基于混沌理论的电化学噪声谱数据解析及其在局部腐蚀检测中的应用

将混沌理论引入电化学噪声(EN)谱的数据解析,对有机涂层失效过程和应力腐蚀过程的EN数据进行分析,采用关联维数表征局部腐蚀过程,取得了一些有意义的结果。分析了环氧酚醛/镀锡薄钢板失效过程的EN特征,通过计算涂覆镀锡薄钢板腐蚀过程的电化学电位噪声(EPN)谱特征,发现EPN对应的关联维数值随着局部腐蚀程度的加剧有增加的趋势。采用混沌相空间重构理论分析了304不锈钢应力腐蚀过程的电流噪声谱,利用关联维数表征应力腐蚀过程。数据计算结果表明应力腐蚀初期其相空间轨迹呈圆球形,应力腐蚀后期则变为椭圆形。研究结果表明,当裂纹萌生和扩展时,关联维数值增大,表明电化学噪声信号的不确定性与复杂性增加。     

Cl-污染大气环境下T91钢孔蚀萌生的电化学噪声检测

采用电化学噪声(EN)技术研究了T91马氏体耐热钢在Cl^-污染大气环境下的电化学行为,并针对EN数据进行统计分析,得到表征腐蚀萌生和发展的特征参数。运用Thevenin等效电路模型得到统计参数与腐蚀速度之间的关系并用实验数据进行验证。实验结果表明,EN技术可以有效监测大气环境下T91钢的腐蚀过程,电流噪声幅值大小一定程度上反映了局部腐蚀萌生和发展过程。理论分析结果表明,溶液电阻可影响电位噪声和电流噪声的测量以及噪声电阻的计算结果,但只要溶液电阻值远小于工作电极的阻抗,其影响可以忽略。谱噪声电阻不等于研究电极的阻抗模值,二者之间存在一定的关系。实验数据的进一步分析证实了理论预测的正确性。     

硫酸盐还原菌诱导腐蚀的电化学噪声分析

基于电化学噪声(EN)和信号处理研究硫酸盐还原菌(SRB)对304不锈钢诱导的腐蚀。将304不锈钢电极分别置于硫酸盐还原菌接种前后的培养基中,利用电化学工作站分别对2种试样的腐蚀进程进行电化学噪声测量,将测得的噪声数据去除直流漂移,再对这些数据进行时域、频域和小波分析。结果表明:通过时域分析得到的标准偏差和噪声电阻可表征腐蚀速率,局部因子则可以区分腐蚀类型。通过频域分析得到的功率谱密度曲线,能表征304不锈钢腐蚀的程度。小波分析则能从不同尺度下分解信号,更加直观、清晰地表征腐蚀进程。利用电化学噪声技术能很好地监测SRB对不锈钢的腐蚀影响,根据不同的需求采用不同的分析方法进行电化学噪声数据分析,才能准确表征腐蚀类型、腐蚀速率以及腐蚀程度。     

304不锈钢管焊缝区碱性腐蚀的电化学噪声检测

利用电化学电位噪声检测304不锈钢管焊缝区在50%NaOH碱液沸腾温度下腐蚀过程的电位噪声谱,观测相应的腐蚀形貌,分析电化学噪声谱特征参数。结果表明：实验过程中焊缝处腐蚀电位呈下降趋势;发生局部腐蚀裂纹时,电位噪声时域谱振幅较大,出现暂态峰;经快速傅里叶变换（FFT）后的功率密度（PSD）谱出现高频白噪声水平,PSD谱高频线性部分的斜率K>-20 dB·dec^-1。测试室温碱液中304不锈钢管焊缝处的电化学噪声表明,不同腐蚀状态的焊缝试样腐蚀电位及噪声时域谱特征不同,可利用K值定性判定是否发生局部腐蚀,为现场检测奠定基础。     

Cl~-污染大气环境下T91钢孔蚀萌生的电化学噪声检测

采用电化学噪声(EN)技术研究了T91马氏体耐热钢在Cl~-污染大气环境下的电化学行为,并针对EN数据进行统计分析,得到表征腐蚀萌生和发展的特征参数。运用Thevenin等效电路模型得到统计参数与腐蚀速度之间的关系并用实验数据进行验证。实验结果表明,EN技术可以有效监测大气环境下T91钢的腐蚀过程,电流噪声幅值大小一定程度上反映了局部腐蚀萌生和发展过程。理论分析结果表明,溶液电阻可影响电位噪声和电流噪声的测量以及噪声电阻的计算结果,但只要溶液电阻值远小于工作电极的阻抗,其影响可以忽略。谱噪声电阻不等于研究电极的阻抗模值,二者之间存在一定的关系。实验数据的进一步分析证实了理论预测的正确性。     

电化学噪声技术对不锈钢表面局部腐蚀监测的应用进展

本文介绍了电化学噪声技术的原理及分析方法,利用恒电流极化在不锈钢表面制造局部腐蚀坑,通过电化学噪声技术对不锈钢表面局部腐蚀进行监测,并通过微观形貌、线性极化、电化学阻抗对电化学噪声的监测效果进行验证.结果表明,采用电化学噪声技术能够有效的对局部腐蚀进行监测,且微观形貌、线性极化与电化学交流阻抗的表征测试结果均与电化学噪...     

基于同心圆三电极阵列的局部电化学测试方法

设计了同心圆三电极阵列,将局部电化学测试方式由扫描探针转变为高速切换离散的电极单元,并基于此发展了一种适用于液滴体系局部腐蚀电化学测试方法。该方法不仅能够实现液滴与电极界面腐蚀电位及电偶电流分布特征的表征,而且能够实现局部电极位置的电化学阻抗谱、极化曲线等电化学测试。基于测试数据的分析,可以获得界面电化学反应及传质等动力学过程的局部电化学信息,用于研究电极/液滴界面双电层以及附近的扩散层等电极过程的动力学机制。该方法可应用于多种非均相介质腐蚀电化学研究体系,也为工业领域电化学工程及腐蚀监测技术发展提供了一种可供选择的解决方案。     

蓝宝石表面形貌的功率谱与分形特征分析

运用二维功率谱和分形理论的关联维数分析了蓝宝石晶片的表面形貌特征。介绍了利用二维快速傅立叶变换计算二维功率谱在蓝宝石表面形貌中的应用方法;通过时间延迟技术重构相空间,利用GP算法计算了蓝宝石表面形貌的关联维数。分别利用二维功率谱和关联维数对蓝宝石的原始表面、加工后表面和单个取样长度的形貌特征进行了实验分析。结果表明:二维功率谱和关联维数能够表征蓝宝石表面形貌,且克服了传统的表征参数只包含有垂直方向上的信息而不能准确表征整个蓝宝石晶片表面形貌特征的缺点,它比传统的表面形貌表征方法具有准确、便捷和信息量大等优势。     

钢制长输油气管道硫化氢腐蚀的电化学研究方法

随着我国油气管道事业的快速发展,硫化氢腐蚀已成为油气管道面临的一项主要的腐蚀失效形式。针对钢制油气管道的硫化氢腐蚀阴极、阳极反应机理进行了介绍,同时阐述了腐蚀的环境影响因素及其作用机理。介绍了动电位极化曲线测试、电化学阻抗谱测试和电化学噪声技术等较为成熟的钢制油气管道的硫化氢腐蚀电化学研究方法,并对电化学噪声信号的深入处理和恒电位脉冲技术的应用进行了展望。     

高剪切力流场下X80管线钢局部腐蚀深坑诱导局部湍流交互机理研究

天然气管道内表面局部腐蚀缺陷会诱发局部流场突变影响局部腐蚀进程,利用高剪切力的冲刷腐蚀实验装置进行流动状态下的电化学腐蚀在线测试,研究了局部腐蚀深坑对局部腐蚀进程的影响。试样在冲刷腐蚀过程中的界面腐蚀电化学信号通过电化学阻抗谱进行分析,腐蚀产物膜的成分及特征通过扫描电子显微镜（SEM）、能量衍射谱图（EDS）以及X射线衍射（XRD）表征,并结合计算流体力学（CFD）分析了流场参数对腐蚀传质过程的影响。结果表明,表面缺陷会诱导局部位置流场发生变化,增强局部位置的传质作用,缺陷表面腐蚀产物也因此随着流速的变化而呈现不同的微观形态。在较高强度流场下,局部增强的壁面剪切力会剥离部分致密腐蚀产物膜,导致测试表面形成大阴极小阳极的电化学分布,促进局部位置的腐蚀进程,从而加速局部腐蚀发生。     

酸性NaCl溶液中304控氮不锈钢腐蚀过程的声发射特征

采用声发射技术和电化学噪声技术研究了304控氮不锈钢C型环试样在0.5mol·L-1NaCl与1.5mol.L-1H2SO4的混合溶液中,恒载荷情况下的腐蚀过程。分析了腐蚀过程中所产生的声发射信号的振铃数随时间分布情况,以及不同阶段的声发射信号的频谱特征。同时对比分析了声发射检测结果与电化学噪声检测结果。结果表明,声发射检测技术对于304控氮不锈钢在酸性NaCl溶液中所产生的腐蚀声发射信号很敏感,在不同腐蚀阶段中,声发射信号特征差异明显,对于判断不同腐蚀阶段具有指导意义;声发射与电化学噪声测试结果基本一致,将声发射检测与电化学噪声检测结合使用,有助于使现场检测结果更加可靠。     

Electrochemical noise (EN) technique: review of recent practical applications to corrosion electrochemistry research

The ability to analyze different electrochemical corrosion phenomena, in–situ, without requiring any form of electrode perturbation has strongly attracted the attention of corrosion researchers towards the application of electrochemical noise (EN) analysis method. With the ability to analyze stochastic and chaotic electrode potential and current fluctuations at E_OCP, the EN analysis method is capable of providing information about the kinetics and mechanism of metallic corrosion with accuracy that can match conventional electrochemical techniques. Herein, we review the recent applications of EN analysis method to electrochemical corrosion research. We discuss briefly the theory behind the measurement of EN, and then highlight some of its application in the evaluation of corrosion inhibitors, pitting corrosion, coatings on metals, microbiologically–induced corrosion, as well as CO₂–corrosion. The drawbacks of the EN analysis method have also been highlighted and future considerations on the use of this important electrochemical technique have also been proposed.     

Self Linear Polarization Resistance-Theory and Examples

Measuring the corrosion rate of a corroding metal is of interest in many situations, including monitoring industrial processes and undertaking fundamental research. The corrosion rate of a metal can be measured electrochemically by determining its polarization resistance, which is inversely proportional to the corrosion rate. What is described in this article is a technique for mathematically extracting from electrochemical noise (EN) data the polarization resistance as well as a measure of the frequency of anodic and cathodic transients. The theoretical framework for self-linear polarization resistance is based on a time-domain analysis of an electrical circuit model of an EN experiment. The analysis indicates that the polarization resistance for one electrode can be interpreted only if the second electrode alone is generating current transients during a given time record. One advantage of this approach, compared with other techniques for obtaining a polarization resistance from EN data, is that short time records, i.e. less than one minute, can be assessed. The self-consistency of the polarization resistance can be assessed with a correlation coefficient. Another advantage is that the nature of localized corrosion events can be attributed to either anodic or cathodic current transients from one of the electrodes.     

Monitoring the degradation of a high solids epoxy coating by means of EIS and EN

This paper reports a study of the degradation processes suffered by steel samples painted with a high solid content epoxy coating. Because this coating shows a high resistance when exposed to NaCl solutions, HCl solutions were employed to accelerate the corrosion processes. Macroscopic images were used to observe the coating degradation. Then electrochemical techniques, electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) were employed to monitor the corrosion behaviour of the system studied. A close correlation was found between EIS and EN data. Several parameters were estimated using these techniques: R_po, R_ct, C_c, C_dl and Z_0.1 Hz using EIS, and R_n using EN. In addition, a new parameter estimated by means of EN was employed, Z_0.1 Hz(EN). The evolution of all these parameters with time enabled the effective monitoring of the degradation stage of the coating.     

Detection of SCC on prestressing steel wire by the simultaneous use of electrochemical noise and acoustic emission measurements

Electrochemical voltage and current noise were measured simultaneously with acoustic emission (AE) measurements during the stress-corrosion cracking (SCC) of prestressing steel wire. Elongation of the specimens was also measured. Constant load tests were performed on specimens made from prestressing steel with a diameter of 3.2 mm: the central wire of a seven-wire strand was used. The specimens were exposed to diluted sodium thiocyanate (a modified version of the test as proposed in EN ISO 15630-3), with and without the addition of an organic corrosion inhibitor. EN was measured between the stressed central cold-drawn wire and the neighbouring wires which acted as reference electrodes for the electrochemical current and voltage measurements. AE was measured by two AE sensors fixed to the specimen.In order to characterize the SCC processes on the prestressing steel wire, the results of all the used techniques were analysed and compared. The effect of the inhibitor on these processes was also studied. A significantly longer time to failure was observed in the experiments with the added inhibitor. The results of the techniques, in combination with SEM and metallographic inspections, confirmed that the inhibitor had a specific influence on SCC. It was concluded that measurements of combined methods are promising for the reliable detection of SCC.     

Phase angle analysis for stress corrosion cracking of carbon steel in fuel-grade ethanol: Experiments and simulation

The stress corrosion cracking (SCC) of carbon steel in simulated fuel-grade ethanol (SFGE) was investigated using electrochemical impedance spectroscopy (EIS) and slow strain rate test (SSRT). Phase angle at low frequency range (<1 Hz) is sensitive to SCC process of carbon steel in SFGE. Phase angle decreases during an active crack growth. Frequency at maximum phase angle also increases towards an active cracking region at around 1 Hz. A transmission line model (TLM) is used to simulate the EIS response for SCC based on real geometrical parameters. By systematically changing the values of the circuit elements, the activities of the sample surface, crack tip and crack wall were studied in detail. By comparing the Bode plots from both experiment and simulation during SCC, a detailed mechanistic picture is derived to describe the behavior of the stress corrosion crack on carbon steel in the fuel-grade ethanolic environment.     

Study on the corrosion behavior of reinforcing steel in cement mortar by electrochemical noise measurements

The corrosion behavior of reinforcing steel in cement mortar has been studied by electrochemical noise (EN) compared with the electrochemical impedance spectroscopy (EIS). The wavelet transform, as well as the statistical methods including the standard deviation of current noise (σ_I) and noise resistance (R_n), has been employed to analyze the EN data of reinforcing steel in mortar. It is revealed that there exist three different corrosion stages of reinforcing steel in cement mortar, including a competition process between breakdown and repassivation of passive film, a pitting development and an active corrosion during the 20 cyclic immersion and drying tests. The energy distribution plot (EDP) is able to provide useful information about the dominant process for the different corrosion stages.     

Noise resistance and shot noise parameters on the study of IGC of aluminium alloys with different heat treatments

In the present paper, the effect of heat treatment on the susceptibility to intergranular corrosion (IGC) of aluminium alloys is analysed. Samples of aluminium alloys AA2024 and AA7075 were first subjected to different heat treatments. Then the susceptibility of these samples to IGC was determined by means of normalized tests, based on the immersion of the samples in an aggressive medium and the subsequent evaluation of the attack, using metallographic analysis. In order to quantity the IGC suffered by the samples, both the degree and the depth of the attacks were measured. In addition, electrochemical noise (EN) signals were recorded during the normalized tests. This technique is especially interesting for the study of corrosion processes of systems with low impedance, such as those faced in this paper, since it does not modify the corrosion potential of the system. Three parameters were used to analyse the EN signals: noise resistance (R_n) and two shot noise parameters, the characteristic charge (q) and the characteristic frequency (f_n). Finally, the relationship between the results of the metallographic analysis and those obtained from the analysis of EN signals was established. Unfortunately, a poor correlation between the shot noise parameters and the degree of IGC was found, due to both the high localization and high activities of all systems.