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钢结构浪溅区腐蚀防护技术及缓蚀剂在干湿交替下的研究

Study on the Anti-corrosion Technology in Splash Zone and Inhibition Effect of Inhibitors in Wet/Dry Cyclic Conditions

【作者】 钱备

【导师】 侯保荣;

【作者基本信息】 中国科学院研究生院(海洋研究所) , 海洋腐蚀与防护, 2014, 博士

【摘要】 浪花飞溅区是海洋环境中腐蚀最严重的区带。复层矿脂包覆防腐技术(PTC)已经被证明为一种长期有效的钢结构浪花飞溅区腐蚀防护技术。矿脂防蚀膏是PTC技术的核心内容,它的性能决定了PTC技术的稳定性和耐久性,对矿脂防蚀膏的配方进行优化具有重要意义。本文采用山东省地方标准《矿脂防蚀膏》中规定的耐温流动性和锥入度检测方法,结合中性盐雾和电化学交流阻抗实验,通过选用不同种类的基础油,添加降凝剂和硬脂酸钙等功能组分,对矿脂防蚀膏的基础配方进行优化。研究结果表明:当硬脂酸钙含量为3%时,以T13号石蜡油为基础油配制的矿脂防蚀膏的各项性能良好。干湿交替是导致钢结构在浪花飞溅区腐蚀严重的一个重要因素,矿脂防蚀膏中含有的缓蚀剂成分可以从腐蚀电化学的角度对碳钢进行保护,研究缓蚀剂在干湿交替环境下对碳钢的缓蚀作用有助于人们理解PTC技术的内在保护机理,同时为人们提供了一种研究缓蚀剂的新方法。本文选取单宁酸和聚天冬氨酸作为缓蚀剂,采用极化曲线和交流阻抗等电化学实验方法,研究了它们在干湿交替环境下对碳钢的缓蚀作用;采用表面扫描电镜、X-射线衍射和傅里叶红外光谱等手段对腐蚀产物进行表征。研究结果表明:单宁酸可以有效抑制碳钢在干湿交替环境下的腐蚀;单宁酸浓度为1g/L时,缓蚀效率可达86%;单宁酸与FeOOH的优先反应抑制了锈层的腐蚀加速作用。含有聚天冬氨酸的复配缓蚀剂对碳钢在干湿交替环境下的缓蚀效果更好;复配缓蚀剂的缓蚀效率为92.6%;经过8次干湿交替后,碳钢表面的腐蚀程度明显减弱。作为对聚天冬氨酸研究的拓展,考察了它在酸洗缓蚀剂领域中的应用。本文利用极化曲线、交流阻抗、扫描电镜和光电子能谱等技术,研究了聚天冬氨酸与碘化钾(KI)复配后对碳钢在硫酸溶液中的缓蚀作用。研究结果表明:聚天冬氨酸与KI复配使用,缓蚀效率达到95%以上;缓蚀效率提高是由于I-的阴离子效应加强了聚天冬氨酸在金属表面的吸附。

【Abstract】 Splash zone is the most severe corrosion damage area in marine environment.Petrolatum tape cover (PTC) has been proved to be an effectively technology toprotect the steel structures away from corrosion in splash zone. Petrolatum is one ofthe important components in PTC, which properties affect the stability and durabilityof PTC. It would be significantly to optimize the composition of petrolatum. Testmethods according to the local standards of Shandong Province such as temperaturefluidity and cone penetration, as well as salt spray and electrochemical impedancespectroscopy were performed to detect the properties of petrolatum. Kinds of base oil,pour point depressant, and calcium stearate were added to improve the petrolatum.The petrolatum based on liquid paraffin make a good performance when the contentof calcium stearate up to3%.Note that wet/dry cyclic conditions greatly account for corrosion of steelstructures in the splash zone. Inhibitors in petrolatum can protect the steels from theviewpoint of electrochemical corrosion. By studying the corrosion in wet/dry cyclicconditions, the important influence factors of corrosion as well as corrosion inhibitionin the real system can be determined. The inhibition effect of tannic acid andpolyaspartic acid on mild steel corrosion in seawater wet/dry cyclic conditions wasstudied by weight loss and electrochemical methods. X-ray diffraction, and Fouriertransform infrared reflection are performed to study the corrosion inhibition. Resultshows that the inhibition efficiency run up to86%when the concentration of tannicacid was1g/L. The inhibition effect of the compound is attributed to ferric tannatefilm formation on the steel surface. The mixed inhibitors contain polyaspartic acidleading to higher inhibition efficiency up to92.6%. The metal surface immersed inmixed inhibitors was in better condition compared to others according to the results ofSEM.In order to enlarge the use of polyaspartic acid, the inhibition effect ofpolyaspartic acid and its synergistic effect with KI on mild steel corrosion in H2SO4 solution are studied by weight loss, electrochemical methods, SEM, and XPS. Theinhibition efficiency increases to95%with the presence of KI. Results show thatiodide ion promotes the film formation of polyaspartic acid greatly.

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