电化学噪声和电化学阻抗谱监测1Cr18Ni9Ti不锈钢的初期点蚀行为

采用电化学噪声和电化学阻抗谱技术,研究1Cr18Ni9Ti不锈钢在3.5%NaCl溶液中的早期腐蚀行为。研究表明,浸泡初期(0h～48h),电化学噪声电位、电流在测量时间范围内漂移较小,电位谱功率(PSDV)曲线的斜率几乎不变;电化学阻抗谱在低频下出现感抗特征,表明研究电极表面发生钝化膜破裂与修复的交替过程,即出现了亚稳态蚀点。浸泡中期(48h～60h),电化学噪声出现尖峰波动,谱功率曲线的斜率产生突变,电化学阻抗谱的低频感抗特征消失,表明研究电极表面的亚稳态蚀点转化为稳定蚀点。扫描电镜表面形貌分析表明,浸泡60h后研究电极表面出现明显蚀点。     

电化学噪声技术研究X80钢的点蚀过程

采用电化学噪声(Electrochemical Noise,EN)方法研究了X80管线钢在NaHCO3+NaCl溶液中亚稳态与稳态点蚀特征。结果表明:在含Cl-溶液中,当试样处于点蚀亚稳态,电位与电流噪声具有典型的快速下降或上升,缓慢恢复的暂态峰(Transient)特征,噪声电流峰平均宽约5~10s,而噪声电位峰宽为100s。随着腐蚀时间的延长,亚稳态点蚀噪声峰数量增多,亚稳态点蚀程度加剧;当点蚀由亚稳态发展到稳态初期,电流噪声峰恢复时间变长,与电位噪声峰寿命趋于一致;而随着稳态点蚀的发展,电位与电流峰出现的频率显著增加,电位与电流峰具有很好的相位同步性。     

铝稀土涂层在盐雾加速试验中的腐蚀行为

采用扫描电镜,X射线衍射仪和电化学噪声技术研究了高速电弧喷涂铝稀土涂层在铜加速醋酸盐雾试验中的腐蚀行为,分析了涂层腐蚀前后的形貌及成分,通过电化学噪声谱阐释了涂层的点蚀过程。研究表明:铝稀土涂层的钝化膜在腐蚀介质中容易发生点蚀和破碎,腐蚀后涂层中的孔隙和微裂纹增多,腐蚀过程中钝化膜由亚稳态点蚀逐渐转变为稳态点蚀。     

静水压力对超纯Fe腐蚀行为的影响

采用失重测试、动电位极化和电化学噪声研究了静水压力对超纯Fe在3.5%NaCl中腐蚀行为的影响。利用离散小波分析方法去除噪声信号的直流漂移,然后进行散粒噪声和随机分析;利用Hilbert-Huang变换对噪声信号进行时频分析;用SEM观察腐蚀试样的表面形貌。失重测试和动电位极化的研究结果表明,增大静水压力提高了超纯Fe在3.5%NaCl中的腐蚀速率。电化学噪声分析结果表明,在整个浸泡期间,增大静水压力促进了点蚀的发展,提高了局部腐蚀的倾向。在浸泡初期,超纯Fe以发生局部腐蚀(如点蚀形核、亚稳态点蚀、点蚀)的模式为主,增大静水压力对点蚀形核过程有一定的抑制作用,降低了点蚀孕育速率,但对亚稳态点蚀和稳态点蚀的发展过程有促进作用,提高了点蚀生长概率;随着浸泡时间的延长,其逐渐转为以均匀腐蚀的模式为主,增大静水压力仍然促进亚稳态点蚀和稳态点蚀的发展,提高点蚀生长概率,但是却相对地抑制了均匀腐蚀过程。     

316L奥氏体不锈钢在不同电位下的点蚀和再钝化行为研究

目的研究外加电位对316L奥氏体不锈钢点蚀和再钝化行为的影响。方法采用循环极化、恒电位极化,电化学阻抗谱(EIS)等多种电化学测试方法,研究了系列电位与混合电位对316L奥氏体不锈钢点蚀敏感性的影响,并采用扫描电子显微镜(SEM)、X射线光电子能谱(XPS)观察分析钝化膜点蚀形貌和元素含量。结果在60℃的饱和CO_2的10 g/L NaCl溶液中,316L奥氏体不锈钢的钝化区间为-0.394～0.168 V,但电位在-0.100～0.168V之间,即亚稳态点蚀区时,电流出现一定的波动。在钝化区极化时,316L奥氏体不锈钢的稳态电流密度非常低,随外加电位的升高而略有增加,极化后试样表面无点蚀;在亚稳态点蚀区,极化的电流密度较高,极化后,试样表面出现明显的点蚀坑;混合区极化时,电位从0.1 V转换到-0.1 V时,电流密度急剧下降,并稳定在一个较低的电流值。XPS结果表明,在钝化区电位极化后,Cr、Mo元素含量有所升高,而Fe元素发生了选择性溶解。结论 Cr、Mo元素是耐蚀性元素,其氧化物或氢氧化物的存在可促进钝化膜的局部修复,因此电位转换到低电位后,试样表面发生再钝化现象,钝化膜的稳定性增强,材料的耐蚀能力提高。     

316L不锈钢在FeCl3溶液中点蚀行为的电化学噪声检测

利用电化学噪声技术检测了316L不锈钢在6％FeCl3溶液中点蚀的电化学噪声谱,观测腐蚀形貌,分析电化学噪声谱特征参数。结果表明,在浸泡初期,电流噪声波动较小,有暂态峰出现,电流功率谱密度（PSD1）的斜率变化不大,表明电极表面出现亚稳态蚀点,钝化膜溶解与修复交替进行。在腐蚀后期,PSD1出现高频白噪声水平,电流噪声波...     

高氮奥氏体不锈钢点蚀行为的电化学噪声特征

通过对电化学噪声数据进行时域、频域和Weibull分布等分析,比较了高氮奥氏体不锈钢(HNSS)和316L不锈钢(316L SS)在6%(质量分数)FeCl_3溶液中的点蚀行为。时域分析结果表明,316L SS在溶液中浸泡5 h后,电位噪声和电流噪声均出现了噪声暂态峰,试样表面发生了亚稳态点蚀,而此时HNSS并没有出现明显的噪声暂态峰,电位噪声和电流噪声仅发生小幅高频波动,表面钝化膜虽发生轻微腐蚀,但仍具有一定的再钝化能力。316L SS的噪声电阻波动幅值较大,而HNSS噪声电阻幅值在小范围内波动,表面钝化膜的自钝化和修复能力优于316L SS。功率谱密度图像表明,316L SS的高频段斜率和白噪声水平强度均高于HNSS,且Weibull分布分析表明316L SS的点蚀孕育速率约是HNSS的2倍,316L SS更容易发生点蚀,HNSS的抗点蚀能力更强。     

16Mn钢局部腐蚀中的电化学噪声特征

通过测量16Mn钢在0.1mol/LCI^- 0.5mol/L HCO3^-溶液中的电化学噪声，发现在点蚀诱导期，亚稳态蚀点的形核速率λ不到0.002s^-1，噪声电流峰平均宽约3～5s，而噪声电位峰却平均宽达200s；在点蚀从亚稳态转变为稳态过程中，λ急剧增加，且电流噪声峰宽度也开始增加，但电位峰宽度却开始减小，随着局部腐蚀进入稳定发展期，噪声中出现了大尺度的波动，且噪声电位峰与电流峰宽度基本相等，但λ却有所下降，宏观点蚀的出现导致噪声电阻Rn迅速下降，并在腐蚀进入稳定发展期后逐渐趋于稳定。     

基于Hilbert-Huang变换的电化学噪声解析及其应用

借助Hilbert-Huang变换 (HHT) 研究了Q345B碳钢在模拟混凝土孔隙液中的电化学噪声信号的时频谱,发现相比离散小波变换 (discretewavelet transform,DWT),HHT在噪声信号识别过程中具有更高的时频分辨率和稳定性,能够从本质上提高对电化学噪声中耦合的亚稳态点蚀信号的解析精度。针对Q345B碳钢处于钝化态、亚稳态点蚀萌发和稳态点蚀生长等不同阶段的噪声特点,提出了一套基于HHT边界谱的腐蚀状态量化指数与腐蚀特征识别方法。借助于在线电化学噪声监测装置,HHT算法将可用于诊断工业环境的腐蚀形态和腐蚀发展趋势。     

铝基水滑石涂层腐蚀行为的电化学噪声特征

采用电化学噪声技术监测了铝基水滑石涂层在3.5%NaCl溶液中的腐蚀行为。通过电化学噪声的时域谱分析、时域统计参数分析、频域分析以及形貌特征分析,对电极的腐蚀过程进行了研究。结果表明,涂层的点蚀发展过程可以分为4个阶段:钝态期,噪声波动较小,各参数比较平稳;亚稳态点蚀核形成期,噪声出现波动,σV、σI、W、k、fc增大,Rn减小;稳态点蚀发展期,电位噪声出现快速下降缓慢上升的典型特征,各参数趋于极值,Li(局部化噪声指数)接近于1;点蚀发展后期,噪声波动减弱,各参数值也趋于减弱。     

Corrosion Behavior of 316LN and 316 Stainless Steels During Long-term Exposure to Aerated 0.5 M NaCl Using Electrochemical Noise Technique

In the present work 316LN as well as 316 stainless steel (SS) coupons each of dimensions (0.025 × 0.018 × 0.006 m³) in well-polished condition were used as two nominal electrodes which were immersed in the aerated solution of 0.5 M NaCl. Correlated current and potential electrochemical noise (EN) signals were collected at 1 Hz sampling frequency for 1 h daily over a period of 30 days. The detrended EN data were used to calculate the noise resistance (R _N) as well as the spectral noise resistance at zero frequency (R _SN^o) values and other statistical parameters. To study the nature of pits and distribution of their diameters as well as depths, extensive observations of the pitted and the blank specimens were carried out using Confocal Laser Scanning Microscopy (CLSM). The current and the potential records of the two alloys showed distinct differences in their corrosion behavior. It was observed that within less than 4 h of immersion, 316SS showed signals indicative of unstable pitting and onset of stable pitting was noticed after 48 h of exposure. However, until about 24 h, 316LN showed just the random signals and unstable pitting was observed after 28 h. The signals clearly indicated continuous growth of the stable pits in 316SS as against the repassivation of the unstable pits in 316LN after 7 days exposure. It was observed that R _N values showed a continuous decrease in the case of 316SS, but were quite stable in the case of 316LN over the exposure period. Concurrent to these observations it was observed that 316SS specimen was extensively pitted. The frequency distributions of pit diameters as well pit depths were observed to be highest at 10-20 μm and 5-10 μm, respectively. However, pits with as large as 70-80 μm diameter and as deep as 20-25 μm too were observed. No pits were observed in case of 316LN even after 30 days of exposure, an observation that corroborates well with the stable R _N values. Thus, in the present investigation, the long-term tests using EN technique coupled with CLSM studies conclusively prove that many unstable pits initiated in 316SS turn into stable ones resulting in insidious localized corrosion attack whereas the unstable pits initiated in 316LN get passivated in the simulated coastal environment.     

304不锈钢点蚀的电化学噪声特征

使用电化学噪声技术,通过长期连续实时监测,对304不锈钢在0.5mol/L FeCl₃溶液中发生局部腐蚀的点蚀发展过程和腐蚀机理进行研究。综合谱图分析、时域统计分析、小波分析等诸多方法进行分析和论证。结果表明：电化学噪声的谱图可以明显地分为4个阶段,分别对应于点蚀发展过程中的钝态期、亚稳态点蚀期、稳态点蚀期及稳态点蚀后期。在时域分析时,先用3阶多项式拟合移除漂移,电流噪声标准偏差Si在亚稳蚀和稳态点蚀阶段发生明显的升高,噪声电阻(R_n)、点蚀指标(PI)在对应时间点表现出相应的降低或升高。小波分析表明,随着反应的进行,能量积累开始逐步增大;亚稳态点蚀期能量开始向d4~d6处累积,当进一步发展为稳态点蚀时d5~d8出现极大值。     

表面粗糙度对304不锈钢早期点蚀行为影响的电化学方法

采用动电位扫描、电化学阻抗谱和电化学噪声等方法研究了4种不同表面粗糙度304不锈钢电极在质量分数为3％的NaCl溶液中的早期腐蚀行为.随着不锈钢电极表面粗糙度的下降,304不锈钢自腐蚀电位与点蚀电位均有所上升;电荷转移电阻噪声电阻明显升高,而电位标准偏差与电流标准偏差则有所降低;粗糙度0.25μm的电极在阻抗谱低频区出...     

Electrochemical noise during non‐stationary corrosion processes

In the present work, electrochemical noise (EN) was measured in three different types of experimental set‐ups in order to obtain and compare various types of corrosion. Simultaneously with EN measurements, a parallel technique was used, regarding the type of experimental set‐up: a computer visualization system combined with optical microscopy, or measurements of mechanical changes. In order to distinguish between these corrosion types and to assess corrosion rate, the measured EN signals were analysed by two different techniques: spectral and statistical. On the basis of estimated significant spectral parameters (power spectral densities of current and voltage noise, spectral noise resistance) and statistical parameters (standard deviation, localisation index and noise resistance), the passive state, localized corrosion types and uniform corrosion can be recognized. However, by these parameters it is not possible to distinguish between certain localized corrosion processes: metastable pitting, initiation and growth of stable pits, stress‐corrosion cracking. It was ascertained that these corrosion processes exhibit unstable nature, and consequently generated EN signals are usually non‐stationary. Since stationarity is required for spectral and statistical analysis, the unstable nature of these processes was recognized as the main reason for unreliable results. It is believed that these types of signal analysis give poor information about corrosion processes which can be easily identified from EN signal itself: transient corrosion processes and transitions between different corrosion processes.     

两种船体钢耐点蚀性能的电化学噪声评估

运用电化学噪声(EN)测量技术和极化曲线技术检测两种船体钢A和B在0.5mol/L NaHCO3+3%NaCl溶液中的腐蚀状况,结果表明,两种钢的噪声图谱都表现出了明显的点蚀特征;在点蚀诱导期,B钢电位噪声波动的幅度和暂态峰的密集程度均比A钢大,而且诱导期持续时间较短;对噪声电阻的分析也表明,在该试验体系中A钢表面状态更稳定。极化曲线的分析结果表明A钢的点蚀电位较高、极化电阻较大、腐蚀电流较小,耐点蚀性能更好,这与电化学噪声分析的结论一致。     

金属亚稳态孔蚀行为的电化学研究

综述了国内外近期在亚稳态孔蚀行为的研究方法,亚稳态小孔形核、生长的统计规律 ,亚稳态蚀孔生长和再钝化过程的机制及控制因素,亚稳态蚀孔向稳定蚀孔转变的临界条件等方面的 研究进展,并对进一步的研究作出了展望。     

Die Bedeutung der metastabilen Lochkorrosion bei hochlegierten Stählen

The importance of metastable pitting corrosion in the case of high alloy steels A suitable computer-aided experimental method allows during potentiostatic tests to recognize and quantitatively treat current transients. The current transients result from metastable pitting phenomena below the pit propagation potential. It is possible under certain conditions to detect metastable pitting which in the SEM appears in the form of small (approximately 1 μm), in most cases hemispherical pits. A detailed study of metastable pitting has brought about fundamental knowledge about the mechanism of pit initiation, stable pit growth and repassivation in pitting and crevice corrosion processes.     

Structure–property quantification of corrosion pitting under immersion and salt-spray environments on an extruded AZ61 magnesium alloy

Extruded AZ61 magnesium coupons were exposed to immersion and cyclical salt spray environments over 60 h in order to characterize their corrosion rates. The characteristics of general corrosion, pitting corrosion, and intergranular corrosion were quantified at various intervals. General corrosion was more prevalent on the immersion surface. In addition, more pits formed on the immersion surface due the continuous exposure to water and chloride ions. However, the pits on the salt spray surface showed larger surface areas, larger volumes, and covered more area on the micrographs as compared to the pits on the immersion surface, due to the dried pit debris that trapped chloride ions within the pits.