Exfoliation corrosion susceptibility of 8090 Al-Li alloy examined by electrochemical impedance spectroscopy

The exfoliation corrosion susceptibility and electrochemical impedance spectroscopy(EIS) of rolled and peak-aged 8090 AI-Li alloys in EXCO solution were studied, and the EIS after exfoliation was simulated. Once exfoliation occurs, two capacitive arcs appear in the EIS at high-mediate frequency and mediate-low frequency respectively. The exfoliation-attacked alloy surface consists of two parts, an original flat alloy surface and a new interface exposed to EXCO solution due to the exfoliation. The capacitance corresponding to the new exfoliation inter-face increases approximately linearly with time at early exfoliation stage, due to the enlargement of the new inter-face.Then it maintains stable, due to the corrosion product covering on the new inter-face. The exfoliation susceptibility can be judged through the average slope of the capacitance vs time curve of the early exfoliation stage. This average slope of the rolled 8090 alloy is much higher than that of the peak-aged 8090 alloy, accordingly the rolled 8090 alloy is more susceptible to exfoliation than the peak-aged 8090 alloy.     

Investigation of exfoliation corrosion of rolled AA8090 Al-Li alloy using electrochemical impedance spectroscopy

1　INTRODUCTIONAl Lialloys ,comparedtotraditionalAlalloys ,havemoreexcellentproperties,suchaslowerdensi ty ,greaterelasticmodulusandhigherspecificstrength[1,2 ] .Inthenearfuture ,theywillbewidelyappliedtoairplanestructures.While ,exfoliation ,amainkindoflocalizedcorrosion ,lowerstheirstrength ,plasticityandfatigueproperties ,andalsodecreasestheirservicelife[35] .Soinvestigatingtheirexfoliationwillbeveryimportanttotheirapplication .　　　　　　Usually ,theexfoliationratingsareobservedbyna…     

Exfoliation corrosion of aluminum alloy AA7075 examined by electrochemical impedance spectroscopy

A typical aluminum alloy, AA7075, was immersed in the EXCO solution, and its corrosion properties during different immersion time were measured repetitively using electrochemical impedance spectroscopy technique (EIS). The EIS data a were simulated using equivalent circuit with ZView program. The results show that once the exfoliation occurs, the low frequency inductive loop in the Nyquist plot associated with the relaxation phenomenon of reaction intermediates disappears, and the Nyquist plane is mainly composed of two capacitive arcs in the high frequency range and low frequency range respectively. The former originates from the original corroded surface, while the latter from the newly formed interface by exfoliation corrosion (EXCO). With the increased immersion time, the high frequency capacitance arc decreases gradually, while the low frequency capacitance arc increases gradually. From the beginning of immersion up to 9 hours, charge transfer resistance gradually decreases, illustrating the acceleration of the corrosion rate, whereas the proton concentration decreases steeply, indicating the cathodic process is pre‐dominant. Then the corrosion rate decreases gradually corresponding to the exhausting of proton ions. The results also show that the exfoliation corrosion is developed from pitting corrosion through intergranular corrosion to general corrosion at the end.     

Long-term corrosion behaviour of carbon steel and stainless steel in Opalinus clay: influence of stepwise temperature increase

ABSTRACT

Carbon steel (C-steel; E24 and S235 grades) and stainless steel (316L) electrodes were corroded in situ in Opalinus clay under anoxic conditions in a vertical descending borehole. The electrodes were exposed at ambient temperature for two years, and then at 85°C for five years. In situ electrochemical impedance spectroscopy showed that the instantaneous corrosion rate of C-steel decreased over time down to 1?µm?year^?1, followed by steady state. Microbial and chemical investigations showed that sulphate and thiosulphate reducing prokaryotes were present in the porewater and at the metal surface. Post mortem characterisation revealed contrasting corrosion aspects. The E24 corrosion interface was thick and contained magnetite, mackinawite, hydroxychloride and siderite, together with more oxidised species (goethite, greigite, elemental sulphur). The S235 corrosion interface was thinner and contained siderite and mackinawite. Corrosion damage of the 316L electrode was negligible, and the surface was covered by a thin fringe of pyrite.     

Electrochemical techniques for monitoring stress corrosion cracking of Type 40Cr steel in acidified chloride solution

Electrochemical impedance spectroscopy （EIS） and electrochemical noise （EN） techniques were used to detect stress corrosion cracking （SCC） on 40Cr steel specimens exposed to the acidified chloride solution at ambient. To test these two techniques, slow strain rate tensile （SSRT） tests were performed with 40Cr specimen in the identical corrosive solution at room temperature. In impedance measurements, phase shifts in frequency range from 1 to 1 000 Hz show a clear difference between the stressed and non-stressed specimens, suggesting that stress corrosion cracks are detected by the impedance measurements. EN signals in the process of SCC were recorded and then analyzed by standard deviation （STD）. On the other hand, the mechanical properties, such as maximum tensile strength （MTS） and fracture strain （FS） measured by the SSRT, decrease significantly when the specimens are exposed to the corrosive solution relative to that in an inert medium. The SSRT results are consistent with fractography of the tested specimens by scanning electron microscopy （SEM）. Analysis of the fracture surface clearly shows intergranular attack, suggesting that stress corrosion cracks are formed.     

P110钢高温高压下CO2腐蚀产物组织结构及电化学研究

模拟油气井深处CO2的超临界流体（35MPa、160℃）状态,在油田采出液中,对P110钢进行4—144h腐蚀测试;采用SEM、XRD、XPS、EIS等分析手段,对试样腐蚀产物膜进行组织结构及电化学交流阻抗分析。结果表明,在CO2含量为4％摩尔分数情况下,腐蚀产物膜在4—8h内迅速生成;48h内腐蚀产物膜由细小的FeCO3晶粒组成;48—144h之间,初始形成的FeCO3膜逐步转化为由（Fe、Ca）CO3、Fe2Ca2O5和CaCO3等腐蚀及沉积产物构成的晶粒细小的复合膜层。该腐蚀-沉积膜与基体结合力强、组织致密、无离子选择性渗透通道,厚度在48h后的腐蚀过程中变化很小。交流阻抗谱分析证明,该膜层对P110钢基体覆盖良好,具有很强的保护作用。     

Effect of sulphate reducing bacteria on corrosion of Al?Zn?In?Sn sacrificial anodes in marine sediment

Microbiologically influenced corrosion (MIC) of Al? Zn? In‐Sn sacrificial anodes in marine sediment was investigated by exposing samples to sulphate reducing bacteria (SRB). Samples exposed to the sterile marine sediment were used as control. The results show that pitting corrosion occurs in both the sterile marine sediment and the SRB‐containing marine sediment. However, the corrosion can be increased sharply by the SRB metabolic activity due to the cathodic depolarization effect. In fact, the effect is based on the consumption of hydrogen which probably results in the acceleration of galvanic corrosion between corrosion products and metal substrate.     

The use of small electrochemical perturbations to assess the corrosion of steel in concrete

In this work an experimental and theoretical comparison has been made between the use of the potentiostatic and coulostatic methods to assess the corrosion rate of steel in concrete. Numerical Laplace transformation was used for preliminary impedance analysis of the coulostatic transients to aid the understanding of the experimental data. The corrosion tests were carried out on a range of reinforced concrete specimens made with various types of cements (plain, flyash and slag blended cements), different water to cement ratios (0.4 and 0.5) and various admixed chloride concentrations varying from 0 to 3% by weight of cement. Despite the inherent variability of concrete, which usually results in a large scatter of results, similar trends in the performance of the different concrete mixes were predicted by the two methods. Curve fitting analysis of the transients obtained from both methods was found to result in a lower estimate of the polarisation resistance parameter than other conventional methods. However, this analysis may represent an improvement over the other estimates of its value as it provides a consistent methodology of excluding the very fast or slow transient processes which may not result from the corroding interface. The differences in the results obtained from the various methods of analysis of the two methods, together with their advantages and disadvantages, are discussed.     

粉土pH对X70钢早期电化学腐蚀行为的影响

采用电化学阻抗(EIS)、极化曲线和扫描电子显微镜观察(SEM)等方法,通过室内模拟试验研究了X70钢在不同pH粉土中的早期电化学腐蚀行为。结果表明:X70钢在酸性(H_2SO_4)、碱性(NaOH)以及中性粉土中的腐蚀差异较明显。在模拟酸性粉土中,X70钢在pH为5的粉土中腐蚀龄期达21d时的自腐蚀电位明显高于在其他环境中的,且X70钢的腐蚀速率随着pH的增大(4~5),呈现出降低的趋势。在模拟碱性粉土中,液相介质中的OH-对X70钢的腐蚀行为有较大的影响,且X70钢的腐蚀速率随着pH的增大(9~11),呈现出升高的趋势。     

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.     

Understanding the effect of nitrogen in austenitic stainless steel on the intergranular stress corrosion crack growth rate in high temperature pure water

Understanding the effect of nitrogen content on the crack growth rate (CGR) due to intergranular stress corrosion cracking (IGSCC) in high temperature (288 °C) pure water, in non-sensitised and strain-hardened stainless steel (SS) type 304 LN was the focus of this study. Non-sensitised SS containing two different levels of nitrogen (0.08 and 0.16 wt.%) in the solution annealed condition was strain-hardened by cross-rolling at 200 °C (warm rolling). It has earlier been reported that SS with a higher nitrogen level in the warm rolled condition has a higher CGR in high temperature pure water. Tensile testing was carried out using both the SS in the warm rolled as well as in the solution annealed condition at 288 °C. Samples were prepared for transmission electron microscopy (TEM) from the warm rolled SS and from the tensile tested (at 288 °C) specimens. TEM studies indicated that twinning and shear band formation were the major modes of deformation due to rolling at 200 °C and these feature were observed to terminate at grain boundaries, leading to regions of higher strain and stresses at grain boundaries. Higher nitrogen SS has higher grain boundary strain and stresses making the grain boundary regions more susceptible to IGSCC, resulting in higher CGR values. At 288 °C dislocation entanglement and cross-slip were the predominant modes of deformation.     

A measurement system based on electrochemical frequency modulation technique for monitoring the early corrosion of mild steel in seawater

The electrochemical frequency modulation (EFM) technique, featuring of obtaining the Tafel constants directly, small polarization and short measuring time, offers a novel way for electrochemical corrosion monitoring. According to current research, the EFM approach should be mostly limited to those corrosion systems with fairly high corrosion rate, such as mild steel or iron in acidic environment. In this paper, a system for EFM measurement was set up with a potentiostat, a laptop, a NI DAQ card and applications developed with LabVIEW 7.0. It was then applied to the mild steel/seawater system. The early corrosion rate for mild steel in Zhoushan seawater was determined in laboratory with EFM technique and another two general electrochemical techniques as well-analysis of the polarization curve in the vicinity of the corrosion potential and electrochemical impedance spectroscopy. The EFM measurements were performed with 0.02 and 0.05 Hz potential perturbation frequencies, and the EFM data were analyzed with activation-controlled equation. It was shown that the corrosion rates determined with EFM technique were higher than the real values, especially at longer exposed times when diffusion-controlled effect became obvious. But they were still at the same order of magnitude as those obtained with polarization curve analysis or weight loss method.     

The effect of heat treatment on the corrosion resistance of 440C stainless steel in 20% HNO<Subscript>3</Subscript> + 2.5% Na<Subscript>2</Subscript>Cr<Subscript>2</Subscript>O<Subscript>7</Subscript> solution

The effect of heat treatment on the corrosion resistance of 440C stainless steel was investigated in a 20% HNO₃ + 2.5% Na₂Cr₂O₇ solution using electrochemical noise (ECN) measurements, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) examinations. The noise resistance (Rn), which has been found to be inversely related to the localized corrosion rate, was measured to be 5.7E + 08 Ω-cm², 4.2E + 08 Ω-cm², and 3.7E + 04 Ω-cm² for the oil-quenched, air-quenched, and vacuum furnace cooled (VFC) samples, respectively, after 1200 s exposures. The Rn for all heat treat conditions stabilized within a range of 1.0E + 07 Ω-cm² to 3.2E + 08 Ω-cm² after 2 h exposures. The EIS response showed a polarization resistance (R _p) on the order of 6.6E + 04 Ω-cm², 5.3E + 04 Ω-cm², and 1.1E + 04 Ω-cm² for the oil-quenched, air-quenched, and VFC samples, respectively, after 2 h exposures. The EIS data are in good agreement with ECN data and indicate that after longer exposures, general corrosion mechanisms dominate and the corrosion rates are comparable. SEM examinations of specimens subjected to 1200 s exposures revealed that severity of pitting and intergranular corrosion damage was consistent with trends in the Rn data. Specifically, the electrochemical noise data as well as SEM examinations of specimens revealed a higher localized corrosion resistance of the hardened specimens during the early stages of passivation. This greater resistance to localized corrosion can be attributed to an increased stability of the natural passive film resulting from a higher concentration of chromium atoms in solution for the martensite phase.     

Effect of Co and W on the corrosion behaviour of 1% Cr steel in flowing synthetic seawater

The aqueous corrosion characteristics of 1% Cr‐steel alloyed with small amounts of Co and W in synthetic seawater was studied by using immersion weight‐loss tests, electrochemical corrosion tests (potentiodynamic tests and electrochemical impedance spectroscopy (EIS) measurements) and analytical techniques. 1% Cr steels containing Co or W from 0.2 to 0.4 wt.% showed higher corrosion resistance than the 1% Cr steel in the immersion and potentiodynamic tests. EIS measurements showed that the Nyquist plot presented one time constant. Furthermore, the Co‐ and W‐bearing steels present higher R_p values than the 1% Cr steel through all the test period. The better corrosion resistance of the Co‐and W‐bearing steels is attributed to the protectiveness of the surface layer. The corrosion products were examined using electron probe microanalysis (EPMA) and X‐ray photoelectron spectroscopy (XPS). The results of EPMA indicated that Cr was concentrated in the inner region of the rust layer, while Co and W were distributed all over the rust layer. XPS results showed that Co existed as a trivalent oxide in the rust layer and W in the rust appeared in the form of a WO₄ compound. These compounds act as a factor for corrosion resistance in aqueous solutions.     

Study of the potential electrochemical noise during corrosion process of aluminum alloys 2024, 7075 and pure aluminum

Properties of the potential electrochemical noises (EN) generated during the corrosion process of aluminum alloys AA2024(T3), AA7075 (aged at 121°C/35 h + 160°C/20 h) and pure aluminum in 3wt% (mass fraction) NaCl solution were investigated in this study. During the initial stage of immersion, the EN amplitude of AA2024 is the largest while the EN amplitude of pure aluminum is negligible. The amplitude of the EN generated by these materials decreases with immersion time except the EN of AA2024 after extremely long immersion time (38 days in this study). Surface morphology corresponding to different stages of immersion and different types of EN were studied by scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) analysis. The result shows that the micro‐galvanic cells formed by the constituent particles and the alloy matrix play an important role on the corrosion process of the aluminum alloys and the EN behaviors of AA2024, AA7075 and pure aluminum is proved to be strongly related to the type and intensity of corrosion process.