本研究使用直流電源供應器電聚合PANI於低碳鋼(SAE 1018)表面形成PANI/steel，探討防鏽效能。固定電壓2.00 V將0.15 M之苯胺加入0.20 M磷酸電解液(pH = 2.19)，於陽極析出p-PANI。p-PANI/steel利用Tafel plot (掃描速率：1 mV/s；掃描範圍：-0.9 V至-0.1 V)發現其腐蝕電位值高於裸鋼111 mV。藉由X-光繞射、FT-IR和UV-Vis分析藍色p-PANI之物理性質。p-PANI粉末擁有2θ = 20.35°和25.48°的繞射峰，推測p-PANI中quinoid或benzenoid重覆單元之鏈長為4.39 Å；而p-PANI層與層間距為3.51 Å。p-PANI的FT-IR圖譜中，quinoid的C=N為1578 cm-1；benzenoid的C=C為1490 cm-1。SEM觀察p-PANI/steel，p-PANI膜為多孔結構。p-PANI溶於鹼性DMF之UV-Vis圖譜中，618 nm為quinoid電子π-π＊躍遷；因此，PANI為emeraldine base形態。藉由PPDT(poly(2-N-phenylamino-4,6-dimercapto-S-triazine))附著於鋼與p-PANI之間能降低水及氧之侵蝕。電聚合雙層膜形成p-PANI/PPDT/steel，其腐蝕電位值高於裸鋼200 mV。因此，p-PANI/PPDT雙層膜的防鏽效果更甚於單層p-PANI。

In this research, p-PANI was prepared in a solution containing 0.15 M aniline and 0.20 M phosphoric acid (pH = 2.19) on a low carbon steel (SAE 1018) substrate by a 2.00 V DC power source in order to study the anti-corrosion effect of the electropolymerized film. Comparing the corrosion potential of p-PANI/steel with the bare steel by the Tafel plot (scanning rate, 1 mV/s; potential range, -0.9 V to -0.1 V), the former is 111 mV higher than the latter. The blue p-PANI had two XRD peaks at 2θ = 20.35° and 25.48°. They are probably due to the long range ordering of the quinoid and benzenoid rings. The rings have a length near 4.39 Å and the parallel packed polymers have a van der Waal distance of 3.51 Å. FT-IR spectra of the p-PANI show absorption bands at 1578 cm-1 and 1490 cm-1 corresponding to the quinoid (C=N) and benzenoid (C=C) rings, respectively. The p-PANI/steel film has a porous morphology observed under SEM. Dissolving the p-PANI in DMF, the 618 nm absorption corresponding to the π-π＊transition is found in the UV-Vis spectra that is a characteristic peak of emeraldine base. Adding a PPDT, poly(2-N-phenylamino-4,6-dimercapto-S-triazine), layer between PANI and steel. PPDT is strongly adsorbed on the surface of steel and allows low permeability of water and oxygen. As a consequence, the corrosion potential of p-PANI/PPDT/steel is further increased, 200 mV higher than the bare steel. Hence, the p-PANI/PPDT bilayer material has a better anti-corrosion effect.

總目錄
中文摘要..................................................I
英文摘要................................................II 
謝誌...................................................III 
目錄....................................................IV 
表索引................................................VIII 
圖索引..................................................IX
目錄
第一章、緒論..............................................1
  1-1 聚苯胺(PANI)........................................2
  1-2 PANI合成............................................4
  1-3 PANI之定性與定量分析................................5
    1-3-1 紅外線吸收光譜法(FT-IR) ........................6
    1-3-2 紫外線可見光吸收光譜法(UV-Vis) .................7
    1-3-3 核磁共振光譜法(NMR) ............................8
    1-3-4 分子量、表面積之分析...........................10
  1-4 腐蝕概論...........................................10
    1-4-1 腐蝕原理.......................................10
    1-4-2 腐蝕熱力學.....................................12
    1-4-3 腐蝕動力學.....................................13
    1-4-4 電化學的防鏽測量與極化.........................14
  1-5 PANI之防鏽應用.....................................18
    1-5-1 PANI之防鏽研究與專利...........................18
    1-5-2 聚苯胺防鏽機制.................................19
    1-5-3 提高聚苯胺防鏽效能.............................20
  1-6 研究動機...........................................23
第二章、實驗.............................................24
  2-1 實驗目的...........................................24
  2-2 實驗方法...........................................26
  2-3 鐡/鋼片的前處理....................................26
  2-4 實驗步驟...........................................26
    2-4-1 磷酸或磷酸緩衝液電聚合PANI.....................26
      2-4-1-1 改變電聚合磷酸濃度與電流...................27
      2-4-1-2 改變電聚合電流與電壓於磷酸緩衝液(pH = 5.51)27
      2-4-1-3 改變電聚合電流與電壓於磷酸緩衝液(pH = 5.51)加
              入氧化劑...................................28
      2-4-1-4 改變電聚合之電流與電壓於磷酸緩衝液(pH =   
              6.98)......................................29
      2-4-1-5 改變磷酸緩衝液pH值.........................30
    2-4-2 電聚合PANI或PANI/PPDT..........................31
      2-4-2-1 草酸電解液電聚合o-PANI.....................31
      2-4-2-2 改變電聚合o-PANI/PPDT雙層膜時間............31
      2-4-2-3 不同電解液電聚合PANI並比較其防鏽效果.......32
      2-4-2-4 改變電聚合p-PANI/PPDT雙層膜時間............32
    2-4-3 尋找電聚合PPDT最佳條件.........................33
      2-4-3-1 尋找電聚合PPDT最佳電解質...................33
      2-4-3-2 尋找電聚合PPDT的C9H8N4S2最佳含量...........34
      2-4-3-3 尋找電聚合PPDT的Na2CO3最佳濃度.............35
    2-4-4 p-PANI物理性質測量.............................36
      2-4-4-1 測量p-PANI X-光繞射光譜....................36
      2-4-4-2 測量p-PANI紅外射光譜.......................36
      2-4-4-3 測量p-PANI紫外線可見光吸收光譜.............36
      2-4-4-4 觀察p-PANI的表面結構.......................36
    2-4-5 電聚合p-PANI/PPDT雙層膜於鐡片上................36
  2-5 實驗儀器...........................................37
    2-5-1 超音波震盪儀...................................37
    2-5-2 數位式電源供應器...............................37
    2-5-3 鹽水噴霧試驗機.................................38
    2-5-4 附著力刮刀.....................................39
    2-5-5 鉛筆式硬度計...................................40
    2-5-6 膜厚測定儀.....................................41
    2-5-7 恆電位儀.......................................42
2-5-7-1 開放電流電位(open circuit potential，OCP)測量....43
2-5-7-2 Tafel plot測量...................................43
2-5-7-3 循環伏安法(CV)測量...............................43
    2-5-8 X-光繞射儀(X-ray)..............................44
    2-5-9 紅外線吸收光譜分析儀(FT-IR) ...................44
    2-5-10 紫外線可見光吸收光譜儀(UV-Vis) ...............44
2-5-11 掃描式電子顯微鏡(SEM) ............................44

第三章、結果與討論.......................................45
  3-1 磷酸或磷酸緩衝液電聚合PANI.........................45
    3-1-1 改變電聚合磷酸濃度與電流.......................45
    3-1-2 改變電聚合電流與電壓於磷酸緩衝液(pH = 5.51)....46
    3-1-3 改變電聚合電流與電壓於磷酸緩衝液(pH = 5.51)加入氧
          化劑...........................................47
    3-1-4 改變電聚合電流與電壓於磷酸緩衝液(pH = 6.98)....48
    3-1-5 改變磷酸緩衝液pH值.............................49
  3-2 電聚合PANI或PANI/PPDT..............................53
    3-2-1 草酸電解液電聚合o-PANI.........................53
    3-2-2 改變電聚合o-PANI/PPDT雙層膜之時間..............57
    3-2-3 不同電解液中電聚合PANI並比較防鏽效果...........58
    3-2-4 改變電聚合p-PANI/PPDT雙層膜之時間..............60
  3-3 尋找電聚合PPDT最佳條件.............................62
    3-3-1 尋找電聚合PPDT最佳電解質.......................62
    3-3-2 尋找電聚合PPDT的C9H8N4S2最佳含量...............67
    3-3-3 尋找電聚合PPDT的Na2CO3最佳濃度.................71
  3-4 p-PANI物理性質分析.................................73
    3-4-1 分析p-PANI X-光繞射光譜圖......................74
    3-4-2 分析p-PANI紅外線光譜圖.........................75
    3-4-3 分析p-PANI紫外線可見光吸收光譜圖...............76
    3-4-4 分析p-PANI表面結構.............................77
  3-5 電聚合p-PANI/PPDT雙層膜於鐡片上....................78
第四章 結論..............................................83
參考資料.................................................84
表索引
表1.1、p-PANI的FT-IR特徵吸收峰............................7
表1.2、PANI的UV-Vis吸收光譜之波長.........................8
表2.1、實驗藥品基本物理性質及來源........................24
表2.2、鋼片(SAE 1018)之化學成份..........................25
表2.3、H3PO4液之實驗條件值...............................27
表2.4、磷酸緩衝液(pH = 5.51)之實驗條件值.................28
表2.5、加氧化劑於磷酸緩衝液(pH = 5.51)之實驗條件值.......29
表2.6、磷酸緩衝液(pH = 6.98)之實驗條件值.................30
表2.7、pH值對應表........................................30
表2.8、改變電聚合PPDT之時間..............................31
表2.9、e、f、g、h電解液的溶質濃度........................32
表2.10、改變電聚合時間...................................33
表2.11、k、l、m、n、o電解液的溶質含量....................34
表2.12、改變C9H8N4S2含量.................................35
表2.13、改變Na2CO3濃度...................................35
表2.14、p液中溶質含量....................................36
表2.15、附著力ISO試驗等級判別表(ISO 2409：1992(E)) ......40
表3.1、H3PO4液之實驗結果.................................45
表3.2、磷酸緩衝電解液(pH = 5.51)之實驗結果...............46
表3.3、加氧化劑於磷酸緩衝液(pH = 5.51)之實驗結果.........48
表3.4、磷酸緩衝電解液(pH = 6.98)之實驗結果...............49
表3.5、改變電聚合PPDT時間之實驗結果......................58
表3.6、改變電解液之Tafel plot參數值..................... 60
表3.7、改變電聚合時間之Tafel Plot參數值................. 61
表3.8、改變C9H8N4S2含量之電化學參數值....................70
表3.9、p-PANI/PPDT膜之厚度、硬度和附著力.................80


圖索引
圖1.1、PANI基本結構.......................................3
圖1.2、PANI五種形態.......................................3
圖1.3、PANI五種形態彼此間的摻雜與去摻雜及氧化還原.........4
圖1.4、PANI結構中官能基的名稱.............................6
圖1.5、13C NMR圖譜........................................9
圖1.6、PANI官能基之化學位移..............................10
圖1.7、Tafel plot圖譜....................................17
圖1.8、PANI防鏽機制......................................20
圖1.9、PANI及磷酸鹽類保護之鋼片......................... 22
圖1.10、PANI/PPDT膜防鏽機制..............................22
圖2.1、Chrom Tech UC-3120B (H)單頻超音波震盪儀...........37
圖2.2、TOPWARD 6303D數位式電源供應器.....................38
圖2.3、Chtek SH-90型鹽水噴霧試驗機.......................38
圖2.4、JL-1540刮刀.......................................39
圖2.5、台灣錦亮B-3084T3鉛筆式硬度計......................41
圖2.6、Fischer Deltascope MP10磁性、電感應式膜厚儀與探針.42
圖2.7、AutoLab PGSTAT100恆電位儀.........................42
圖3.1、磷酸緩衝液pH = 6.00電聚合PANI之CV圖譜............ 50
圖3.2、磷酸緩衝液pH = 6.50電聚合PANI之CV圖譜.............51
圖3.3、磷酸緩衝液pH = 7.00電聚合PANI之CV圖譜.............51
圖3.4、磷酸緩衝液pH = 7.50電聚合PANI之CV圖譜.............52
圖3.5、磷酸緩衝液pH = 7.50反應性最佳.....................52
圖3.6、磷酸根之UV-vis譜圖................................53
圖3.7、草酸鈍化之CV圖譜..................................55
圖3.8、草酸電聚合PANI之第一次循環CV圖譜..................56
圖3.9、草酸電聚合PANI之CV圖譜............................56
圖3.10、o-PANI/steel於草酸之CV圖譜.......................57
圖3.11、PANI/steel之Tafel plot圖譜.......................59
圖3.12、p-PANI/PPDT/steel之Tafel plot圖譜................61
圖3.13、acetonitrile電聚合PPDT之CV圖譜...................62
圖3.14、草酸電聚合PPDT之CV圖譜...........................63
圖3.15、碳酸氫鈉電聚合PPDT之CV圖譜.......................64
圖3.16、草酸鈉電聚合PPDT之CV圖譜.........................65
圖3.17、碳酸鈉電聚合PPDT之CV圖譜.........................66
圖3.18、碳酸鈉電聚合PPDT之第一次循環CV圖譜...............67
圖3.19、改變C9H8N4S2含量電聚合PPDT之CV圖譜...............68
圖3.20、取圖3.19氧化電位值0.80至1.20 V的CV函數圖譜.......69
圖3.21、圖3.20 CV函數圖譜一次微分........................69
圖3.22、C9H8N4S2溶質克數對應電流密度值...................70
圖3.23、改變碳酸鈉莫耳濃度電聚合PPDT之CV圖譜.............72
圖3.24、圖3.23的CV函數一次微分...........................72
圖3.25、碳酸鈉濃度對應電流密度值.........................73
圖3.26、直流電源供應器電聚合p-PANI.......................74
圖3.27、p-PANI之X-ray圖譜................................75
圖3.28、p-PANI之FT-IR圖譜................................76
圖3.29、p-PANI之UV-Vis圖譜...............................77
圖3.30、p-PANI之SEM圖譜放大3000倍........................78
圖3.31、p-PANI/PPDT/iron，SST實驗結果....................79
圖3.32、p-PANI/PPDT雙層膜電聚合於鐡片上之厚度............80
圖3.33、p-PANI/PPDT/iron之OCP圖譜........................81
圖3.34、p-PANI/PPDT/iron之Tafel plot圖譜.................82

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