摘要
锈层/金属腐蚀是复杂腐蚀体系之一,锈层下腐蚀是金属腐蚀发展过程中最主要的、持续时间最长的腐蚀形态。锈层存在引起的腐蚀电化学行为复杂化和可靠解析腐蚀电化学参数困难增大。传统腐蚀电化学方法测定的锈层下腐蚀速度偏离失重法测量数据,测定的界面电容也偏离合理的数值。可靠测定和解析锈层下金属腐蚀电化学参数成为当前腐蚀电化学研究方法面临的重要任务之一。
本文采用失重法和多种电化学方法(包括极化曲线、线性极化法、电化学阻抗技术和恒电位阶跃法)研究了碳钢在静态海水和动态海水中的长期腐蚀规律,结果发现在静态海水中电化学方法测定的8周以前短期浸泡的腐蚀速度与失重法持续下降的变化趋势一致,数值相近；而8周以后长期浸泡的腐蚀速度发生“逆转”,与失重测定结果之间存在偏差,并随时间逐渐增大。在动态海水中电化学方法与失重法从浸泡初期开始变化趋势就完全相反,时间越长数值相差越大。
为了探寻电化学方法测定的腐蚀速度产生偏差的原因,采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、环境扫描电子显微镜(ESEM)、氮吸附(BET)等技术研究了锈层的形貌、结构、组成及各种锈层组分的物理化学性质,结果表明产生偏差的主要原因是当金属/锈层界面间的电位正移到某一电位值时,在金属表面会形成一层黑色的比较致密的内锈层,其中含有具有较高电化学活性的β-FeOOH,当进行电化学极化测试时,发生阴极反应而增加了阴极反应速度,导致测定的腐蚀速度数值偏高。
为了进一步证实β-FeOOH的生成与电位有关,采用扫描微电极技术(SMET)和丝束电极技术(WBE)研究了碳钢在海水中阴极区和阳极区的分布特征和随时间的变化情况,通过对腐蚀产物的分析说明了腐蚀产物的组分与电位分布的相关性。同时采用电化学极化的方法控制了锈层的生成条件,结果证实β-FeOOH确实是在电位数值比较正的条件下生成。
为了使用电化学方法测定锈层下碳钢的腐蚀行为,测定了除氧条件下阴极反应速度,即锈层还原速度,然后将其从总阴极反应速度中扣除,获得无锈层参与的阴极反应速度。结果表明,采用这一方法修正的腐蚀速度与失重测试结果数值和变化趋势一致,证实这是一种有效可行的锈层下碳钢腐蚀速度补偿型电化学测试方法。
Rust/metal structure is one of the multiphase and multiple interface complex systems. The corrosion under rust is the uppermost and longest form of metallic corrosion evolution. It is difficult to accurately determine the electrochemical parameters because the existence of rust complicates the electrochemical corrosion process. Corrosion rate measured by traditional electrochemical methods deviates from the weight-loss measurement result and the interface capacitance also deviates from reasonable value. Reliable measurement and analysis for rusted steel become one of the important tasks in metallic corrosion research.
In this paper, weight-loss measurement and several kinds of electrochemical methods (including polarization curves (PC), linear polarization resistance measurement (LPR), electrochemical impedance spectra technique (EIS) and potential step (PS)) were employed to study the long-term corrosion behaviour of carbon steel in immobile and flowing seawater. The results show that the electrochemical and weight-loss measurement estimations have the same degressive trends and values during the first 8 weeks'immersion period, while the electrochemical measurement result turns to increase after 8 weeks'immersion in immobile seawater. The longer the immersion time, the bigger the deviation. In flowing seawater, electrochemical measurement result is opposite to that determined by weight-loss measurement from the beginning and the deviation becomes larger with increasing of immersion time.
In order to explore the reasons for the deviations between electrochemical and weight-loss measurement results, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), environmental scanning electron microscope (ESEM), nitrogen adsorption (BET), etc were used to study the morphologies, structures, compositions and physicochemical properties of rust layers. Analysis indicates that a dense and black inner rust layer, which containsβ-FeOOH with high electrochemical activity, will form when the potential in the metal/rust interface achieve a noble value. In electrochemical polarization tests,β-FeOOH can participate in cathodic reduction reaction, which leads to increasing the cathodic reaction rate and overestimating the corrosion rate.
In order to further confirm that the formation ofβ-FeOOH was related to the potential, scanning micro-electrode technique (SMET) and wire beam electrode (WBE) were used to study the distribution characteristics of cathode and anode regions for rusted carbon steel in seawater. The relationship between the compositions of corrosion products and potential distribution was illustrated by the analysis of corrosion products. At the same time, electrochemical polarization method was applied to control the formation conditions of rust layer. The results confirm thatβ-FeOOH is indeed produced in the noble potential.
In order to study the corrosion behaviour of rusted steel by electrochemical measurement, cathodic reaction rate, that is rust reduction rate, was measured in deaerated conditions. Then deduct it from total cathodic reaction rate, the rest is oxygen reduction rate. The results show that the corrosion rate modified by this method is consistent with the weight-loss measurement result and confirm that it is a feasible and effective compensatory method to determine corrosion rate of rusted steel by electrochemical measurement.
引文
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