Corrosion behaviour and galvanic coupling of titanium and welded titanium in LiBr solutions

Corrosion resistance and galvanic coupling of Grade 2 commercially pure titanium in its welded and non-welded condition were systematically analyzed in LiBr solutions. Galvanic corrosion was evaluated through two different methods: anodic polarization (according to the Mixed Potential Theory) and electrochemical noise (using a zero-resistance ammeter). Samples have been etched to study the microstructure. The action of lithium chromate as corrosion inhibitor has been evaluated. Titanium and welded titanium showed extremely low corrosion current densities and elevated pitting potential values (higher than 1 V). The results of both methods, anodic polarization and electrochemical noise, showed that the welded titanium was always the anodic element of the pair titanium-welded titanium, so that its corrosion resistance decreases due to the galvanic effect.     

Electrochemical noise analysis: detection of electrode asymmetry

One major application of electrochemical noise (EN) analysis for corrosion studies is the estimation of corrosion rate via impedance measurement. The measurement involves coupling two electrodes, whereupon the associated EN is measured and the noise resistance and the spectral noise impedance are computed. However, the two electrodes are required to be “nominally identical” (i.e. symmetrical) for the noise resistance and spectral impedance techniques to be valid. This paper proposes that the correlation between the measured potential and the current noise can be used to detect an asymmetric electrode pair and thus provides a necessary but not sufficient test for electrode symmetry. The potential/current coefficient of correlation is derived based on an equivalent circuit to demonstrate the concept and experimental data is presented to support the theory.     

Electrochemical noise analysis for estimation of corrosion rate of carbon steel in bicarbonate solution

We have investigated the electrochemical noise behavior of carbon steel in fully deaerated aqueous bicarbonate solutions, and discussed the optimum conditions of the noise analysis for estimating corrosion rate of the steel. Noise of the potential difference and of the short-circuit current between two identical steel coupons were successfully measured. The time-series noise patterns were transformed into frequency domain by fast Fourier transformation, and then their power spectrum densities (PSDs) at a frequency were determined to be compared with the corrosion rate. The PSDs of the potential and of the current varied with changing environmental factors of bicarbonate concentration, pH, and immersion time. The factors also controlled the corrosion rate of the steel. The PSDs were associated with the corrosion rate, and then it was found that the PSDs of the potential and of the current showed linear correlation with the corrosion rate in log-log scale. There was also linear relationship between the corrosion rate and a spectral noise resistance obtained from the PSDs of the potential and the current. The linearities of the three correlations were better at a lower analyzed frequency. Furthermore, the PSDs of the current and the noise resistance indicated more linear correlation with the corrosion rate than that of the potential. As the simplicity of the measurement system is additionally considered, it is concluded that the PSD of the current noise at an analyzed frequency of 3 mHz is the optimum conditions for estimating the corrosion rate from 10⁻² to 10⁰ A m⁻² in this study.     

Quantitative evaluation of general corrosion of Type 304 stainless steel in subcritical and supercritical aqueous solutions via electrochemical noise analysis

Electrochemical noise (EN) sensors have been developed to measure the corrosion rate of Type 304 stainless steel (SS) in subcritical and supercritical environments. The EN sensors were tested in flowing aqueous solutions containing NaCl and HCl at temperatures from 150°C to 390°C, a pressure of 25 MPa, and flow rates from 0.375 to 1.00 ml/min. The potential and coupling current noise were recorded simultaneously and the noise resistance (R_n) was calculated from the standard deviations in the potential and current records. We found that the inverse noise resistance correlated very well with the corrosion rate evaluated from separate mass loss experiments, and that both the inverse noise resistance and the average corrosion rate were functions of temperature and flow rate. In the temperature range from 200°C to 390°C, the corrosion rate was found to be proportional to the inverse noise resistance and hence the Stern-Geary relationship can be used to evaluate the corrosion rate. However, at 150°C, the relation between inverse noise resistance and corrosion rate significantly deviated from the Stern-Geary relationship. It was found that the deviation was related to the low corrosion rate of Type 304 SS and 150°C.     

Improvement of the corrosion characteristics of 1.4713 ferritic steel in 0.1 M sulfuric acid by heat treatment and Al2O3–TiO2 coating

This study addresses the influence of heat treatment and alumina coating on the corrosion of EN 1.4713 steel in 0.1 mol dm⁻³ sulfuric acid. The corrosion characteristics of three different samples are examined using the open circuit potential measurements, Tafel extrapolation, linear polarization resistance, weight-loss method, and electrochemical impedance spectroscopy. The results showed that the application of the weight-loss method yielded similar values to the electrochemical method in the first 24 h. A decrease in corrosion rate, in a similar manner, was observed for all three samples. The largest deacceleration was obtained for the alumina/titania-coated sample. It was obtained that the heat treatment significantly increased the corrosion resistance, but only in the first 24 h. The alumina/titania coating decreases the corrosion rate by approximately 30 times at the beginning of the corrosion exposure and by nearly 300 times after 240 h. This coating could have a significant influence on construction design, which uses ferritic stainless steel as the material.     

On-line corrosion monitoring in geothermal district heating systems. II. Localized corrosion

Corrosion monitoring in district heating systems has traditionally been performed by using off-line methods, such as weight loss. The disadvantage is that the method is very slow, especially in low-corrosive environments, and that it only provides information about the past corrosion (accumulated over period of time). The purpose of the work is to test on-line monitoring methods in geothermal hot water in the district heating system in Reykjavik, Iceland. Geothermal water poses certain problems with regards to corrosion monitoring due to low conductivity, high pH and the presence of sulphide. These conditions make the geothermal environment low corrosive. However, a quality control is needed, especially since the sulphide causes the steel pipes to be more vulnerable towards localized corrosion. The methods used in this study were: linear polarization resistance (LPR), harmonic analysis (HA), electrochemical noise (EN) and zero resistance ammetry (ZRA). The Pitting Factor was measured with EN and showed promising results for measuring-localized corrosion on-line. A crevice corrosion cell also gave good results but had a low lifetime. However, the results of a galvanic corrosion cell (Fe/Cu) proved more difficult to interpret since they were dependent both on the dissolved oxygen and the sulphide level.     

The application of electrochemical noise resistance to evaluate the corrosion resistance of AISI type 304 SS in nitric acid

The paper presents the application of noise resistance to evaluate the corrosion behaviour of sensitized AISI type 304 SS in nitric acid of varying concentration (4 N, 12 N, 16 N) and temperature (298 K, 323 K, 348 K). Electrochemical noise data was acquired from a three identical electrode configuration in the required conditions at open circuit potential. The noise resistance was evaluated as the ratio of the standard deviation of the potential to that of the current noise after removing the DC component. The inverse relationship between noise resistance and corrosion rate was exploited to qualitatively assess the corrosion behaviour of AISI type 304 SS in nitric acid. Noise resistance decreased with increase in concentration implying an increase in corrosion rate with increase in nitric acid concentration. An increase in temperature from 298 K to 323 K and 348 K decreased the noise resistance in 4 N and 12 N nitric acid implying higher corrosion rates at higher temperatures. The corrosion rates were similar at 323 K and 348 K in these concentrations. The simultaneous measurement of current and potential noise facilitated the evaluation of the frequency dependence of the noise data to determine the spectral noise resistance (R_sn) and the DC limit of the spectral noise resistance . The results from R_sn and also indicated higher corrosion rates at higher concentration and temperature. Also R_n and correlated well in 4 N and 12 N nitric acid at 323 K and 348 K while disparity was observed at room temperature in 4 N and 12 N nitric acid.     

Corrosion behaviour of bulk ultra-fine grained AZ91D magnesium alloy fabricated by equal-channel angular pressing

Effect of microstructure change on corrosion behaviour of equal-channel angular pressed (ECAPed) AZ91D Mg alloy was investigated. The ECAPed alloy with ultra-fine grained (UFG) α-phase matrix and refined β-phase particles displays a significantly lower corrosion resistance, resulting in more pits after in-situ corrosion, higher mass-loss rate immersed in NaCl solution, larger I_corr values in polarization curves and lower fitted R_t values in EIS plots. Two factors weaken the corrosion resistance: the first is the strains-induced crystalline defects providing the α-phase matrix more corrosion activation, the second is the refined β-phase particles losing barrier to the corrosion propagation in α-phase matrix.     

Corrosion estimates from the transient response to a potential step

A numerical method is developed which allows electrochemical estimates of the corrosion rate to be made in experimental circumstances in which the application of conventional methods yields erroneous values. The method is especially suitable with systems that respond very slowly to an applied electrical stimulus, like when the corroding electrode presents very high capacitance values. The polarisation resistance (and corrosion rate) is determined from the current transient response to the application of a potential step. A computational algorithm for fitting the kinetic parameters of the corrosion model to the experimental transient current data series is described. The properties of the proposed method are discussed on the basis of the results obtained from numerical experiments and laboratory tests. Special attention is paid to the typical case of rusted steel specimens.     

A novel experimental arrangement for corrosion study of X60 pipeline steel weldments at turbulent flow conditions

Electrochemical noise (EN) measurements were carried out to study the effect of turbulent flow conditions on corrosion kinetic of API X60 pipeline steel weld immersed in synthetic seawater. In order to control the hydrodynamic conditions, two rotating cylinder electrodes were used. The EN data were analysed by three different statistical methods: currents transients, noise resistance and localisation index (LI). On the other hand, the spectral method was used in order to get the noise impedance. The superficial analysis using a scanning electron microscopy was carried out. According to EN analyses, the current transients indicate that the aggressiveness of the corrosion increased as the rotation speed also increased. The highest corrosion rate values were obtained at turbulent flow conditions. In the superficial analysis, a localised corrosion form was found in all corrosion processes; these results are agreed with the results obtained by LI.     

Corrosion of the component phases presents in high copper dental amalgams. Application of electrochemical impedance spectroscopy and electrochemical noise analysis

The corrosion resistance of three of the constituent phases in high copper dental amalgams has been investigated by electrochemical methods in 0.9% NaCl solution. Polarization curves show corrosion potentials most positive for γ₁-Ag₂Hg₃, followed by Ag-Cu, and γ-Ag₃Sn in agreement with the order of corrosion resistance deduced from the corrosion currents. Complex plane impedance plots at the open circuit potential showed distorted semicircles with diffusional components at low frequency for Ag-Hg and Ag-Cu, while for γ-Ag₃Sn a layer of corrosion products is formed, partially or completely covering the surface of the electrode. Impedance and noise spectra have been compared in the frequency domain, and show good agreement.     

Corrosion of barium aluminosilicates by water-vapour: An investigation from first principles

Theoretical studies on the water-vapour corrosion resistance of barium aluminosilicates were carried out using Mulliken analysis based on first principles. The Mulliken population of Si–O bonds in different barium aluminosilicates was calculated. The water-vapour corrosion resistance of them was predicted based on these calculation results. In order to verify the prediction results, four barium aluminosilicate powders were synthesized by sol–gel method, and the water-vapour corrosion behaviour of these materials was studied at 1250 °C in an atmosphere of 50%H₂O–50%O₂ water-vapour flowing at a rate of 0.85 mm/s. The experimental results were consistent with the predictions by first principles. This work suggested a methodology for design and selection of silicate materials with good water-vapour corrosion resistance.     

Corrosion behavior of equal-channel-angular-pressed pure magnesium in NaCl aqueous solution

Effect of microstructure change on corrosion behavior of equal-channel-angular-pressed (ECAPed) pure Mg was investigated. The ECAPed sample after 6 passes obtained finer grains (50-100 μm) compared with as-cast one (800-1500 μm). The strain-induced grain refinement with more crystalline defects weakened corrosion resistance of pure Mg, resulting in more and deeper pits after in-situ corrosion, higher mass-loss rate immersed in NaCl solution, larger I_corr values in polarization curves and lower fitted R_t values in EIS plots. However, the enhanced initial OCP values indicate better weather resistance. Furthermore, corrosion improvement can be expected by reducing defects via subsequent annealing.     

有机涂层防护性能的电化学研究进展

曝晒、盐雾、浸泡、干湿循环、老化等传统的有机涂层防护性能研究方法,因测试周期长,测试结果多为定性分析,不能使涂层材料进行快速检验而投入评估使用.正是由于传统测试方法存在许多局限性,故综述了稳态电化学测试方法和暂态电化学测试方法这两种新技术在有机涂层防护性能中的应用与进展.介绍了动电位极化曲线法、极化电阻法等稳态电化学测试方法,这类方法主要反映涂层的极化电阻和腐蚀速度,并且方法简单,可直接分析实验数据,被广泛应用于有机涂层的失效分析中.而暂态电化学测试方法主要包括电化学阻抗法(EIS)、局部阻抗法(LEIS)、扫描Kelvin探针法(SKP)及电化学噪声(EN)等,主要用于研究涂层防护机制和局部缺陷.目前,在有机涂层防护性能和机理研究中,应用最多的是电化学交流阻抗法.丝束电极法(WBE)、扫描电化学显微镜(SECM)以及原子力显微镜(AFM)用于研究金属/涂层界面物理化学变化规律.阐述了上述方法在涂层防护研究中的应用成果及其优势和不足,指出对于深层次的涂层防护研究,需要应用多种测试手段,从不同的角度和方面综合分析,全面评估涂层的使用寿命.     

Measurement of low corrosion rates: Comparison of A.C. impedance and thin layer activation methods

The very low corrosion rate (0.05–1 μm per year) of 18Cr-13Ni-1Nb stainless steel in 7.8 M HNO₃ at room temperature was determined with some confidence in a period of a few days by the combination of a.c. impedance and a radiotracer technique, Thin-Layer Activation. Both techniques were taken to their limits. It is argued that the a.c. method gives an upper estimate for the corrosion rate whilst the tracer method gives a lower estimate. Application of the a.c. method requires an estimate of the Tafel parameter relating corrosion rate and polarization resistance: an approximate method, utilizing the variation of the apparent value of the polarization resistance with the amplitude of the a.c. signal, is given in this paper. The corrosion rate decreased steadily with time over the first few days of exposure of the polished steel surface to the acid. Comparison of the results of the two methods suggested that there was a burst of active dissolution within the first few seconds of exposure, and some speculation about causes and consequences of this phenomenon is made.     

含铜低合金耐磨钢在盐雾环境中的腐蚀行为

对含铜和不含铜实验钢在中性盐雾试验箱中连续喷雾120、240、480和720 h,研究了在盐雾环境下Cu对低合金耐磨钢耐腐蚀性能的影响规律,通过失重法计算腐蚀速率,并利用XRD和SEM对腐蚀产物进行表征,利用动电位扫描、电化学阻抗谱 (EIS) 对比分析Cu在低合金耐磨钢腐蚀过程中起到的作用。结果表明：低合金耐磨钢的腐蚀产物主要包括γ-FeOOH、α-FeOOH、Fe₃O₄、γ-Fe₂O₃,前期腐蚀产物疏松多孔,后期产物致密难剥落,腐蚀速率先升高后下降,含铜实验钢的腐蚀速率明显低于不含铜实验钢,添加Cu后,实验钢的自腐蚀电位上升,阻抗谱容抗弧增大,电荷转移难度增加,说明Cu能有效降低实验钢腐蚀速率,增强其耐腐蚀性能。     

Co2 corrosion inhibition of X-120 pipeline steel by a modified imidazoline under flow conditions

A study of the effect of flow conditions on the performance of a carboxyethyl-imidazoline as CO₂-corrosion inhibitor for API X-120 pipeline steel has been evaluated. Testing techniques include polarization curves, linear polarization resistance, electrochemical impedance spectroscopy and electrochemical noise measurements under stirred conditions (0, 250, 500, 1000 and 2500 rpm). All these techniques show that for the uninhibited solution, corrosion rate increases with an increase in the rotation speed, but for the inhibited solution, the lowest corrosion rate is obtained at 500 rpm, and it increases at lower or higher rotation speeds.     

Erosion-corrosion of mild steel in hot caustic. Part II: The effect of acid cleaning

Corrosion rates of 1020 steel in 2.75 M NaOH solution at a temperature of 160 °C and velocities of 0.32 and 2.5 m/s were studied. The focus was on the effect of the acid cleaning which was performed by using strong, inhibited sulphuric acid in between the exposures to caustic. In situ electrochemical methods were used to measure the corrosion rate such as the potentiodynamic sweep and the polarization resistance method. Also used were the weight-loss method and scanning electron microscopy (SEM).Eight electrodes/coupons were used to monitor the metal loss rate, four were placed at the low velocity section, while the other four were placed in the high velocity section of a high temperature flow. The first three coupons in each section were placed within the disturbed flow region, while the fourth was placed in a fully developed flow region.During the exposure of mild steel to the inhibited acid, following the first caustic period, the corrosion rate increased significantly to between 3 and 10 mm/y with a few electrodes experiencing as high as 50 mm/y. The second caustic period following the acidic period typically started with very high corrosion rates (20-80 mm/y). The length of this corrosion period was typically 2-3 h with a few exceptions when the high corrosion period lasted 7-10 h. Following the very high corrosion rates experienced at the beginning of the second caustic period, the corrosion rates were reduced sharply (as the corrosion potential increased) to nearly the same levels as those observed during the passive part of the first caustic period.     

Effect of heat treatment on H2S corrosion of a micro-alloyed C–Mn steel

The H₂S corrosion resistance of a C–Mn pipeline steel with three different microstructures has been evaluated using electrochemical techniques with a 3% wt. NaCl solution at 50 °C. Microstructures included martensite, ferrite, and ferrite + bainite. Electrochemical techniques included potenthiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), and electrochemical noise (EN) measurements. Most of the tests lasted 24 h. All techniques showed that the highest corrosion rate corresponded to the steel with a martensitic microstructure; up to one order of magnitude higher than the corrosion rate for steels with a ferritic + bainitiic microstructure, whereas the steel with the ferritic microstructure showed the lowest corrosion rate. EIS tests showed that the corrosion process was under charge transfer control, whereas EN results indicated that the three steels exhibited a clear tendency towards a localized type of corrosion. However, for longer immersion times, the steel with a martensitic microstructure tended to exhibit a mixture of uniform and localized attack. Results were discussed in terms of grain size, grain boundary energy, amount and distribution of particles found in each steel.     

The effect of temperature on the galvanic corrosion of the copper/AISI 304 pair in LiBr solutions under hydrodynamic conditions

The corrosion behaviour of copper and AISI 304 stainless steel and the galvanic corrosion generated by the copper/AISI 304 pair, have been studied by electrochemical methods. These materials have been tested in an 850 g/L LiBr solution at different temperatures (25-75 °C) and at different Reynolds numbers (1456-5066) in order to study their performance in absorption machines. Results show that copper was always the anodic element of the pair and its corrosion resistance decreases due to the AISI 304 stainless steel galvanic effect. Galvanic corrosion increases with temperature and Reynolds number. However, it was proved that the effect of temperature on galvanic corrosion is more influential than the Reynolds number effect. This fact is also certain for corrosion of uncoupled copper and for corrosion of AISI 304 stainless steel. Experimental values of the corrosion current densities fit well the Arrhenius plot at all the Reynolds numbers analysed and a potential relation between the corrosion current densities and the Reynolds number has been found.