基于电化学噪声研究模拟海洋大气环境下304不锈钢的点蚀行为

基于电化学噪声技术建立了不锈钢海洋大气点蚀监测系统,利用该系统对处于干湿循环环境下不锈钢的点蚀行为进行监测. 使用时域谱图、时域统计、频域谱图和散粒噪声理论等分析方法对采集到的电化学噪声数据进行处理分析,并结合动电位极化法,形貌分析法共同研究不锈钢的点蚀行为. 研究结果表明,304不锈钢在模拟海洋大气环境下的点蚀行为分为钝化、亚稳态点蚀和稳态点蚀三个阶段. 在钝化阶段,电位电流噪声信号出现少量的同步异向波动,腐蚀事件发生频率高,平均电量低;在亚稳态点蚀阶段,电位电流噪声信号出现大量的同步同向波动,腐蚀事件发生频率降低,平均电量上升,通过扫描电镜观察蚀点;在稳态点蚀阶段,电位电流噪声信号不仅存在大量的同步同向波动,还出现了同步异向波动,腐蚀事件发生频率较低,平均电量大幅度上升,通过扫描电镜观察到电极表面出现小而浅的蚀点. 而动电位极化法可以证实304不锈钢点蚀的发生. 两种分析方法所得结果具有较好的一致性,证明该监测系统很好地实现了对模拟海洋大气环境下304不锈钢点蚀行为的连续监测,并能判断点蚀的发生.     

利用小波变换检测电化学噪声信号波形

简述了应用小波变换检测点蚀电化学噪声信号的基本原理,对在3.5％ NaCl溶液中工业纯铝发生点蚀的电化学噪声信号检测分析表明：小波变换能够提取发生点蚀的电化学噪声信号和测量系统噪声在多惊讶分辨空间中的波形特征,根据表征该特征的小波系数模极大值在不同尺度下的传播特性,可实现对点蚀电化学噪声信号波形的检测。     

Online Monitoring of the Atmospheric Corrosion of Aluminium Alloys Using Electrochemical Noise Technique

In this work, an electrochemical system based on electrochemical noise (EN) technique for online detection and monitoring of atmospheric corrosion of LY12CZ aluminium alloys has been established. A detecting probe and a monitoring instrument with a software have been developed to perform the electrochemical noise measurements with zero resistance ammeter (ZRA) mode. Experimental results show that the atmospheric corrosion behaviour of aluminium could be effectively detected and monitored by the analysis of the electrochemical potential and current noise, also by the noise resistance variation.     

Detrending and Other Features of Data Processing in the Measurements of Electrochemical Noise

Russian Journal of Electrochemistry - Measurements of electrochemical noise in solid-state electrochemical cells with a heteropolycompound- based electrolyte are carried out. The noise power...     

Q235碳钢缝隙腐蚀的电化学噪声研究

应用电化学噪声和电化学阻抗技术研究Q235碳钢在NaHCO3+NaCl溶液中的缝隙腐蚀行为.结果显示,缝隙腐蚀过程可以被清楚地划分为3个阶段:孕育期、快速转换期和稳定发展期.电化学噪声的特征和噪声电阻在各阶段有着显著的变化.缝隙外、内表面积比(r)对缝隙腐蚀的孕育和发展有着十分重要的影响:r越大,孕育期越长.但是,在缝隙腐蚀稳定发展期,r较小时,缝隙外电极表面处于活性溶解状态,缝隙内外电位差很小,缝隙内腐蚀速率较小;倘如r很大时,则缝隙外电极表面处于钝态,缝隙内外电位差大,最终将导致严重的缝隙腐蚀.     

Wavelet transform-based analysis for electrochemical noise

Wavelet transforms are presented as a useful tool to analyse electrochemical noise data. Various concepts developed in the framework of wavelet transforms have been adapted to study electrochemical noise measurements. The most relevant feature of this method of analysis is its capability of decomposing electrochemical noise records into different sets of wavelet coefficients, which contain information about corrosion events occurring at a determined time-scale. Thus, this mathematical approach could become an alternative tool which solves the limitations of other more established procedures for the analysis of electrochemical noise data, such as statistical or Fourier transform-based methods.     

The fractal theory of electrochemical diffusion noise: Correlations of the third and fourth order

Based on the Langevin linear stochastic equation, the correlations of the 3rd and 4th order for thermal fluctuations of the electrode potential are studied in an electrochemical ac circuit involving an electric double layer capacitance, a resistance of steady-state diffusion, and a Warburg impedance. The presence of the noisy Warburg impedance in the ac circuit makes the Langevin linear stochastic equation fractal. The analogy with the steady-state diffusion noise and with the noise of the barrierless-activationless slow discharge is used. Equations for bispectrum and trispectrum of electrode-potential activation are shown. It is demonstrated that the intensity of bispectrum and trispectrum is determined exclusively by the noise of the steady-state diffusion resistance if one of frequency arguments in the polyspectrum is zero. It is found that in an electrochemical ac circuit containing the noisy Warburg impedance, the asymptotics of establishment of equilibrium values of asymmetry and excess of electrode-potential fluctuations (thermalization) obeys the power law rather than the exponential law. Furthermore, the excess thermalization proceeds faster as compared with asymmetry thermalization. The performed theoretical analysis of correlations of the 3rd and 4th order of the fractal noise of electrochemical diffusion is of practical interest. For instance, the concepts of the fractal electrochemical noise can be used in the noise diagnostics of devices of electrochemical power engineering and in the noise methods for studying corrosion systems.     

Software and Instrumentational Methods of Enhancing the Resolution in Electrochemical Noise Measurements

Several methods of enhancing the signal-to-noise ratio for instrumentation designed to measure electrochemical noise are practically tested. The experiments are carried out using model RC-circuits and lielectrolyte electrochemical cells. Strong limitations in the tested objects’ impedance values are found due to the input current noise of the instrumentation, especially during the parallel connection of several channels. The advantages of a two-channel scheme for automatically compensating the instrument’s self noise are demonstrated. Different methods of lowering the dispersion of the frequency dependences of the spectral power density of electrochemical noise are compared. It is shown that averaging over segments with an overlap is the most effective method but averaging over frequencies can lead to large distortions when investigating electrochemical systems.

     

电化学噪声测量分析系统设计与实现

根据电化学噪声原理,利用微机技术设计实现了电化学噪声测量分析系统。该系统具有高灵敏度,自动选择量程,多回路自动测量,可调整采样参数等功能,并在时／频域内对所测量的电化学噪声进行分析。     

On the measure of non-gaussianity of a nearly Gaussian noise

A procedure for the determining of the measure of non-gaussianity of nearly Gaussian noise is suggested, which used trimmed interval of concentration. The procedure is based on the Parseval finite-interval theorem. The following notions have been introduced: the scalar measure of non-gaussianity, the vector measure of non-gaussianity, and multicomponent partial measure of non-gaussianity. The method allows decreasing the probability of the mistaking of a purely Gaussian noise for nearly Gaussian one. The procedure was validated using a mixed normal distribution. The testing showed the finite-interval analog of the Gram-Charlier expansion to have only a few main (meaningful) components. The procedure for the determining of the measure of non-gaussianity of nearly Gaussian noise can be used in the noise diagnostics of various electrochemical systems and for noise monitoring of objects and processes in the electrochemical power engineering.     

Electrochemical noise generated by anodic dissolution or diffusion processes

A model of the noise generated by electrochemical reactions and by diffusion is proposed. The elementary fluctuations are supposed to be the particle fluxes which are Poisson white noise. This model is successfully used to describe the experimental stochastic behaviour of two cases of non-equilibrium electrochemical interfaces: the noise generated by anodic dissolution of iron in acidic medium and that by diffusion of a reacting species in the bulk of the electrolyte.     

Electrochemical noise spectroscopy: Method of secondary Chebyshev spectrum

A new method of electrochemical noise diagnostics is presented: the method of the secondary Chebyshev spectrum based on the splitting of an individual spectral line in the primary Chebyshev spectrum with formation of a system of spectral lines of the secondary Chebyshev spectrum. Algorithm for calculation of the secondary Chebyshev spectrum is developed. The suggested method based on analysis of noises measured in a specific electrochemical system is tested. It is shown that the new method allows determining the differences in the state of the electrochemical system more reliably, than the method of primary Chebyshev noise spectra.     

Theory of the wavelet analysis for electrochemical noise by use of the Laguerre functions

It is shown that the wavelet transform that uses the Laguerre function as a basis function is a useful tool to analyse the stationary electrochemical noise. Knowledge of the variance of the Laguerre wavelet of noise allows the Laplace transform of the correlation function to be found. The Laplace transform of the correlation function may be referred to the spectral density in the Laplace domain as well as to the operational spectral density of noise. It is shown that the operational spectral density of noise can be found not only by averaging over the ensemble of realizations of the noise process but also by averaging over the ensemble of Laguerre wavelets. The results obtained can be useful not only for analysis of electrochemical noise but also for analysis of any stationary random process, in particular for the time series analysis in econometric research.     

Theory for a wavelet analysis of electrochemical noise in the laplace space with use of two operational frequencies

The image of a random process in the Laplace space may be viewed as resulting from use of a oneway continuous wavelet transform with an exponential as the basic function, i.e. as resulting from the application of the Laplace wavelet. If the Laplace-wavelet variance of an electrochemical noise allows one to determine the Laplace transform of a time-correlation function, i.e. a factual operational spectral density of the noise, then the covariance of two Laplace waveletes of an electrochemical noise, each of which corresponds to its own operational frequency, allows one to verify a local consistency of the initial experimental noise data. The Laplace waveletes are applied rather widely. In fact, any stationary random process and stationary random time sequence can be described with operational noise spectra. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

The Kramers-Moyal expansion for electrochemical stochastic diffusion

It is proved that there is a general stochastic equation, according to which any random process in the transient mode can be presented by spatially homogeneous Kramers-Moyal expansion. In the electrochemical stochastic diffusion, an integral of the fluctuation component of electrode potential over the time plays the role of spatial coordinate. Based on these two facts, we derived a spatially homogeneous Kramers-Moyal expansion for the propagator of electrochemical stochastic diffusion. By using the limiting transition to long observation times, we obtained a time and spatially homogeneous asymptotic Kramers-Moyal expansion for the propagator of asymmetric non-Gaussian electrochemical stochastic diffusion. Under the conditions of Gaussian electrochemical noise, the asymptotic Kramers-Moyal expansion turns into the Einstein stochastic diffusion equation. The method of determining time and spatially homogeneous asymptotic Kramers-Moyal expansion for the propagator of asymmetric non-Gaussian electrochemical stochastic diffusion may be useful in the stochastic theory of slow electrochemical discharge and in the electrochemical noise diagnostics.     

Analyzing electrochemical noise with Chebyshev’s discrete polynomials

The principles underlying a novel method intended for analyzing experimental data obtained when studying fluctuation processes are considered. The method in question is Chebyshev’s spectroscopy. The application of this method allows one to determine statistic characteristics of steady-state electrochemical noise against the background of severe deterministic interference without invoking the procedure of the fitting of the initial data. The potentialities of this novel method, which is intended for treating noise experiment, are demonstrated by examining model examples and analyzing the electrochemical noise generated by a lithium electrode placed in an aprotic organic electrolyte.     

Étude des comportements déterministe et stochastique de l'interface électrochimique à l'aide de corrélateurs numériques

It is shown that correlation methods are particularly suited for analysing the deterministic and stochastic behaviour of an electrochemical interface. The electrode impedance, which exhibits the deterministic behaviour, can be measured by correlation by means of a white noise; this method allows us to perform very fast measurements. The electrochemical noise, which exhibits the stochastic behaviour, is measured by a crosscorrelation method. Characteristics and performances of these methods are analysed in detail taking account of requirements of the polarization control. These methods are applied to the experimental study of some electrochemical interfaces.     

Electrochemical Noise Measurement of Polymer Membrane Fuel Cell under Load

Electrochemical noise of a polymer membrane hydrogen–air fuel cell under different currents is measured. Frequency and amplitude dependences of the current-noise power spectral density are calculated. In the frequency interval from 10 to 200 Hz a linear segment of the frequency characteristic has a slope of ?2. The current-noise power spectral density is found to be proportional to the 4th power of the fuel cell loading DC current. Thus found frequency dependence of the fuel cell electrochemical noise was shown to differ markedly from that of the electrochemical impedance real component.     

Discrete version of Wiener-Khinchin theorem for Chebyshev’s spectrum of electrochemical noise

A discrete version of Wiener-Khinchin theorem for Chebyshev’s spectrum of electrochemical noise is developed. Based on the discrete version of Wiener-Khinchin theorem, the theoretical discrete Chebyshev spectrum for the Markov random process is calculated. It is characterized by two parameters: the dispersion and the relaxation frequency (or relaxation time). The noise of corrosion process and the noise of recording equipment are measured. Using the theoretical Chebyshev spectrum, the Markov parameters were found both for the noise of the corrosion process and for the noise of the measuring equipment.     

腐蚀金属电极的电化学频域测量研究进展──金属腐蚀与防护研究所电化学研究介绍之一

腐蚀金属电极的电化学频域测量研究进展──金属腐蚀与防护研究所电化学研究介绍之一曹楚南（金属腐蚀与防护国家重点实验室,金属腐蚀与防护研究所,沈阳１１００１５）腐蚀电化学是研究与腐蚀有关的电化学问题,具体的研究对象为腐蚀金属电极。虽然电化学中的基本原理和...