CPANi防腐涂料的性能和防腐机理的研究
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摘要
煤基聚苯胺（CPANi）是利用天然煤的大分子结构、化学结构和聚集态结构，以及煤表面有极性酚羟基和羧基的结构特点，以煤为模板，在其中引入苯胺单体，然后引发苯胺在位聚合，得到具有互穿网络结构和插层结构的CPANi化合物。所制得的CPANi在导电性、稳定性和耐候性方面都与文献中所述的纯聚苯胺（PANi）相差不大。能否将其用于防腐涂料中并开发出相应的CPANi防腐涂料是本论文的研究方向，这为开拓出煤功能材料化利用的新途径，具有重要的理论和现实意义。本论文选择防腐涂料中应用广泛的三种型号的环氧树脂（它具有优异的附着力和耐水性）作为基料，按照相关文献介绍的方法选取相应的固化剂，并选择相应的溶剂将其配制成双组分溶液。利用相应的性能测试方法（如测量涂层的均匀性、韧性、干/湿态附着力、以及用ASTM D610-85和D714-87的标准评价加速浸泡过程中涂层表面的腐蚀和鼓泡等级，检测和比较不同组分配比下涂层相关性能的差异，并采用优选法筛选出综合性能具佳的CPANi防腐涂料配方（CPANi：环氧树脂XK-3型：固化剂=20～30：100：6）。然后，利用电化学测试（如测量涂层电极的自腐蚀电位、线性极化电阻和动电位Tafel极化曲线）和X衍射、扫描电镜等方法研究了涂料中煤基聚苯胺不同含量下的相关防腐性能；在所确定的配方中保持环氧树脂和固化剂配比不变，以常规的防腐填料（如锌粉、红丹等）替代CPANi前后涂层的防腐性能的变化情况；还比较了该配方与聚氨酯防腐漆、环氧富锌底漆、银粉漆等在防腐性能上的区别。研究结果表明，所研制的煤基聚苯胺防腐涂料具有良好的综合防腐性能。在长期浸泡过程中它对介质中腐蚀性物质具有良好的屏蔽作用，从而能保持涂层对基体良好的附着力，并能对碳钢能起到阳极保护作用，将碳钢表面的电位正向提升了500mV左右。与空白涂层（不加任何填料）相比，其腐蚀速度降低达三个数量级以上，从而起到防止金属基体腐蚀的功效。最后，在这些研究结果的基础上建立了CPANi的防腐模型，并通过所建立的模型解释了CPANi防腐涂料的屏蔽作用、缓蚀作用和阳极保护作用对金属基体共同保护结果。
故而煤基聚苯胺防腐涂料具有一定的开发价值和前景。
Coal Base Polyaniline (CPANi) was polymerized by inducing aniline monomer into template of coal to get interlinked network and intercalate compound, which utilized macromolecular structure, chemical state and accumulating state, carboxyl group and pheonol hydroxyl group of natural coal. The CPANi is similar to polyaniline in conductivity, stability and endurance. The investigation aspect of this paper is whether CPANi can be used in anti-corrosion coating, which has more important signification in academic and practical for new approach to make use of coal in function material.
Three types expoxy resin used in anti-corrosion coating widely were chosen to be essential stuff because expoxy resin has more excellent adhesion and waterproof, and were confected solution with solvent. Then the relevant harder was chosen. The testing methods including uniformity, tension, dry and wet adhesion, blister and corrosion degree of coating after accelerating immersion by ASTM D610-85 and D714-87 were used to test coating relevant performance. Through these test results, the proportion of CPANi, expoxy resin and harder was selected, which is CPANi：epoxy Model XK-3：harder=20～30：100：6 with excellent anti-corrosion performance.
Then the electrochemical testing including open circuit potential, line polarization resistance and Tafel polarization, and XRD, SEM were used to investigate anti-corrosion performance and mechanism of CPANi anti-corrosion coating. The content of study include: the relevant anti-corrosion performance with different proportion of CPANi in coating; maintaining the proportion of expoxy and harder, the anti-corrosion performance with different filling such as Zn, red lead and CPANi; the similarities and differences anti-corrosion performance of CPANi coating with polyamicester anti-corrosion coating, expoxy rich zine primer and sliver powder coating;
The result of investigation indicate CPANi anti-corrosion coating has excellent anti-corrosion performance. CPANi in coating can provide good shield performance for
coating during immersion so that the coating can maintenance good adhesion with fundus. The CPANi anti-corrosion coating can provide carbon steel with anodic protection, because the OCP of carbon steel can be increased 500mV. The corrosion rate of carbon steel can be decreased three magnitude comparing with blank coating. At last, basing on the testing results, the anti-corrosion model of CPANi coating was built, which was used to explain shield, inhibition and positive protection performance of CPANi coating.
Therefore, CPANi anti-corrosion coating is worth developing and has applicable foreground.
故而煤基聚苯胺防腐涂料具有一定的开发价值和前景。
Coal Base Polyaniline (CPANi) was polymerized by inducing aniline monomer into template of coal to get interlinked network and intercalate compound, which utilized macromolecular structure, chemical state and accumulating state, carboxyl group and pheonol hydroxyl group of natural coal. The CPANi is similar to polyaniline in conductivity, stability and endurance. The investigation aspect of this paper is whether CPANi can be used in anti-corrosion coating, which has more important signification in academic and practical for new approach to make use of coal in function material.
Three types expoxy resin used in anti-corrosion coating widely were chosen to be essential stuff because expoxy resin has more excellent adhesion and waterproof, and were confected solution with solvent. Then the relevant harder was chosen. The testing methods including uniformity, tension, dry and wet adhesion, blister and corrosion degree of coating after accelerating immersion by ASTM D610-85 and D714-87 were used to test coating relevant performance. Through these test results, the proportion of CPANi, expoxy resin and harder was selected, which is CPANi：epoxy Model XK-3：harder=20～30：100：6 with excellent anti-corrosion performance.
Then the electrochemical testing including open circuit potential, line polarization resistance and Tafel polarization, and XRD, SEM were used to investigate anti-corrosion performance and mechanism of CPANi anti-corrosion coating. The content of study include: the relevant anti-corrosion performance with different proportion of CPANi in coating; maintaining the proportion of expoxy and harder, the anti-corrosion performance with different filling such as Zn, red lead and CPANi; the similarities and differences anti-corrosion performance of CPANi coating with polyamicester anti-corrosion coating, expoxy rich zine primer and sliver powder coating;
The result of investigation indicate CPANi anti-corrosion coating has excellent anti-corrosion performance. CPANi in coating can provide good shield performance for
coating during immersion so that the coating can maintenance good adhesion with fundus. The CPANi anti-corrosion coating can provide carbon steel with anodic protection, because the OCP of carbon steel can be increased 500mV. The corrosion rate of carbon steel can be decreased three magnitude comparing with blank coating. At last, basing on the testing results, the anti-corrosion model of CPANi coating was built, which was used to explain shield, inhibition and positive protection performance of CPANi coating.
Therefore, CPANi anti-corrosion coating is worth developing and has applicable foreground.
引文
[1]刘秀晨，安成强.金属腐蚀学. 北京:国防工业出版社,2002
[2]朱日彰.金属腐蚀学.北京：冶金工业出版社，1989
[3]曹楚南.腐蚀电化学基础.北京：化学工业出版社，1985
[4]黄永昌.金属腐蚀与防护原理.上海：上海交通大学出版社，1989
[5]赵麦群，雷阿丽.金属的腐蚀与防护.北京:国防工业出版社,2002
[6]张天胜,缓蚀剂.北京:化学工业出版社,2001
[7]虞兆年,防腐蚀涂料和涂装.北京: 化学工业出版社,2002
[8]宣兆光，易建政，杜仕国等.金属防腐涂料的研究进展. 现代化工，1999（4）：23～24
[9]杨锋,吴庆余,李淑柱等. 防腐蚀涂料. 涂料工业，1999(9):32～35
[10]付文静. 国内外防腐蚀涂料的技术现状与发展. 全面腐蚀控制,2001(1):24～27
[11]周海晖，许岩，罗胜联等.我国防腐蚀涂料的现状及其发展.表面技术,2002,(2):5～8
[12]姜英涛.涂料基础.北京: 化学工业出版社,1997,9
[13]刘素琴，刘建生，黄可龙．功能高分子聚苯胺及其应用研究进展．湖南化工，1999，29（4）：1～3
[14]W.DeBerry. Modification of the Electrochemical and Corrosion Behavior of Stainless Steels With an Electroactive Coating , .Electrochemical Society 132 (1985 ): 102
[15]王光国. 国外聚苯胺防腐涂料工业研发概况.全面腐蚀控制，2002，16（2）：23～24
[16]张金勇，李季，王献红. 导电聚苯无溶剂防腐涂料的制备方法.中国专利，98116978.3
[17]王献红，孙祖信，耿延候等. 导电聚苯胺防污防腐涂料的制备方法.中国专利，97115977.7
[18]井新利，王杨勇. 一种聚苯胺防腐涂料的制备工艺.中国专利，01138153.1
[19]张金勇，李季，王献红等. 聚苯胺在防腐领域的应用.功能高分子学报，1999，12（3）：350～356
[20]苏慈生.导电聚苯胺在防腐涂料中的应用.现代涂料与涂装，2001，（1）：1～4
[21]M.C.Bernard, A. Hugot-LeGoff,S.Joiret. Polyaniline Layer for Iron Protection in Sulfate Medium. Synthetic Metal, 1999, 102:1383～1384
[22]Camalet JL, Lacroix JC, Aeiyach S, Chaneching K, Lacaze PC. Electrosynthesis of Adherent Polyaniline Films on Iron and Mild Steel in Aqueous Oxalic Acid Medium. Synthetic Metal, 1998, 93:133～142
[23]Yen Wei, Jianguo Wang, Xinru Jia and Jui-Ming Yeh. Polyaniline as Corrosion Protection Coatings on Cold Rolled Steel. Polymer, 1995, 36:4535～4537
[24]Lu WK, Elsenbaumer RL, Wessling B. Corrosion Protection of Mild Steel by Coatings Containing Polyaniline . Synthetic Metal, 1995, 71:2163～2166
[25]A. Talo, P. Passiniemi, O. Forsen, et. Polyaniline Epoxy Coating With Good Anticorrosion Properties . Synthetic Metal, 1997, 85: 1333～1334
[26]Schuman TP, Thames SF (1999) In: Proc 26th Int Waterborne, High-Solids, Powder Coat Symp, pp318～335; (2000) Chem Abstr 133:5892
[27]李忠东.涂料防腐蚀机理研究进展.化工新型材料.1995.6～8
[28]黄永昌.金属腐蚀与防护原理.上海：上海交通大学出版社.1989.5
[29]Dennis E.Tallman, Geoff Spinks, Anton Dominis, et. Electroactive conducting polymers for corrosion control: Part 1. General introduction and a review of non-ferrous metals . J Solid State Electrochem, 2002, 6: 73～84
[30]Dennis E.Tallman, Geoff Spinks, Anton Dominis, et. Electroactive conducting polymers for corrosion control: Part 2. Ferrous metals . J Solid State Electrochem, 2002, 6: 85～100
[31]Wessling B. Passivation of Metals by Coating with Polyaniline: Corrosion Potential Shift and Morphological Changes. Advanced Materials, 1994, 6:226～228
[32]Wei Y, Wang JG, Jai XR, Yeh, JM, Spellane P. Polyaniline as Corrosion Protection Coatings on Cold Rolled Steel . Polymer, 1995, 36:4535～4537
[33]Schauer T, Joos A, Dulog L, Eisenbach CD. Protection of Iron Against Corrosion with Polyaniline Primers . Progress in Organic Coatings, 1998, 33:20～27
[34]Santos JR, Mattoso LHC, Motheo AJ. Investigation of Corrosion Protection of Steel by Polyaniline Films. Electrochemical Acta, 1998, 43:309～313
[35]郑家乐.金属电化学和缓蚀剂保护技术.上海：上海科学技术出版社，1984，7
[36]Kinlen PJ, Silverman DC, Jefferys CR. Corrosion Protection Using Polyaniline Coating Formulations . Synthetic Metal, 1997, 85:1327～1332
[37]Fahlman M, Guan H, Smallfield JAO, Epstein AJ (1998) In: 56th Annu Tech Conf Soc Plast Eng 1238～1241; (1998) Chem Abstr 130:44596
[38]Ahmad N, Macdiarmid AG. Inhibition of corrosion of steels with the exploitation of conducting polymers. Synthetic Metal,1996, 78:103～110
[39]Talo A, Forsen O, Ylasaari S. Corrosion Protective Polyaniline Epoxy Blend Coatings on Mild Steel. Synthetic Metal, 1999,102:1394～1395
[40]Fahlman M, Jasty S, Epstein AJ. Corrosion Protection of Iron/Steel by Emeraldine Base Polyaniline: An X-ray Photoelectron Spectroscopy Study. Synthetic Metal, 1997, 85:1323～
1326
[41]Zhou Anning，Zhang Baizhan．Study of Polyaniline/Coal Conductive Composite Material．6th Pacific Polymer Conference，1999，12
[42]汪晓芹. 煤基聚苯胺的合成、性能、聚合机理及其应用的研究：[学位论文].西安：西安科技学院，1998
[43]武利民，李丹，游波. 现代涂料配方设计. 北京：化学工业出版社，2000.3
[44]陈平，刘胜平.环氧树脂.北京：化学工业出版社，1999
[45]周润根.涂料用溶剂的组成与性能,,电镀与涂饰，1999（1）33～36
[46]Jhon N. Murray. Electrochemical test methods for evaluating organic coatings on metals: Part 1. Introductions and generalities regarding electrochemical testing of organic coatings . Progress in Organic Coatings, 1997, 30:225～233
[47]Jhon N. Murray. Electrochemical test methods for evaluating organic coatings on metals: Part 2. Singel test parameter measurements . Progress in Organic Coatings, 1997, 31:255～264
[48]Jhon N. Murray. Electrochemical test methods for evaluating organic coatings on metals: Part 2. Multiple test parameter measurements . Progress in Organic Coatings, 1997, 31:375～391
[49]C.H.Tsai, F.Mansfeld. Determiantion of Coating Deterioation With EIS: Part 2 Development of a Method for Field Testing of Protective Coatings . Corrosion 1993 (9):726～737
[50]A.A. Pud, G.S. Shapoval, P. Kamarchik, et. Electrochemical behavior of mild steel coated by polyaniline doped with organic sulfonic acids . Synthetic Metal, 1999, 107:111～115
[2]朱日彰.金属腐蚀学.北京：冶金工业出版社，1989
[3]曹楚南.腐蚀电化学基础.北京：化学工业出版社，1985
[4]黄永昌.金属腐蚀与防护原理.上海：上海交通大学出版社，1989
[5]赵麦群，雷阿丽.金属的腐蚀与防护.北京:国防工业出版社,2002
[6]张天胜,缓蚀剂.北京:化学工业出版社,2001
[7]虞兆年,防腐蚀涂料和涂装.北京: 化学工业出版社,2002
[8]宣兆光，易建政，杜仕国等.金属防腐涂料的研究进展. 现代化工，1999（4）：23～24
[9]杨锋,吴庆余,李淑柱等. 防腐蚀涂料. 涂料工业，1999(9):32～35
[10]付文静. 国内外防腐蚀涂料的技术现状与发展. 全面腐蚀控制,2001(1):24～27
[11]周海晖，许岩，罗胜联等.我国防腐蚀涂料的现状及其发展.表面技术,2002,(2):5～8
[12]姜英涛.涂料基础.北京: 化学工业出版社,1997,9
[13]刘素琴，刘建生，黄可龙．功能高分子聚苯胺及其应用研究进展．湖南化工，1999，29（4）：1～3
[14]W.DeBerry. Modification of the Electrochemical and Corrosion Behavior of Stainless Steels With an Electroactive Coating , .Electrochemical Society 132 (1985 ): 102
[15]王光国. 国外聚苯胺防腐涂料工业研发概况.全面腐蚀控制，2002，16（2）：23～24
[16]张金勇，李季，王献红. 导电聚苯无溶剂防腐涂料的制备方法.中国专利，98116978.3
[17]王献红，孙祖信，耿延候等. 导电聚苯胺防污防腐涂料的制备方法.中国专利，97115977.7
[18]井新利，王杨勇. 一种聚苯胺防腐涂料的制备工艺.中国专利，01138153.1
[19]张金勇，李季，王献红等. 聚苯胺在防腐领域的应用.功能高分子学报，1999，12（3）：350～356
[20]苏慈生.导电聚苯胺在防腐涂料中的应用.现代涂料与涂装，2001，（1）：1～4
[21]M.C.Bernard, A. Hugot-LeGoff,S.Joiret. Polyaniline Layer for Iron Protection in Sulfate Medium. Synthetic Metal, 1999, 102:1383～1384
[22]Camalet JL, Lacroix JC, Aeiyach S, Chaneching K, Lacaze PC. Electrosynthesis of Adherent Polyaniline Films on Iron and Mild Steel in Aqueous Oxalic Acid Medium. Synthetic Metal, 1998, 93:133～142
[23]Yen Wei, Jianguo Wang, Xinru Jia and Jui-Ming Yeh. Polyaniline as Corrosion Protection Coatings on Cold Rolled Steel. Polymer, 1995, 36:4535～4537
[24]Lu WK, Elsenbaumer RL, Wessling B. Corrosion Protection of Mild Steel by Coatings Containing Polyaniline . Synthetic Metal, 1995, 71:2163～2166
[25]A. Talo, P. Passiniemi, O. Forsen, et. Polyaniline Epoxy Coating With Good Anticorrosion Properties . Synthetic Metal, 1997, 85: 1333～1334
[26]Schuman TP, Thames SF (1999) In: Proc 26th Int Waterborne, High-Solids, Powder Coat Symp, pp318～335; (2000) Chem Abstr 133:5892
[27]李忠东.涂料防腐蚀机理研究进展.化工新型材料.1995.6～8
[28]黄永昌.金属腐蚀与防护原理.上海：上海交通大学出版社.1989.5
[29]Dennis E.Tallman, Geoff Spinks, Anton Dominis, et. Electroactive conducting polymers for corrosion control: Part 1. General introduction and a review of non-ferrous metals . J Solid State Electrochem, 2002, 6: 73～84
[30]Dennis E.Tallman, Geoff Spinks, Anton Dominis, et. Electroactive conducting polymers for corrosion control: Part 2. Ferrous metals . J Solid State Electrochem, 2002, 6: 85～100
[31]Wessling B. Passivation of Metals by Coating with Polyaniline: Corrosion Potential Shift and Morphological Changes. Advanced Materials, 1994, 6:226～228
[32]Wei Y, Wang JG, Jai XR, Yeh, JM, Spellane P. Polyaniline as Corrosion Protection Coatings on Cold Rolled Steel . Polymer, 1995, 36:4535～4537
[33]Schauer T, Joos A, Dulog L, Eisenbach CD. Protection of Iron Against Corrosion with Polyaniline Primers . Progress in Organic Coatings, 1998, 33:20～27
[34]Santos JR, Mattoso LHC, Motheo AJ. Investigation of Corrosion Protection of Steel by Polyaniline Films. Electrochemical Acta, 1998, 43:309～313
[35]郑家乐.金属电化学和缓蚀剂保护技术.上海：上海科学技术出版社，1984，7
[36]Kinlen PJ, Silverman DC, Jefferys CR. Corrosion Protection Using Polyaniline Coating Formulations . Synthetic Metal, 1997, 85:1327～1332
[37]Fahlman M, Guan H, Smallfield JAO, Epstein AJ (1998) In: 56th Annu Tech Conf Soc Plast Eng 1238～1241; (1998) Chem Abstr 130:44596
[38]Ahmad N, Macdiarmid AG. Inhibition of corrosion of steels with the exploitation of conducting polymers. Synthetic Metal,1996, 78:103～110
[39]Talo A, Forsen O, Ylasaari S. Corrosion Protective Polyaniline Epoxy Blend Coatings on Mild Steel. Synthetic Metal, 1999,102:1394～1395
[40]Fahlman M, Jasty S, Epstein AJ. Corrosion Protection of Iron/Steel by Emeraldine Base Polyaniline: An X-ray Photoelectron Spectroscopy Study. Synthetic Metal, 1997, 85:1323～
1326
[41]Zhou Anning，Zhang Baizhan．Study of Polyaniline/Coal Conductive Composite Material．6th Pacific Polymer Conference，1999，12
[42]汪晓芹. 煤基聚苯胺的合成、性能、聚合机理及其应用的研究：[学位论文].西安：西安科技学院，1998
[43]武利民，李丹，游波. 现代涂料配方设计. 北京：化学工业出版社，2000.3
[44]陈平，刘胜平.环氧树脂.北京：化学工业出版社，1999
[45]周润根.涂料用溶剂的组成与性能,,电镀与涂饰，1999（1）33～36
[46]Jhon N. Murray. Electrochemical test methods for evaluating organic coatings on metals: Part 1. Introductions and generalities regarding electrochemical testing of organic coatings . Progress in Organic Coatings, 1997, 30:225～233
[47]Jhon N. Murray. Electrochemical test methods for evaluating organic coatings on metals: Part 2. Singel test parameter measurements . Progress in Organic Coatings, 1997, 31:255～264
[48]Jhon N. Murray. Electrochemical test methods for evaluating organic coatings on metals: Part 2. Multiple test parameter measurements . Progress in Organic Coatings, 1997, 31:375～391
[49]C.H.Tsai, F.Mansfeld. Determiantion of Coating Deterioation With EIS: Part 2 Development of a Method for Field Testing of Protective Coatings . Corrosion 1993 (9):726～737
[50]A.A. Pud, G.S. Shapoval, P. Kamarchik, et. Electrochemical behavior of mild steel coated by polyaniline doped with organic sulfonic acids . Synthetic Metal, 1999, 107:111～115