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At least 649 records · Page 36

CO{sub 2} Corrosion Behavior of Calcite-Covered API 5L X52 Carbon Steel in Aqueous Solutions

The CO{sub 2} corrosion of API 5L X52 steel in the presence and absence of calcite scale has been investigated. The scale was precipitated from a supersaturated solution at temperatures of 25 and 80 °C. The crystalline phase, cross section and surface morphologies of scale were studied by x-ray diffraction and scanning electron microscopy, respectively. It was found that the scale deposit mostly consisted of calcite. The corrosion behavior of bare and calcite-covered samples was investigated by electrochemical impedance spectroscopy and cyclic polarization techniques in aqueous CO{sub 2} solutions at 30, 50 and 70 °C. The presence of calcite scale on carbon steel surface decreased the adsorption of intermediate corrosion products as the scale uniformly covered the bare surface which resulted in reduction of general CO{sub 2} corrosion rate. The results of cyclic polarization tests revealed that the bare and calcite-covered samples were not susceptible to localized CO{sub 2} corrosion under conditions studied in this research.

36 MATERIALS SCIENCE↗

Influence of Two Different Salt Mixture Combinations of Na{sub 2}SO{sub 4}-NaCl-NaVO{sub 3} on Hot Corrosion Behavior of Ni-Base Superalloy Nimonic263 at 800 °C

Isothermal hot corrosion behavior of Nimonic263 alloy was studied under the influence of two different salt mixtures of 87.5 wt.% Na{sub 2}SO{sub 4} + 5 wt.% NaCl + 7.5 wt.% NaVO{sub 3} (3SM) and 74 wt.% Na{sub 2}SO{sub 4} + 21.7 wt.% NaCl + 4.3 wt.% NaVO{sub 3} (3SM-A) and also without salt mixtures up to 500 h at 800 °C. Corrosion kinetics showed that 3SM-A is more aggressive than 3SM. Multiple oxides, spinels, sulfides, vanadate compounds, and volatile compounds were observed during various hot corrosion reactions. The volatile compounds NaClO{sub 3} and CrMoO{sub 3}, and SO{sub 3} gas are attributed to the weight loss under both 3SMs. The Na{sub 2}SO{sub 4} of 3SM prevailed till 400 h, but that of 3SM-A disappeared within 5 h, as established conclusively by Raman spectra analysis. The sulfides plus internal oxide zone increased with the increased exposure duration as evident from the extensive EPMA analysis. Based on the critical analysis of corrosion kinetics and detailed microstructural characterization, fluxing and sulfidation followed by oxidation are identified as plausible hot corrosion mechanisms under both 3SMs. Besides, chlorination and high-temperature oxidation mechanisms occur under 3SM-A condition.

36 MATERIALS SCIENCE↗

Mechanistic modeling of copper corrosions in data center environments

Air-side economizers are increasingly used to take advantage of “free-cooling” in data centers with the intent of reducing the carbon footprint of buildings. However, they can introduce outdoor pollutants to indoor environment of data centers and cause corrosion damage to the information technology equipment. Here, to evaluate the reliability of information technology equipment under various thermal and air-pollution conditions, a mechanistic model based on multi-ion transport and chemical reactions was developed. The model was used to predict Cu corrosion caused by Cl2-containing pollutant mixtures. It also accounted for the effects of temperature (25 °C and 28 °C), relative humidity (50%, 75%, and 95%), and synergism. It also identified higher air temperature as a corrosion barrier and higher relative humidity as a corrosion accelerator, which agreed well with the experimental results. The average root mean square error of the prediction was 13.7 Å. The model can be used to evaluate the thermal guideline for data centers design and operation when Cl2 is present based on pre-established acceptable risk of corrosion in data centers’ environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Localized corrosion at nm-scale hardening precipitates in Al-Cu-Li alloys

The localized corrosion of Li-containing nm hardening precipitates in the 3rd generation of Al-Cu-Li alloys was investigated based on a quasi in situ approach by sequentially exposing the material to NaCl solution and characterizing the structural, chemical, and electrochemical evolution at atomic scale using electron microscopy, spectroscopy, 3D tomography, electrochemical measurements, and DFT calculations. Localized corrosion of Al 7.5 Cu 4 Li (TB phase) initiated along {001} family of planes through the dealloying of Al and Li due to a low surface work function. Cu was enriched along the Cu (110) // T B (011) // Al (100) orientations on and around corroded T B precipitates. No strong galvanic interactions were observed at the T B and Al matrix interface due to the formation of a Li-C-O rich passivation layer during electrolyte exposure. Similarities and differences between T B and other common Al-Cu-Li precipitates (Al 2 CuLi, Al 6 CuLi 3 , and Al 3 Li) with respect to corrosion are discussed. Overall, the reported corrosion mechanism can assist in the assessment of the localized corrosion susceptibility of precipitation-hardened Al alloys and assist in the design of new alloys.

36 MATERIALS SCIENCE↗

Corrosion rate of carbon steel in carbonated concrete – A critical review

Reinforced concrete with lower environmental footprint (lower CO{sub 2} emission) can be obtained by reducing the clinker content in the cements. As the carbonation of concrete is faster, corrosion of steel in carbonated concrete during the propagation phase is becoming important both for science and practice. The present literature review summarizes the state of the art, reporting corrosion rate data for a broad range of cement types, w/b ratios and environmental conditions. Correlations between corrosion rate and the main influencing parameters are elaborated and discussed. It confirms that the corrosion rate of steel in carbonated concrete is not under ohmic control. More important are the degree of pore saturation and the effective steel area in contact with water filled pores. It also emerges that the new blended cements have to be systematically studied with respect to the corrosion behavior of steel in carbonated concrete in order to make reliable service life prediction.

36 MATERIALS SCIENCE↗

Cathodic corrosion: 21st century insights into a 19th century phenomenon

Cathodic corrosion is an enigmatic electrochemical process that etches metallic electrodes at potentials below 0 V versus the normal hydrogen electrode. Although this phenomenon was discovered in the late 1800s by Fritz Haber, it remained mostly unnoticed during the 20th century and only attracted increased attention in the past decade. This recent attention has generated marked improvements in both the fundamental knowledge and the applications of cathodic corrosion. Fundamental new insights were gained into the effects and possible reaction intermediates of cathodic corrosion. Complementing these insights, recent advances involve applications of cathodic corrosion for nanoparticle synthesis and electrocatalyst modification. Both these applied and fundamental advances will be discussed in this short review on cathodic corrosion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of substrate orientation and anisotropic strength on corrosion pits

The complexities of pitting corrosion and its associated pit morphologies are critical for predicting and preventing pit-related failure in materials. With the advances in computational tools, modeling of pitting corrosion has lately gained momentum. We recently developed a phase field model for 3-D pit morphology, and in the current work, the model is utilized to gain insight into the role of substrate orientation and anisotropic strength on crystallographic pits. The influence of these parameters on pit morphology and corrosion metrics such as pit volume, current, pit area, current density, and pit depth are studied. The crystallographic pit morphology changes with substrate orientation but not significantly with anisotropic strength. Finally, the anisotropic strength strongly influences the corrosion metrics whereas most corrosion metrics remain unaffected by substrate orientation.

36 MATERIALS SCIENCE↗

Corrosion mechanism of cold forged 316 stainless steel in molten FLiNaK salt

This study examined how cold forging (CF) affects the corrosion of 316 stainless steel (SS) in molten FLiNaK salt at 700 °C for 48 h. CF samples had two corrosion areas: one near the top and another displaying intergranular corrosion (IGC). Samples with lower CF (5–30 %) showed more IGC, while the 50 % CF sample had less IGC but the shallowest corrosion depth. This was due to the increased number of grain boundaries, which raised the potential corrosion initiation sites, and certain grain boundaries promoting chromium dissolution, thus enhancing IGC.

FLiNaK↗

Effect of MgSO 4 addition on alkali sulphates induced hot corrosion of a β-NiAl coating

The effect of MgSO 4 addition on alkali sulphates induced hot corrosion of a β-NiAl coating was studied by performing a series of tests with deposits of Na 2 SO 4 , Na 2 SO 4 -20 %K 2 SO 4 and Na 2 SO 4 -12 %K 2 SO 4 -35 %MgSO 4 (mol.% for all) at 700 °C in air with addition of SO 2 . For elucidating the observed corrosion phenomena, various salt-oxide/NiAl powder mixtures were exposed to the same hot corrosion test conditions. Two pseudo-binary phase diagrams of the Na, K, Mg-sulphate systems were calculated using an in-house developed thermodynamic database. Addition of MgSO 4 to Na 2 SO 4 -20 %K 2 SO 4 deposit salt inhibited the hot corrosion attack during 24 h exposure, which is related to consumption of aggressive K 2 SO 4 by the formation of solid K 2 Mg 2 (SO 4 ) 3 . However, extending the exposure with Na 2 SO 4 -12 %K 2 SO 4 -35 %MgSO 4 deposit to 100 h resulted in severe corrosion attack. The latter observation is explained by a reaction between K 2 Mg 2 (SO 4 ) 3 and NiAl causing formation of a Mg, Ni and Al containing spinel accompanied by release of the aggressive K 2 SO 4 into the liquid phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer during the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.

08 HYDROGEN↗

Aggregation and data analysis of corrosion studies in molten chloride and fluoride salts

Corrosion studies in molten fluoride and chloride salts were surveyed, and key data were aggregated into a single dataset. Studies were graphed by salt purity, temperature, sample material, container material, and experimental method (loop, capsule, crucible). To elucidate and quantify the factors that affect corrosion in molten salts, a data analysis using a newly-defined corrosion resistance score and a correlation analysis using techniques borrowed from machine learning were performed. It is shown that salt purity had the strongest correlation with corrosion rates in molten chlorides and fluorides. As a result, data analysis across varied works was inconsistent due to the lack of standardization among molten salt corrosion studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Corrosion behavior of ferritic FeCrAl alloys in simulated BWR normal water chemistry

Ferritic iron-chromium-aluminum (FeCrAl) alloys with varying Cr content were subjected to in-situ irradiation-corrosion with energetic protons or electron beams in pure water with various oxygen concentrations. Oxide microstructure and composition were characterized to compare the corrosion under irradiation with the thermal corrosion in the same water conditions. The dominant effect seems to be the production of H 2 O 2 at the surface by the intense proton and electron beams. The corrosion potential of FeCrAl under BWR-NWC condition is somewhat above the Cr 2 O 3 /CrO 4 2- phase boundary, oxidizing the Cr(III) to Cr(VI) in the outer part of the film, but with some Cr(III) remaining in the interior of the oxide. The beam increases the corrosion potential, significantly reducing Cr(III) content throughout the oxide. Finally, the crystallites on the surface, which form by re-precipitation from solution, do not contain Cr because at low potential Cr(III) is not soluble, and at high potential Cr(VI) is quite soluble.

36 MATERIALS SCIENCE↗

Investigation of breakaway corrosion observed during oxide growth in pure and low alloying element content Zr exposed in water at 360°C

The addition of small concentrations of alloying elements to pure zirconium can prevent nuclear fuel cladding material from undergoing unstable oxide growth in aqueous environments at light water reactor operating temperatures. The role of alloying elements in stabilizing the oxide growth is examined in this paper, to better understand the oxide growth stabilization mechanism. To this end, a set of initial, short-duration corrosion experiments were performed, followed by oxide layer characterization. Specifically, ten model Zr alloys were selected to test the effect of small alloying additions on the alloy corrosion rate and corrosion breakaway. Additionally, these alloys were corrosion tested in pure water in an autoclave at 360°C for up to 70 days. The alloys included crystal bar Zr, sponge Zr, and model alloys with small concentrations of Sn, Fe, and Cr. After testing, the alloys were characterized using scanning electron microscopy (SEM) and synchrotron µ-X-ray fluorescence (µXRF) to study how the structure of the oxide and alloying element distribution related to unstable oxide growth. Initial results in the 360°C water environment showed breakaway oxidation may be caused by unstable oxide growth due to heterogeneous distribution of the alloying elements. Heterogeneous distribution of alloying elements was correlated to the occurrence of unstable oxide growth (either nodule-like, grain boundary penetration, or differential grain-to-grain growth). It is possible that this heterogeneity, made possible by low alloying element content, can cause breakaway corrosion, but further study is warranted.

36 MATERIALS SCIENCE↗

Corrosion of 316L & 316H stainless steel in molten LiF-NaF-KF (FLiNaK)

The corrosion behavior of 316L and 316H stainless steels (low and high carbon, respectively) in molten LiF-NaF-KF (FLiNaK) salt at 700 °C for 500 h has been investigated. Tests were performed in 316L stainless steel, pyrolytic boron nitride, and glassy carbon capsule materials. The capsule material had a notable effect on the corrosion behavior of the two stainless steels. Further, the modes of corrosion for the two types of stainless steel in various capsule materials were classified into three categories, namely, uniform surface recession, selective grain boundary Cr dissolution, and the dissolution of Cr in the bulk grains. By most metrics, the 316H stainless steel exhibited slightly superior corrosion resistance, while by others the two stainless steels were comparable. These differences in corrosion behavior are attributed to the differences in grain size and the degree of sensitization.

36 MATERIALS SCIENCE↗

3D study of intermetallics and their effect on the corrosion morphology of rheocast aluminium alloy

In the present study, the effect of heat treatment T6.1 on the microstructure and corrosion behaviour of rheocast aluminium alloy A356 is investigated on the basis of 2D/3D characterization techniques and electrochemical and SKPFM measurements. Heat treatment strengthens the α-Al matrix, modifies the intermetallic particles and spheroidizes eutectic Si. These changes do not modify significantly the corrosion behaviour of the alloy. 3D SEM-Tomography clearly shows that the corrosion advances in the shape of narrow paths between closely spaced intermetallics without a major influence of eutectic Si. - Highlights: • T6.1 spheroidizes Si, strengthens the matrix and modifies the intermetallics. • Electrochemical behaviour of untreated and heat-treated alloys is similar. • 3D SEM-Tomography provides additional information on the corrosion morphology. • Corrosion advances as paths between intermetallics with little influence of Si.

36 MATERIALS SCIENCE↗

Advanced 3D characterisation of iodine induced stress corrosion cracks in zirconium alloys

Highlights: • Macroscopic crack direction is affected by metallurgical state. • High resolution XCT reveals complex crack morphology. • 3D-EBSD used to fully characterise attacked grain boundaries. • Evidence of iodine segregation ahead of a crack tip. - Abstract: In this study, a range of advanced techniques have been used to characterise iodine-induced stress corrosion cracks, and investigate their interaction with microstructure in zirconium alloys used as cladding material in nuclear power reactors. C-ring samples, machined from cladding tubes in a recrystallised and cold worked condition, were subjected to compressive stress while submerged in an iodine-ethanol solution to simulate stress corrosion cracks arising from pellet cladding interaction. The complex morphology of these stress corrosion cracks was imaged in 3D using X-ray computed tomography (XCT), and subsequent analysis using both 2D and 3D electron backscatter diffraction (EBSD) allowed for the interaction of these cracks with microstructure to be investigated. Intergranular cracking modes were observed to dominate in the recrystallised microstructure, resulting in cracking in the radial direction with variations on the order of the grain size. Crack propagation in the cold worked microstructure was observed to be correlated with the direction of the elongated grains, resulting in a more tangential crack path with less local variation and a microstructure potentially more susceptible to iodine-induced stress corrosion cracking. 3D-EBSD using serial sectioning allows for the determination of the full five-parameter grain boundary description, and opens up the possibility of a statistical analysis of susceptible boundaries to SCC. Nanoscale secondary ion mass spectrometry (NanoSIMS) was also used to map the chemical distribution in the crack tip region and provides possible evidence of iodine segregation ahead of the crack tip. The results provide new insight into crack propagation mechanisms in recrystallised and cold worked microstructures, and pave the way for a more mechanistic understanding of crack propagation through advanced characterisation of iodine-induced stress corrosion cracks in zirconium alloys.

36 MATERIALS SCIENCE↗

Corrosion properties of phase reversion induced nano/ultrafine grained AISI 304 metastable austenite stainless steel

Highlights: • AISI 304 stainless steel was cold rolled under 3 cryogenic temperatures and room temperature, after annealing bulk nano/ultrafine grained material was obtained. • Microstructure of samples was studied by TEM, −120 °C rolled sample had an equiaxed microstructure. • Corrosion resistance of samples was studied by polarization curve, EIS, and Mott-Schottky plot, −120 °C rolled sample had the best corrosion performance. • The distinctive polarization curve of −120 °C rolled sample indicated its passive film had peculiar feature, the M-S plot showed its abnormal semiconductor character. - Abstract: AISI 304 metastable austenite stainless steel was cold rolled under cryogenic temperature and transformed into martensite completely, after reverse transformation by annealing, bulk nano/ultrafine grained material was obtained. The material’s microstructure was observed by TEM, and the corrosion resistance was studied by polarization curve, EIS, and Mott-Schottky plot. Results showed that samples cold rolled at −120 °C had an equiaxed microstructure and displayed the best corrosion performance. The distinctive polarization curve shape indicated that its passive film had a peculiar feature, and the M-S plot showed its abnormal semiconductor character. XPS measurements are used to directly characterize the composition of passive film formed on specimens. Heterogeneous microstructures might help with the improvement on corrosion resistance of the nano/ultrafine grained stainless steel.

36 MATERIALS SCIENCE↗

Solar energy protects steels against corrosion: Enhanced protection capability achieved by NiFeOx decorated BiVO4 photoanode

Highlights: • Steel corrosion is inhibited by coupling to irradiated photoanode. • NiFeO{sub x} promotes charge transfer from BiVO{sub 4} to connected steel. • BiVO{sub 4} composite photoanode decreases the self-corrosion potential of 316 steel by 256 mV. - Abstract: Coupling n-type semiconductor photoelectrode with steels provides protection from corrosion for the latter by pumping electrons produced by water oxidation reaction in a sustainable way. Although the concept of the photocathodic protection of steels has been proposed for about two decades, this technique is still far away from practical applications due to the limited protection capability. In this work, we reported that the BiVO{sub 4} photoanode significantly decreases the self-corrosion potential of 316 steel by 166 mV, and the decoration of NiFeO{sub x} films onto BiVO{sub 4} further shifts the self-corrosion potential by ∼90 mV negatively, which exhibits an excellent protection capability. The protection capability of the photoelectrode to steel is limited by the relative position of the Fermi level of the semiconducting material, and confined by the thermodynamics of the surface reactions on the semiconductor-electrolyte interface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗