且因加入的TMPTA和UV-Epoxy產生架橋，而在金屬表面上形成緻密穩定的表面塗層。接著再進一步塗佈具疏水性官能基的面漆(Top coat)，行紫外光交聯後，讓金屬、底漆與面漆產生緊密的結合，使得塗佈的底漆與面漆緻密覆蓋於金屬上達到相當好的抗腐蝕效果。

An aqueous tannic acid solution is used as steel surface coating primer; This characteristic can form black stablely complex with steel metal. In this experiment, we modify different ratio of UV-Epoxy, TMPTA and Zinc powder as base coat, then we use spin-coating method to spread them on steel metals’ surface. After that we add appropriate amount of Photo-initiator(e.g. 1173) to UV-curing. Exposing in UV light produce free radicals which lead compositions to crosslinking. Then a top coat resins consists of hydrophobicity of UV-reactive UV-PU and a tri-acrylate UV-reactive diluent (TMPTA) as a reactive diluent are applied on metal surface as a top coat. A photo-initiator are added and cured respectively with UV-radiation. The treated steel metal surface coating properties has been evaluated by salt spray to exhibit its anti-corrosion. The best results in our experiments are that the top coat containing PDMS-function which could put in salt-spray test without corrosion more than 750 hours.

總                  目                 錄
中文摘要................................................
英文摘要.............................................
謝誌....................................................

一、	序論............................................1
1-1前言...................................................1
1-2腐蝕原理.............................................2
1-3腐蝕形態.............................................4
1-4防蝕機制.............................................7
1-5研究動機與目的......................................11

二、	文獻回顧..............................................
2-1聚胺酯簡介............................................12
2-1-1聚胺酯發展歷程...................................12
2-1-2聚胺酯的基本材料................................13
2-2單寧酸簡介............................................17
2-2-1單寧酸之化學性.............................17
2-2-2單寧酸之分類..............................18
2-2-3單寧酸之存在............................19
2-2-4單寧酸之應用............................................21
2-3磷酸鹽膜化簡介........................................22
2-4紫外光交聯技術........................................24
2-5環氧樹脂簡介..........................................31
    2-5-1環氧樹脂的特性..................................34
    2-5-2環氧樹脂的應用..................................35
    2-5-3環氧化合物之反應性..............................38
    2-5-4環氧樹脂之改質..................................39
2-6有機/無機奈米複合材料.................................40

三、	實驗................................................44
3-1化學藥品..............................................44
3-2儀器..................................................47
3-3底漆的製備..................................................48
    3-3-1自由基硬化環氧樹脂(UV-Epoxy)合成........................48
    3-3-2 PTMEG-DMPA-IPDI Prepolymer之合成........................49
    3-3-3 PTMEG-DMPA-IPDI-HEMA Prepolymer(UV-PU-CO2H)之合成..................................................50
3-4含長碳鏈面漆的製備(Top Coat).............................................51
    3-4-1 Glycerol-IPDI Oligomer之合成......................................51
    3-4-2 Glycerol-IPDI-Cetyl Oligomer之合成...........................52
    3-4-3 Glycerol-IPDI-Cetyl-PTMEG Prepolymer之合成...............53
    3-4-4 Glycerol-IPDI-Cetyl-PTMEG-HEMA Prepolymer之合成...54
3-5含氟素面漆的製備(Top Coat) .............................................55
    3-5-1 Glycerol-IPDI-OFP Oligomer之合成.........................55
    3-5-2 PTMEG-IPDI Prepolymer(diol)之合成.........................56
    3-5-3 Glycerol-IPDI-OFP-PTMEG-IPDI Prepolymer之合成.......57
    3-5-4 Glycerol-IPDI-OFP-PTMEG-IPDI-HEMA Prepolymer之
合成(F%=7.7%).............................58
    3-5-5 Glycerol-IPDI-OFP-PTMEG-IPDI Prepolymer之合成......59
    3-5-6 Glycerol-IPDI-OFP-PTMEG-IPDI-HEMA Prepolymer之
合成(F%=8.89%)..................................60
3-6 含聚二甲基矽氧烷面漆的製備(Top Coat)........................61
    3-6-1 PDMS Prepolymer (diisocyanate)之合成......................61
    3-6-2 PDMS-IPDI-PTMEG Prepolymer之合成.....................62
    3-6-3 PDMS-IPDI-PTMEG-HEMA Prepolymer (UV PDMS-PU 
11.6 Blend型)之合成........................................63
    3-6-4 PTMEG-2000 Prepolymer (diisocyanate)之合成.................64
    3-6-5 PTMEG-IPDI-PDMS Prepolymer之合成....................65
    3-6-6 PTMEG-IPDI-PDMS-HEMA Prepolymer (UV PDMS-PU 11.6 Block型)之合成..........................................66
3-7單寧酸(Tannic acid)對鋼板防蝕效果探討(Primer)..................67
    3-7-1配置單寧酸水溶液(旋轉塗佈加工)..........................67
3-8底漆(Base Coat)對鋼板防蝕效果探討.............................68
3-8-1 UV-Epoxy混摻鋅粉及TMPTA(旋轉塗佈加工)................68
    3-8-2 UV-PU混摻鋅粉及TMPTA(旋轉塗佈加工)....................69
3-9底漆(Base Coat)與面漆(Top Coat)對鋼板防蝕效果探討............70
3-9-1底漆與Glycerol-IPDI-Cetyl-PTMEG-HEMA Prepolymer旋轉塗佈加工.....................................................70
3-9-2底漆與Glycerol-IPDI-OFP7.7-PTMEG-IPDI-HEMA Prepolymer旋轉塗佈加工.......................................71
3-9-3底漆與Glycerol-IPDI-OFP8.9-PTMEG-IPDI-HEMA Prepolymer旋轉塗佈加工........................................72
3-9-4 底漆與PDMS-IPDI-PTMEG-HEMA Prepolymer(UV PDMS-PU 11.6 Blend型)旋轉塗佈加工..................................73
3-9-5 底漆與PTMEG-IPDI-PDMS-HEMA Prepolymer (UV PDMS-PU 11.6 Block型)旋轉塗佈加工..........................74
3-10固含量測試....................................................75
3-11聚胺酯預聚物異氰酸酯含量(NCO %)測定...........................75
    3-11-1藥品配置..................................................75
3-11-2分析步驟.....................................76
3-12紅外線光譜(FT-IR)鑑定..................................77
3-13 薄膜物理性質測試.....................................77
3-13-1 膠含量(Gel Content)測定................................77
3-13-2 吸水性(Water-Uptake，WA %)及對水損失率(Weight Loss，WL%)測定.........................................77
3-13-3 吸酒精性(Ethanol-Uptake，EA %)及對酒精損失率(Weight Loss in Ethanol，EL%)測定.................................78
3-13-4 薄膜接觸角(Contact Angle)測定............................79
3-14 附著度測試(Cross-cut Test)......................................80
3-15鉛筆硬度測試(Pencil Test).........................................81
3-16 鹽霧試驗(Salt Spray Test).......................................82
3-17掃描式電子顯微鏡測試(Scanning Electron Microscope,SEM)….83
3-18能量散射光譜儀測試 (Energy Dispersive Spectrometer)………..83
3-19原子力顯微鏡(Atomic Force Microscope,AFM).....................84
3-20電化學分析(Electronchemical).................................84


四、	結果與討論...........................................................87
4-1 底漆製備之紅外線光譜鑑定............................................87
    圖4-1-1a Epoxy-904之FT-IR光譜圖..........................88
圖4-1-1b UV-Epoxy之FT-IR光譜圖.........................88
圖4-1-2 PTMEG-IPDI-DMPA-HEMA Prepolymer(UV-PU-CO2H)之FT-IR光譜圖.............................................89
4-2含長碳鏈面漆之FT-IR紅外線光譜鑑定...............................90
4-2-1 Glycerol-IPDI Oligomer之FT-IR紅外線光譜鑑定............90
圖4-2-1a Glycerol monomer之FT-IR光譜圖.........................91
圖4-2-1b Glycerol-IPDI Oligomer之FT-IR光譜圖..................91
4-2-2 Glycerol-IPDI-Cetyl Oligomer之FT-IR紅外線光譜鑑定.....92
圖4-2-2 Glycerol-IPDI-Cetyl Oligomer之FT-IR光譜圖.............92
4-2-3 Glycerol-IPDI-Cetyl-PTMEG-HEMA Prepolymer之FT-IR紅外線光譜鑑定.....................................................93
圖4-2-3 Glycerol-IPDI-Cetyl-PTMEG-HEMA Prepolymer之FT-IR紅外線光譜圖...............................................93
4-3含氟素面漆製備之FT-IR紅外線光譜鑑定................................94
4-3-1 Glycerol-IPDI Oligomer之FT-IR紅外線光譜鑑定..............94
圖4-3-1a Glycerol之FT-IR光譜圖................................95
圖4-3-1b Glycerol-IPDI Oligomer之FT-IR光譜圖..................95
4-3-2 Glycerol-IPDI-OFP Oligomer之FT-IR紅外線光譜鑑定.......96
圖4-3-2 Glycerol-IPDI-OFP Oligomer之FT-IR光譜圖..............96
4-3-3 PTMEG Prepolymer(diol) 之FT-IR紅外線光譜鑑定..........97
圖4-3-3 PTMEG Prepolymer(diol)之FT-IR光譜圖.................97


4-3-4Glycerol-IPDI-OFP7.7-PTMEG-IPDI-HEMA Prepolymer之FT-IR紅外線光譜鑑定........................................98
圖4-3-4 Glycerol-IPDI-OFP7.7-PTMEG-IPDI-HEMA Prepolymer之FT-IR光譜圖...............................................98
4-3-5 Glycerol-IPDI-OFP8.9-PTMEG-IPDI-HEMA Prepolymer之FT-IR紅外線光譜鑑定.........................................99
圖4-3-5 Glycerol-IPDI-OFP8.9-PTMEG-IPDI-HEMA Prepolymer之FT-IR光譜圖..............................................99
4-4 含聚二甲基矽氧烷面漆製備之FT-IR紅外線光譜鑑定
4-4-1 PDMS Prepolymer (diisocyanate)之FT-IR紅外線光譜鑑定..98
圖4-4-1 PDMS Prepolymer (diisocyanate)之FT-IR光譜圖..........100
4-4-2 PDMS-IPDI-PTMEG-HEMA Prepolymer之FT-IR紅外線光譜鑑定......................................................101
圖4-4-2 PDMS-IPDI-PTMEG-HEMA Prepolymer之FT-IR紅外線光譜圖.......................................................101
4-4-3 PTMEG-2000 Prepolymer(diisocyanate)之FT-IR紅外線光譜鑑定..............................................102
圖4-4-3 PTMEG-2000 Prepolymer (diisocyanate)之FT-IR紅外線光譜圖................................................102
4-4-4 PTMEG-IPDI-PDMS-HEMA Prepolymer之FT-IR紅外線光譜鑑定........................................................103
圖4-4-4 PTMEG-IPDI-PDMS-HEMA Prepolymer之傅式紅外線光譜圖.........................................................103
4-5單寧酸(Primer)對鋼板的效果探討..................................104
圖4-5-1單寧酸之FT-IR光譜圖......................................104
圖4-5-2 Tannic acid/FeCl3不同比例的FT-IR圖........................105
圖4-5-3 Tannic acid/Zn powder不同比例的FT-IR圖..................105
圖4-5-4空白、塗佈Tannic acid之鋼板鹽霧測試.................106
圖4-5-5 空白Fe金屬及塗佈Tannic acid之Tafel Plot................107
4-6底漆(Base Coat)對鋼板防蝕效果探討....................................108
   表4-6-1不同比例底漆的膠含量測試.......................................109
   表4-6-2不同比例底漆之附著度測試......................................109
   表4-6-3不同比例底漆之鉛筆硬度測試..................................110
   圖4-6-1 Tannic acid/不同Base coat之鋼板鹽霧測試24hrs......111
   圖4-6-2 Tannic acid/不同比例Base coat之鋼板鹽霧測試48hr.........................................................111
圖4-6-3 Fe金屬塗佈不同比例的Base coat之Tafel Plot...........112
4-7底漆(Base Coat)與面漆(Top Coat)對鋼板防蝕效果探討.............113
   4-7-1底漆與面漆......................................................113
表4-7-1 Top coat膠含量測試.......................................114
表4-7-2 Top coat+TMPTA膠含量測試.............................114
表4-7-3 Top coat+TMPTA之吸水性及對水損失性測試...........115
表4-7-4 Top coat+TMPTA之接觸角測試................................116
表4-7-5 Base coat/Top coat塗佈鋼板附著度測試..............117
表4-7-6 Base coat/(Top coat+TMPTA)塗佈鋼板附著度測試.......117
表4-7-7 Base coat/(Top coat+TMPTA)塗佈鋼板之鉛筆硬度測試............................................................................................118
圖4-7-1 Base coat/(Top coat+TMPTA)之鋼板鹽霧測試120hrs.................................................................119
圖4-7-2 Base coat/(Top coat+TMPTA)之鋼板鹽霧測試312hrs.......................................................................120
圖4-7-3 Base coat/(Top coat+TMPTA)之鋼板鹽霧測試...........120
圖4-7-4 Fe金屬塗佈不同Top Coat之Tafel Plot.............................121
圖4-7-5 塗佈Base coat之鋼板SEM圖放大倍率一千倍..........123
圖4-7-6 塗佈Base coat之鋼板SEM圖放大倍率三千倍..........123
圖4-7-7塗佈Base coat/GICPH之鋼板SEM圖放大倍率一千倍...................................................................124
圖4-7-8 塗佈Base coat/GICPH之鋼板SEM圖放大倍率三千倍..................................................................124
圖4-7-9 塗佈Base coat/OFP7.7之鋼板SEM圖放大倍率一千倍............................................................125
圖4-7-10 塗佈Base coat/OFP7.7之鋼板SEM圖放大倍率三千倍..............................................................125
圖4-7-11 塗佈Base coat/PDMS11.6(blend型)之鋼板SEM圖放大倍率一千倍...................................................126
圖4-7-12塗佈Base coat/PDMS11.6(blend型)之鋼板SEM圖放大倍率三千倍......................................................126
圖4-7-13塗佈Base coat/GICPH之鋼板EDS圖..................127
圖4-7-14塗佈Base coat/OFP7.7之鋼板EDS圖.................128
圖4-7-15塗佈Base coat/PDMS11.6(blend型)之鋼板EDS圖............................................................128
圖4-7-16 塗佈Base coat之鋼板AFM圖............................129
圖4-7-17 塗佈Base coat/GICPH之鋼板AFM圖.................130
圖4-7-18 塗佈Base coat/PDMS11.6(blend型)之鋼板AFM圖........................................................130
圖4-7-19 塗佈Base coat之鋼板AFM-3D圖........................131
圖4-7-20 塗佈Base coat/GICPH之鋼板AFM-3D圖............131

五、	結論..................................................................132

六、	參考資料.......................................................134

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