Oxide properties and stress corrosion cracking behaviour for Alloy 600 in leaded caustic solutions at high temperature

The stress corrosion cracking behaviour of Alloy 600 in caustic solutions with and without PbO at 315 °C was investigated by means of slow strain rate tension tests. The characterisation of the oxide that formed on Alloy 600 was derived from transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. Lead was incorporated into the oxide in a metallic lead state and a lead oxide state, which degraded the passivity and induced PbSCC susceptibility. NiB was used as an inhibitor. It reduced the lead incorporation level in the oxide layer and decreased PbSCC susceptibility.     

The influence of the cathodic process on the interpretation of electrochemical noise signals arising from pitting corrosion of stainless steels

The use of electrochemical noise (EN) measurements for the investigation and monitoring of corrosion has allowed many interesting advances in the corrosion science in recent years. A special advantage of EN measurements includes the possibility to detect and study the early stages of localized corrosion. Nevertheless, the understanding of the electrochemical information included in the EN signal is actually very limited. The role of the cathodic process on the EN signals remains uncertain and has not been sufficiently investigated to date. Thus, an accurate understanding of the influence of the cathodic process on the EN signal is still lacking. On the basis of different kinetics of the oxygen reduction it was established that the anodic amplitude of transients arising from pitting corrosion on stainless steel can be decreased by the corresponding electron consumption of the cathodic process. Therefore, the stronger the electron consumption, the weaker the anodic amplitude of the EN signal becomes. EN signals arising from pitting corrosion on stainless steel can be measured because the cathodic process is inhibited by the passive layer. This was confirmed by means of EN measurements under cathodic polarisation. Since the cathodic process plays a decisive role on the form of transients arising from pitting corrosion, its influence must be considered in the evaluation and interpretation of the EN signals.     

Detection and characterization of stress-corrosion cracking on 304 stainless steel by electrochemical noise and acoustic emission techniques

This paper focuses on the corrosion process of 304 stainless steel in acidic NaCl solution during slow strain rate testing experiment by using electrochemical noise (EN) and acoustic emission (AE) techniques. Meanwhile, the EN and AE characteristics of corrosion process were studied. The results show that stress corrosion occurs easily in the experimental system, and corrosion forms develops gradually from localized corrosion including stress corrosion and pitting corrosion to general corrosion. The AE signal characteristics of pitting corrosion, crack and bubble break-up are significantly different during the corrosion process.     

In situ study of dew point corrosion by electrochemical measurement

Dew point corrosion (DPC) is an electrochemical process in a dynamic electrolyte layer, which makes it difficult to carry out conventional electrochemical measurements and thus is not conducive to corrosion mechanism study. In situ electrochemical measurements including electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) are realized by a novel DPC simulation set-up and special electrode arrangements in this work. DPC of carbon steel is studied by in situ test method and ex situ test method, respectively. Different corrosion mechanisms are obtained from two methods. Thus, it is significant to study DPC by in situ test method so as to understand DPC essentially.     

Effect of microcrystallization on pitting corrosion of pure aluminium

A microcrystalline aluminium film with grain size of about 400 nm was prepared by magnetron sputtering technique. Its corrosion behaviour was investigated in NaCl containing acidic solution by means of potentiodynamic polarization curves and electrochemical noise (EN). The polarization results indicated that the corrosion potential of the sample shifted towards more positive direction, while its corrosion current density decreased compared with that of pure coarse-grain Al. The EN analysis based on stochastic model demonstrated that there existed two kinds of effect of microcrystallization on the pitting behaviour of pure aluminium: (1) the rate of pit initiation is accelerated, (2) the pit growth process was impeded. This leads to the enhancement of pitting resistance for the microcrystallized aluminium.     

Assessment of intergranular corrosion (IGC) in 316(N) stainless steel using electrochemical noise (EN) technique

In the present work, an attempt was made to demonstrate the use of electrochemical noise (EN) technique in assessment of intergranular corrosion (IGC) in 316(N) stainless steel (SS). Degree of sensitization (DOS) in the specimens aged at 923 K for 24, 40, 50 and 100 h was determined using double loop electrochemical potentiodynamic reactivation (DLEPR) technique. Immediately after applying a prior preconditioning treatment, current and potential noise measurements were made. The DOS was determined from standard deviation of current noise (σ_I) versus time plot and it was found to bear a good correlation with the values obtained by DLEPR. Shot noise analysis of the EN data confirmed the above results.     

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.     

Effect of SO2 in flue gas on coal ash hot corrosion of Inconel 740 alloy – A high temperature electrochemical sensor study

Our newly developed high temperature electrochemical sensor was applied to study the effect of SO₂ in flue gas on thin film coal ash corrosion of Inconel 740 superalloy at 750 °C. The response of electrochemical noise (EN), electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization (PDP) test data from the sensor is compared with the results from a weight loss test. There is a good correlation between the electrochemical data and the actual degradation processes. The current noise analysis in time and frequency domains for the quantitative determination of hot corrosion rate in service is discussed.     

An electrochemical study of the effect of Li on the corrosion behavior of Ni3Al intermetallic alloy in molten (Li + K) carbonate

A study of the effect of lithium content (1, 3 and 5 wt.%) and heat treatment (400 °C during 144 h) on the corrosion behavior of Ni₃Al alloy has been carried out in a 62 mol.%Li₂CO₃-38 mol.%K₂CO₃ mixture at 650 °C using electrochemical techniques. Employed electrochemical techniques included potentiodynamic polarization curves, linear polarization resistance, LPR, electrochemical impedance spectroscopy, EIS, and electrochemical noise, measurements EN. Results have shown that the alloys exhibited an active-passive behavior regardless of the heat treatment. For alloys without heat treatment, the most corrosion resistant was the Ni₃Al base alloy, but when they were heat treated, the most corrosion resistant was the alloy containing 3%Li. EIS results showed that for short immersion tests, the corrosion process was under diffusion control, but for longer exposure times, the presence of a protective scale was evident. All the alloys were highly susceptible to a localized type of corrosion according to EN measurements and supported by SEM micrographs.     

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.     

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.     

Effects of non-metallic inclusions on the initiation of pitting corrosion in 11% Cr ferritic stainless steel examined by micro-droplet cell

This paper explores the effects of non-metallic inclusions (NMIs) on the initiation of pitting corrosion in type 409L stainless steels refined by the argon oxygen decarburization (AOD) and vacuum oxygen decarburization (VOD) processes. The dominant NMIs in the AOD and VOD samples were (Ti, Ca)-oxides and Ti-nitrides, respectively. In-situ electrochemical noise (EN) and micro-electrochemical analyses were conducted to investigate quantitatively the inherent effects of the NMIs on the pitting corrosion of the alloys. Pitting corrosion was initiated mostly around the (Ti, Ca)-oxides in the AOD samples, while little such corrosion occurred around the Ti-nitrides in the VOD samples. In addition, the pitting resistance of the AOD samples increased with increasing Ti content and decreasing Ca content in the (Ti, Ca)-oxides.     

Electrochemical behaviour of aluminium/steel rivet joints

The galvanic corrosion behaviour of a rivet joint of two sheets of the aluminium alloys EN AW-6014-T4 and EN AW-6082-T5 joined by an electrogalvanized steel blind rivet was investigated. The potentiodynamic polarization curves in a 5 wt.% NaCl solution show a potential reversion of the anodic and cathodic regions of the rivet joint. The surface potential was investigated with a capillary electrode before and after corrosion. From the measurements by the capillary electrode and SEM-observations an improved resistance against galvanic corrosion is expected after the dissolution of the zinc layer of the blind rivet.     

Performance of NiB inhibitor for PbSCC of alloy 600 in Pb-contaminated water and caustic solutions

Nickel-based iron-chromium alloys are used as steam generator (SG) tubing materials in nuclear power plants (NPPs) but experience intergranular stress corrosion cracking (IGSCC) and lead stress corrosion cracking (PbSCC) due to the harsh operating conditions of NPPs. In order to improve the integrity of SGs, many studies have sought suitable inhibitors for IGSCC, while those for PbSCC have been sought to a limited extent. In this study, the performance of nickel boride (NiB) as an inhibitor for PbSCC was evaluated. Nickel boride has been shown to be a good inhibitor for IGSCC of Alloy (or Inconel) 600 in a caustic aqueous solution containing no lead (Pb). No significant SCC was observed to occur in Alloy 600 tested in pure water under the slow strain rate test (SSRT) condition in this study. A mixed mode of IGSCC and TGSCC, however, occurred relatively easily in Alloy 600 tested in pure water containing lead oxide (PbO) at 315 °C. The susceptibility of Alloy 600 to SCC decreased with the addition of NiB, implying that NiB can be used as an inhibitor for PbSCC in Pb-contaminated water.     

Corrosion protection of Mg–5Li alloy with epoxy coatings containing polyaniline

The protective ability of epoxy coating containing polyaniline (PANI coating) on Mg–5Li alloy in 3.5% NaCl aqueous solution has been studied by means of EIS and electrochemical noise measurements (EN). The results of EN and EIS revealed that the PANI coating protected Mg–5Li alloy from corrosion perfectly. XPS results indicated that the presence of polyaniline changed the chemical structure of the corrosion film on the alloy surface. An analysis of the electrochemical noise data based on stochastic analysis indicated that the corrosion growth probability of Mg–5Li alloy beneath the coating was decreased by the addition of polyaniline.     

Protective coating on Mg AZ91D alloy - The effect of electroless nickel (EN) bath stabilizers on corrosion behaviour of Ni-P deposit

The effects of the electroless nickel (EN) bath stabilizers; thiourea (TU) and maleic acid (MA), on the corrosion of the EN coatings on Cu and Mg substrates were investigated in an aggressive oxygenated chloride environment.Corrosion was limited to the external EN layer, and thus, the intermediate Cu layer as well as Mg AZ91D substrate remained intact. On the EN surface, two different types of corrosion morphologies were observed. Specimens prepared with TU showed preferential attack along particle boundaries, while pitting corrosion was observed for specimens prepared either without a stabilizer or with MA. The latter deposits showed higher corrosion resistances due, in part, to the formation of a P-enriched layer on the surface. The poorer corrosion performance of EN specimens prepared with TU was attributed to the presence of the particle boundaries and the trace impurities adsorbed on, or included in, them. The key impurity was sulphur incorporated during formation of deposits in TU-stabilized baths.It was clearly shown that the corrosion behaviour of the EN specimens was predominantly influenced by the morphological and surface compositional aspects of the deposits.     

In situ measurement of corrosion on the nanoscale

Measurement of the electrochemical properties phase-by-phase on the nanoscale in real (commercial) alloys is critical to understanding the microstructure-corrosion relationship and subsequently controlling it. This work presents a novel AFM based in situ corrosion probing methodology (for the first time) that is capable of resolving the electrochemical activity (impedance response) into the nanometer range; the method subsequently having major ramifications in the study of aluminium alloy corrosion, the interpretation of corrosion propagation, and the subsequent development of corrosion resistant aluminium alloys.     

Effect of hydrostatic pressure on the corrosion behaviour of Ni-Cr-Mo-V high strength steel

Effect of hydrostatic pressure on the corrosion behaviour of Ni-Cr-Mo-V high strength steel was investigated by electrochemical measurements and SEM observation. The electrochemical noise (EN) data was analyzed based on non-linear dynamic theory. The experimental results revealed that hydrostatic pressure decreased the corrosion resistance of Ni-Cr-Mo-V steel and the corrosion at high hydrostatic pressure was more uniform due to the higher initiation rate and lower growth probability of metastable pitting.     

Steel corrosion and corrosion-induced cracking in recycled aggregate concrete

This study investigated four reinforced concrete mixtures with different replacement percentages of recycled coarse aggregate (RA). The corrosion rate was measured using an electrochemical workstation, and the corrosion-induced cracks on the concrete surface were observed using digital microscopy. The results show that the use of RA introduces more interfaces in concrete, which accelerates the steel corrosion process and corrosion-induced crack propagation in concrete cover. However, steel corrosion and the corrosion-induced cracking process in concrete are not significantly influenced by replacing a small amount (33% in the study) of coarse aggregate with RA.     

Electrochemical noise analysis on the pit corrosion susceptibility of Mg–10Gd–2Y–0.5Zr, AZ91D alloy and pure magnesium using stochastic model

Pit corrosion susceptibilities of Mg–10Gd–2Y–0.5Zr alloy, AZ91D alloy and pure magnesium were investigated by means of electrochemical noise (EN). The EN data have been analyzed based upon the combined stochastic theory and shot-noise theory. Pit initiation process has been modeled as a nonhomogeneous Poisson process and analyzed using a Weibull distribution function. Pit growth process has been simulated by a nonhomogeneous Markov process and analyzed using Gumbel distribution function. The EN results implied that Mg–10Gd–2Y–0.5Zr alloy had the highest pit initiation rate and pit growth probability, which revealed that Mg–10Gd–2Y–0.5Zr alloy had the highest pit susceptibility.