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Crystallography of intergranular corrosion in sensitized austenitic stainless steel
Highlights: • Intergranular corrosion (IGC) in stainless steel was crystallographically discussed. • Grain boundaries (GBs) were classified based on the coincidence site lattice (CSL). • Influence of the Σ value on their IGC susceptibility had a wide range scatter. • IGC susceptibility was characterized by the Σ value and unit cell area of CSL GBs. - Abstract: This study deals with the susceptibility to intergranular corrosion (IGC) in type 304 austenitic stainless steel from a crystallographic viewpoint. An IGC test was conducted using oxalic acid and sensitized stainless steel, whose crystal orientation was analyzed by electron backscattered diffraction (EBSD). GBs were classified according to the misorientation of adjacent grains, and subclassified using the Σ value based on the coincidence site lattice (CSL) model. The width of corroded groove was measured for each GB category, and the effect of GB category on the susceptibility to IGC was examined. Then, the area of the unit cell of CSL boundaries was used to characterize the susceptibility to IGC of CSL boundaries. It was found that no IGC occurred in low-angle GBs with a misorientation of 15°, the width of corroded groove at each Σ boundary exhibited large scatter. The relationship between the width and unit cell area was characterized by a sigmoid curve, and the susceptibility to IGC was well described by the unit cell area.
Intergranular corrosion resistance of Zn modified 5××× series Al alloy during retrogression and re-aging treatment
Highlights: • Increase the strength due to precipitation hardening of T-Mg{sub 32}(AlZn){sub 49} phase in the Zn modified Al-Mg alloy. • Both high corrosion resistance and high strength are achieved by retrogression and re-aging treatment in Al-5Mg-3Zn alloy. • Large Mg and Zn content difference between GBP and PFZ results in relatively high IGC susceptibility. • The intergranular corrosion mechanism of Zn modified Al-Mg alloy during retrogression and re-aging treatment is clarified. - Abstract: The effects of retrogression and re-aging treatment on the intergranular corrosion behavior of Al-5.0Mg-3.0Zn alloys are systematically studied. The alloy's strength increases when retrogression temperature increases from 390 °C to 420 °C. Samples retrogressed at 390 °C then re-aged are very susceptible to intergranular corrosion and those retrogressed at 405 °C and 420 °C express good corrosion resistance. Then the alloy's corrosion susceptibility rises with increasing retrogression temperature. Grain boundary precipitates are coarsened and distributed discontinuously with decreasing retrogression temperature. Higher retrogression temperature results in higher Mg and Zn content difference and intergranular corrosion susceptibility.
Intergranular corrosion of Ni-30Cr in high-temperature hydrogenated water after removing surface passivating film
Abstract High-resolution transmission electron microscopy and atom probe tomography are used to characterize the initial passivation and subsequent intergranular corrosion of degraded grain boundaries in a model Ni-30Cr alloy exposed to 360 °C hydrogenated water. Upon initial exposure for 1000 h, the alloy surface directly above the grain boundary forms a thin passivating film of Cr 2 O 3 , protecting the underlying grain boundary from intergranular corrosion. However, the metal grain boundary experiences severe Cr depletion and grain boundary migration during this initial exposure. To understand how Cr depletion affects further corrosion, the local protective film was sputtered away using a glancing angle focused ion beam. Upon further exposure, the surface fails to repassivate, and intergranular corrosion is observed through the Cr-depleted region. Through this combination of high-resolution microscopy and localized passive film removal, we show that, although high-Cr alloys are resistant to intergranular attack and stress corrosion cracking, degradation-induced changes in the underlying metal at grain boundaries make the material more susceptible once the initial passive film is breached.
Effect of aging treatment on microstructures, tensile properties and intergranular corrosion behavior of Al–Cu–Li alloy
Highlights: • T8 duplex aging greatly promoted the precipitation of strengthening phases. • Heavy precipitation of strengthening phases led to enhancing of tensile properties. • Intergranular corrosion sensibility can be reduced by T8 duplex aging greatly. - Abstract: The influence of aging treatment on microstructures, tensile properties and corrosion properties of Al–Cu–Li alloy was investigated. The results show that the T8 duplex aging treatment was more effective than T6 and T8 single aging treatment in enhancing the tensile properties and improving the intergranular corrosion (IGC) resistance. Based on the microstructure observation, tensile test, electrochemical experiment and IGC measurement, the factors which affect the microstructures, tensile properties and IGC behavior changing of Al–Cu–Li alloy during aging treatments were discussed in detail.
Proton irradiation-decelerated intergranular corrosion of Ni-Cr alloys in molten salt
The effects of ionizing radiation on materials often reduce to "bad news". Radiation damage usually leads to detrimental effects such as embrittlement, accelerated creep, phase instability, and radiation-altered corrosion. Here we report that proton irradiation decelerates intergranular corrosion of Ni-Cr alloys in molten fluoride salt at 650 °C. We demonstrate this by showing that the depth of intergranular voids resulting from Cr leaching into the salt is reduced by proton irradiation alone. Interstitial defects generated from irradiation enhance diffusion, more rapidly replenishing corrosion-injected vacancies with alloy constituents, thus playing the crucial role in decelerating corrosion. Our results show that irradiation can have a positive impact on materials performance, challenging our view that radiation damage usually results in negative effects.
Intergranular Corrosion of Feedstock Modified—Additively Manufactured Stainless Steel After Sensitization
Laser powder bed fusion (LPBF), a metal additive manufacturing technique, was conducted on feedstock-modified 316L stainless steel (316L) powder produced by ball-milling of commercial 316L and 1 wt% additive (cerium oxide—CeO 2 , lanthanum (III) nitrate hexahydrate—La(NO 3 ) 3 ·6H 2 O, and chromium nitride—CrN). The feedstock-modified LPBF-316L specimens were sensitized at 675°C for 24 h, and the influence of additives on intergranular corrosion (IGC) was investigated following ASTM G108-94 and A262-14 standards. The LPBF-316L with La(NO 3 ) 3 ·6H 2 O showed higher IGC resistance. Furthermore, the microstructure of the LPBF specimen was investigated and correlated to understand the improved IGC resistance of LPBF-316L with La(NO 3 ) 3 ·6H 2 O additive.
Aluminum alloys with improved intergranular corrosion resistance properties and methods of making and using the same
Disclosed herein are embodiments of aluminum-based alloys having improved intergranular corrosion resistance. Methods of making and using the disclosed alloy embodiments also are disclosed herein.
Microstructure evolution during low-strain thermo-mechanical processing and its repercussion on intergranular corrosion in alloy 600H
Highlights: • GBE microstructure in alloy 600H is realized through the sole activation of SIBM. • Higher TRD size and lower fractal dimension are characteristics of GBE microstructure. • Partially/fully recrystallized specimen shows higher DOS than as-received condition. • GBE specimen shows remarkable resistance against percolation and grain dropping. • Extent of percolation is governed by residual strain and random HAGBs connectivity. - Abstract: The current investigation deals with the evolution of microstructures as a consequence of varying processing parameters viz. extent of deformation, annealing temperature and time during grain boundary engineering (GBE) type thermo-mechanical processing in alloy 600H. Furthermore, the influence of the various product microstructures (viz. partially recrystallized, fully recrystallized and GBE) on intergranular corrosion is evaluated and compared with the as-received condition. Detailed characterization of the as-processed specimens have revealed that lower extent of deformation (7.5%) followed by a longer annealing treatment (i.e. 60 min) at a higher temperature (1373 K) could lead to a GBE microstructure with a higher proportion of Σ3{sup n} boundaries (~72%) due to the predominant activation of multiple twinning. In contrast, the specimens associated with moderately higher extent of deformation (10% and 15%) have revealed the occurrence of static recrystallization. The GBE specimen has demonstrated an excellent resistance against percolation essentially due to its discontinuous random high angle boundaries (HAGBs) network. In contrast, the nucleation of the finer grains in the recrystallized specimens caused the regeneration of random HAGBs network (as substantiated by the fractal analysis) that leads to higher percolation and severe grain dropping. In spite of the similar grain boundary character distribution, the severity of corrosion is relatively lesser in the as-received condition than the completely recrystallized specimen owing to its coarse-grained microstructure that commendably retarded the diffusion of chromium from the grain interior to the boundary.
The effect of grain boundary character evolution on the intergranular corrosion behavior of advanced Al-Mg-3wt%Zn alloy with Mg variation
Highlights: • The relationship among GBCD, GBPs, IGC behavior and Mg content in the age hardenable Al-Mg-3.0wt%Zn alloy is established. • None of grain boundaries are found to be immune to the GBPs. • GBPs along low angle grain boundaries are more discontinuous than high angle grain boundaries. • The IGC mechanism of Al-Mg-3.0wt%Zn alloy is clarified. • A new method for the statistical analysis of the continuity of GBPs is used in this paper. The characteristics of grain boundary and grain boundary precipitates of Al-Mg-3wt%Zn alloy with different Mg contents were systematically investigated. Observation by optical microscopy, transmission electron microscopy, scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy show that the morphology and composition of the grain boundary precipitates change little with the variation in the Mg content. Based on the statistical analysis of the spacings between two adjacent grain boundary precipitates, we find that the decrease in the Mg content reduces the continuity of the grain boundary precipitates. Comparing this result with the electron backscattered diffraction analysis, it can be concluded that the continuity of grain boundary precipitates is affected by the proportion of low angle grain boundaries. The observations of grain boundary precipitates at both low angle grain boundaries and high angle grain boundaries using transmission electron microscopy indicate that low angle grain boundaries have more discontinuous grain boundary precipitates. Combining these results with the results of the intergranular corrosion test, the microscopic features of this corrosion behavior and corrosion mechanism are revealed.
Understanding a novel form of intergranular corrosion of stainless steel 316L exposed to molten LiCl-Li 2 O-Li
We report stainless steel 316 L exposed to LiCl-Li2O molten salt containing Li metal for 500 and 1000 h experiences deep intergranular attack and bulk void formation. This degradation is due to a synergistic corrosion mechanism, different than other forms of molten salt corrosion, where Cr and Mn oxides and carbides form along grain boundaries and are dissolved by Li metal. Synchrotron transmission X-ray microscopy 3D imaging is used to show corrosion morphology and Cr enrichment and depletion in a novel format that has not previously been used for bulk corrosion samples.
Quantitative Nanoscale 3D Imaging of Intergranular Corrosion of 304 Stainless Steel Using Hard X-Ray Nanoprobe
Multi-modal imaging, which visualizes changes in the structure and chemistry of the same region of interest in materials by combining various techniques, is becoming attractive to material scientists. Here, we describe a multi-modal approach to investigate intergranular (IG) corrosion of sensitized stainless steels using synchrotron-based nanoscale X-ray imaging with sensitivity to microstructure and chemical composition. Three-dimensional tomography of 304 stainless steel samples deteriorated by IG corrosion, was carried out using X-ray fluorescence and differential phase contrast imaging. These findings were further supported with surface imaging and chemical analysis using scanning electron microscopy and energy dispersive X-ray spectroscopy. The combined quantitative structural and chemical analysis indicates that chromium segregates along grain boundaries, cracking is due to IG corrosion, and Cr-enrichment occurs on the cracked surfaces. Such quantitative 3D imaging of Cr 23 C 6 nucleation at grain boundaries and Cr enriched oxides at cracked surfaces is a powerful tool to correlate IG corrosion mechanisms at nanoscale with buried grain boundary structure and alloy composition. Such understanding of IG corrosion mechanisms is critical for both the development of predictive multiscale corrosion models, and the engineering of corrosion resistant materials.
Author Correction: Proton irradiation-decelerated intergranular corrosion of Ni-Cr alloys in molten salt
In the original version of this article, numbers for the beam current densities were incorrectly given as 1.5, 2.0, and 2.5 mA cm -2 in various locations, instead of the correct values 0.3, 0.4, and 0.5 mA cm -2 . This was owing to a measurement error coming from the indirect correspondence between the Faraday cup and the beam profile monitor (BPM) on the accelerator as the proton beam traveling along the beamline resulted in mismatching between calculated values and real beam currents, which were obtained by ex-situ calibration. The following changes have been made in the correct version. The eighth sentence of the Results, and the figure legend of Fig. 2j state '0.3, 0.4, 0.5 mA cm -2 ' in place of '1.5, 2.0, 2.5 mA cm -2 '. The figure legend of Fig. 1j–l states '0.5, 0.4, 0.3 mA cm -2 ' in place of '2.5, 2.0, 1.5 mA cm -2 '. Figure 1e states '0.5 mA cm -2 ' in place of '2.5 mA cm -2 ', Fig. 1h states '0.4 mA cm -2 ' in place of '2.0 mA cm -2 ', and Fig. 1k states ‘0.3 mA cm -2 ' in place of ‘1.5 mA cm -2 '. Figure 2c states '0.5 mA cm -2 ' in place of '2.5 mA cm -2 ', Fig. 2d states '0.4 mA cm -2 ' in place of '2.0 mA cm -2 ', and Fig. 2e states '0.3 mA cm -2 ' in place of '1.5 mA cm -2 '. Figure 2j and k states ‘0.3 mA cm -2 ', '0.4 mA cm -2 ', '0.5 mA cm -2 ' in place of '1.5 mA cm -2 ', '2.0 mA cm -2 ', and '2.5 mA cm -2 ', respectively. The figure legend of Fig. 3b states '0.4 mA cm -2 ' in place of '2.0 mA cm -2 '. The figure legend of Supplementary Fig. 1 states '0.5 mA cm -2 ' in place of '2.5 mA cm -2 '. This has been corrected in the PDF and HTML versions of the Article.
A Multiscale Inelastic Internal State Variable Corrosion Model
We present a corrosion internal state variable (ISV) damage model based upon the integrated computational materials engineering (ICME) hierarchical multiscale paradigm. Structure–property experiments for magnesium alloys were used where the only inputs were the volume fractions of each element of the periodic table. This macroscale ISV corrosion model finds its basis in Horstemeyer’s mechanical damage model, which includes three separate ISVs for damage nucleation, growth, and coalescence, as well as Walton’s inclusion of corrosion, which introduces five new ISVs for pit nucleation, growth, and coalescence, along with general corrosion and intergranular corrosion. While Walton’s corrosion ISVs are phenomenological in nature, herein we develop a multiscale physical basis for the corrosion ISVs. The parameters for the macroscale corrosion ISVs were garnered from the mesoscale Butler–Volmer equations. Pure magnesium with differing amounts of aluminum were used in corrosion tests to exemplify the different pitting, general corrosion, and intergranular corrosion rates, and the macroscale ISV model was calibrated with said data, in which the only inputs to the model are the volume percentages of the elements magnesium and aluminum. Although magnesium alloys were used to motivate and calibrate the model, the model is abstract enough to possibly capture other material systems as well.
Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water
The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300-360°C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N2 gas. Results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.
Effects of In Situ Intermetallics on the Microstructural Array and Saline Corrosion Performance of Cast Al/WCp Composites
Al-matrix composites, ex situ reinforced with WC nanoparticles and in situ reinforced with Al{sub 3}(Ti,W), Al{sub 12}W, Al{sub 5}W and Al{sub 4}W, have been fabricated by casting assisted by K{sub 2}TiF{sub 6} wetting agent addition and mechanical stirring. A satisfactory particle incorporation and distribution accompanied by a high reactivity have been attained. The presence, topography, chemical composition of all included phases and their occurrence as clusters or single particles are clarified and justified. Al{sub 12}W is the predominant aluminide phase at WC ≤ 1.5 vol.%. Al{sub 4}W (primarily) and Al{sub 5}W (secondarily) are the predominant aluminide phases at WC ≥ 2.0 vol.%. WC nanoparticles have acted as heterogeneous nucleation sites to Al{sub 3}Ti particles. Reverse polarization tests in 3.5 wt.% NaCl show that the governing form of corrosion is intergranular corrosion of Al around Al{sub 3}FeSi{sub 2} eutectic, fine plates. The corrosion steps/mechanisms are identified. Clusters of aluminides and carbide nanoparticles, as well as intergranular WC nano-dispersoids and their Al-matrix have remained corrosion-free. The role of the aluminides combined with WC remaining nano-cores as inhibitors of the eutectic Al{sub 3}FeSi{sub 2} cathodic activity is highlighted.
How irradiation promotes intergranular stress corrosion crack initiation
Irradiation assisted stress corrosion cracking (IASCC) is a form of intergranular stress corrosion cracking that occurs in irradiated austenitic alloys. It requires an irradiated microstructure along with high temperature water and stress. The process is ubiquitous in that it occurs in a wide range of austenitic alloys and water chemistries, but only when the alloy is irradiated. Despite evidence of this degradation mode that dates back to the 1960s, the mechanism by which it occurs has remained elusive. Here, using high resolution electron backscattering detection to analyze local stress-strain states, high resolution transmission electron microscopy to identify grain boundary phases at crack tips, and decoupling the roles of stress and grain boundary oxidation, we are able to unfold the complexities of the phenomenon to reveal the mechanism by which IASCC occurs. The significance of the findings impacts the mechanical integrity of core components of both current and advanced nuclear reactor designs worldwide.
Corrosion Behavior of Laser-Brazed Surface Made by Joining of AA6082 and Galvanized Steel
In the present study, a galvanized steel and a AA6082 aluminum alloy sheet of 2 mm thick were weld-brazed by applying laser and using 2-mm-diameter solid Al-12% Si filler wire at 2.5 m/min wire feed rate and 2 m/min laser scan speed at varying laser power (4.0, 3.5, 3.0 kW) in flange configuration. The microstructural investigation of the laser weld-brazed joints revealed the presence of two-layered intermetallic compound at steel/braze seam interface. The corresponding x-ray diffraction analysis of the steel/braze seam interface showed the presence of Al-Fe-Si-based ternary intermetallic phases. SEM and EDS analysis of the braze seam revealed the presence of α-Al grains surrounded by Mg{sub 2}Si phase in the grain boundary region. Fine intermetallic layer was observed at lower heat-input condition. The corrosion performance of the brazed joints was studied with the help of immersion, salt spray, and electrochemical polarization tests in different electrolytes containing NaCl salt. Brazed joints experienced galvanic corrosion during immersed in corrosive media. From the salt spray test, it was revealed that galvanized steel was highly susceptible to corrosion compared to Al-rich phase. The polarization results showed a substantial change in corrosion resistance from steel interface to the brazed region due to the variation in microstructure. The samples brazed with low heat-input showed better corrosion resistance as compared to the joints made with high heat-input. Post-corrosion microstructure revealed intergranular corrosion at the brazed joint along with pit formation.