环氧涂层在不同温度海水中的失效行为研究
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摘要
目的研究环氧涂层在不同温度海水环境中的腐蚀失效行为。方法采用电化学阻抗谱(EIS)技术研究两种海水环境中涂层的EIS特征,同时分析涂层电阻和涂层电容的变化,以研究环氧涂层防护性能随浸泡时间的变化。结果涂层在15℃海水中浸泡1440 h时,阻抗值下降至106?·cm2以下,而在30℃海水中仅浸泡72h时,阻抗值就已下降至106?·cm2。随着浸泡时间的增加,涂层在15℃海水中的EIS响应由高阻抗的单容抗弧变为双容抗弧,而在30℃的海水中,EIS响应首先由单容抗弧演变为双容抗弧,随后又出现了明显的Warburg扩散阻抗特征。涂层电容在两种温度的海水中均呈上升趋势,电阻呈下降趋势。结论涂层在30℃海水中的劣化速度加快,是因为升高温度能够降低涂层与金属间的结合力,加快了海水向涂层内部渗透的速率。由于温度的升高加快了溶解氧的扩散速率,使得氧扩散过程成为腐蚀反应的控制步骤,从而导致了涂层在30℃海水中的EIS响应出现了明显的Warburg扩散阻抗特征。当环氧涂层在15℃与30℃的海水中浸泡1800 h时,其防护性能的变化可以分为快速下降、缓慢下降、趋于稳定三个阶段。
Objective To study failure behaviors of epoxy coatings in seawater at different temperatures. Methods EIS technique was used to study the EIS characteristics of coatings in two seawater environments. Meanwhile, changes of coating resistance and coating capacitance were analyzed to study protective properties of the epoxy coatings with immersion time. Results When the coating was immersed in seawater at 15 ℃ for 1440 h, the impedance value dropped below 106 ?·cm2; while the impedance value dropped to 106 ?·cm2 when the coating was immersed for only 72 h in seawater at 30 ℃. With the increase of immersion time, the EIS of the coating immersed in seawater at 15 ℃ changed from a single capacitive loop to double capacitive loop, and the EIS of the coating immersed in seawater at 30 ℃ firstly evolved from a single capacitive loop to double capacitive loop, followed by obvious Warburg resistance characteristic. When the coatings were immersed in seawater at two temperatures, the coating capacitance presented a rising tendency, and the coating resistance showed a decreasing tendency.Conclusion The degradation rate of epoxy coatings in seawater at 30 ℃ is accelerated, which is attributed to that the high temperature reduces the binding force between the coating and the metal, and speeds up the rate of permeation of seawater into the interior of the coating. As the temperature rises, the diffusion process of dissolved oxygen is also accelerated, and thus the oxygen diffusion process becomes a control step of the corrosion reaction, which leads to obvious Warburg resistance characteristics of the EIS of the coating immersed in seawater at 30 ℃. When the epoxy coating is immersed in seawater at15 ℃ and 30 ℃ for 1800 h, the changes of protective properties could be divided into three stages: rapid decline, slow decline,and stabilization.
Objective To study failure behaviors of epoxy coatings in seawater at different temperatures. Methods EIS technique was used to study the EIS characteristics of coatings in two seawater environments. Meanwhile, changes of coating resistance and coating capacitance were analyzed to study protective properties of the epoxy coatings with immersion time. Results When the coating was immersed in seawater at 15 ℃ for 1440 h, the impedance value dropped below 106 ?·cm2; while the impedance value dropped to 106 ?·cm2 when the coating was immersed for only 72 h in seawater at 30 ℃. With the increase of immersion time, the EIS of the coating immersed in seawater at 15 ℃ changed from a single capacitive loop to double capacitive loop, and the EIS of the coating immersed in seawater at 30 ℃ firstly evolved from a single capacitive loop to double capacitive loop, followed by obvious Warburg resistance characteristic. When the coatings were immersed in seawater at two temperatures, the coating capacitance presented a rising tendency, and the coating resistance showed a decreasing tendency.Conclusion The degradation rate of epoxy coatings in seawater at 30 ℃ is accelerated, which is attributed to that the high temperature reduces the binding force between the coating and the metal, and speeds up the rate of permeation of seawater into the interior of the coating. As the temperature rises, the diffusion process of dissolved oxygen is also accelerated, and thus the oxygen diffusion process becomes a control step of the corrosion reaction, which leads to obvious Warburg resistance characteristics of the EIS of the coating immersed in seawater at 30 ℃. When the epoxy coating is immersed in seawater at15 ℃ and 30 ℃ for 1800 h, the changes of protective properties could be divided into three stages: rapid decline, slow decline,and stabilization.
引文
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[14]高伟.纳米改性环氧防腐涂料的制备与性能评价[D].成都:西南石油大学,2012.
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[17]MISZCZYK A,DAROWICKI K.Effect of Environmental Temperature Variations on Protective Properties of Organic Coatings[J].Progress in Organic Coatings,2003,46(1):49-54.
[18]郑会保.有机涂层环境适应性及表征技术研究进展[J].合成材料老化与应用,2014,43(6):51-56.
[19]张源.阵列电极方法研究破损涂层阴极剥离行为[D].青岛:中国海洋大学,2015.
[20]张伟,王佳,李玉楠,等.WBE联合EIS技术研究缺陷涂层下金属腐蚀[J].物理化学学报,2010,26(11):2941-2950.
[21]张伟,王佳,赵增元,等.有机涂层失效过程的电化学阻抗和电位分布响应特征[J].高等学校化学学报,2009,30(4):762-766.
[22]徐安桃,张振楠,张睿,等.军绿有机涂层和金属漆涂层全浸泡下的腐蚀行为对比研究[J].装备环境工程,2017,14(5):69-73.
[23]杨霜,唐囡,闫茂成,等.温度对X80管线钢酸性红壤腐蚀行为的影响[J].中国腐蚀与防护学报,2015,35(3):227-232.
[24]张伟,王佳,赵增元,等.电化学阻抗谱对比研究连续浸泡和干湿循环条件下有机涂层的劣化过程[J].中国腐蚀与防护学报,2011,31(5):329-335.
[2]侯健,郭为民,邓春龙.深海环境因素对碳钢腐蚀行为的影响[J].装备环境工程,2008,5(6):82-84.
[3]孙晓华,高瑾,郭为民,等.海水温度对深海用环氧涂层防护性能的影响[J].北京科技大学学报,2011,33(5):570-574.
[4]刘杰.模拟深海环境下有机涂层/低合金钢体系失效过程的研究[D].青岛:中国海洋大学,2011.
[5]王震宇,柯伟,张立新,等.高温下环氧粉末涂层中介质传输行为研究[J].中国腐蚀与防护学报,2001,21(1):41-46.
[6]徐安桃,李锡栋,周慧.EIS评价有机涂层防腐性能的应用研究进展[J].装备环境工程,2018,15(6):48-52.
[7]曹楚南,张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2002.
[8]孙志华,蔡建平,刘明,等.金属/有机涂层体系环境失效的电化学研究方法[J].装备环境工程,2007,4(4):1-5.
[9]薛玉娜,任国琪,王荣.温度对J55钢铬铝合金化后电化学阻抗谱的影响[J].材料保护,2013,46(11):70-72.
[10]丁锐,桂泰江,蒋建明,等.应用EIS研究改性无溶剂环氧防腐涂层的防护性能和腐蚀特征[J].真空科学与技术学报,2017,37(2):165.
[11]刘杰,李相波,王佳,等.阴极极化对人为破损907A涂层钢腐蚀行为的影响[J].装备环境工程,2010,7(3):1-5.
[12]DEFLORIAN F,FEDRIZZI L,BONORA P L.Influence of the Photo-oxidative Degradation on the Water Barrier and Corrosion Protection Properties of Polyester Paints[J].Corrosion Science,1996,38(10):1697-1708.
[13]FEDRIZZI L,DEFLORIAN F,BONI G,et al.EIS Study of Environmentally Friendly Coil Coating Performances[J].Progress in Organic Coatings,1996,29(1):89-96.
[14]高伟.纳米改性环氧防腐涂料的制备与性能评价[D].成都:西南石油大学,2012.
[15]张伟.干湿交替环境中有机涂层失效过程的研究[D].青岛:中国海洋大学,2010.
[16]HIRAYAMA R,HARUYAMA S.Electrochemical Impedance for Degraded Coated Steel Having Pores[J].Corrosion,1991,47(12):952-958.
[17]MISZCZYK A,DAROWICKI K.Effect of Environmental Temperature Variations on Protective Properties of Organic Coatings[J].Progress in Organic Coatings,2003,46(1):49-54.
[18]郑会保.有机涂层环境适应性及表征技术研究进展[J].合成材料老化与应用,2014,43(6):51-56.
[19]张源.阵列电极方法研究破损涂层阴极剥离行为[D].青岛:中国海洋大学,2015.
[20]张伟,王佳,李玉楠,等.WBE联合EIS技术研究缺陷涂层下金属腐蚀[J].物理化学学报,2010,26(11):2941-2950.
[21]张伟,王佳,赵增元,等.有机涂层失效过程的电化学阻抗和电位分布响应特征[J].高等学校化学学报,2009,30(4):762-766.
[22]徐安桃,张振楠,张睿,等.军绿有机涂层和金属漆涂层全浸泡下的腐蚀行为对比研究[J].装备环境工程,2017,14(5):69-73.
[23]杨霜,唐囡,闫茂成,等.温度对X80管线钢酸性红壤腐蚀行为的影响[J].中国腐蚀与防护学报,2015,35(3):227-232.
[24]张伟,王佳,赵增元,等.电化学阻抗谱对比研究连续浸泡和干湿循环条件下有机涂层的劣化过程[J].中国腐蚀与防护学报,2011,31(5):329-335.