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At least 19 records

Localized corrosion: Passive film breakdown vs. Pit growth stability, Part VI: Pit dissolution kinetics of different alloys and a model for pitting and repassivation potentials

Here, the pitting resistance of SS316L, SS304, SS430, and pure Fe was studied in chloride-containing solution. Among these alloys, SS316L exhibits the highest pit initiation rate, but also the highest pitting potential. To explain this phenomenon, the maximum pit dissolution current density (i diss,max ) of the alloys in saturated pit solution was measured using one-dimensional artificial pit electrodes. A lower i diss,max was found to correlate with higher pitting and repassivation potentials. Based on a recently proposed pitting framework, a conceptual model for pitting and repassivation potentials was established, based on which the effect of i diss,max on pitting resistance was discussed.

one-dimensional artificial pit electrode↗

The Shape Factor for Pits and Its Impact on Pit Stability

This study employs the finite element method (FEM) to predict the impact of pit shape on pit stability via shape factors of various pit geometries relevant to localized corrosion. Lower values of the shape factor indicate an increased ease in maintaining pit stability. Analyzed geometries include undercut pits, bispherical pit-within-pit structures, and covered pits with perforated (lacy) covers. The effect of the water layer thickness, transport properties of the electrolyte inside and outside the pit, and cathode location on the pit shape factor were also explored. Results show that occluded pits exhibit lower shape factors than open ones, with disk-shaped pits decreasing further as c/r ratio and occlusion angle increase. The findings also suggest minimal influence from a secondary pit if the primary remains active. An equation is presented that quantifies the impact of lacy covers, revealing significant shape factor value reduction. Additionally, high salt concentrations inside pits have a limited stabilizing effect compared to geometry, while thin water layers and adjacent cathodic/sinks reduce pit stability.

Shehi, A. (ORCID:0009000271548041)↗

Pit rim decomposition into multiple quantum dots on surfaces of epitaxial thin films grown on pit-patterned substrates

Here, we report results of dynamical simulations according to an experimentally validated surface morphological evolution model on the formation of regular arrays of quantum dot molecules (QDMs) consisting of 1D arrays of smaller interacting quantum dots (QDs). These QD arrays form along the sides of each pit rim on the surface of a coherently strained thin film epitaxially deposited on a semiconductor substrate, the surface of which consists of a periodic pattern of inverted prismatic pits with rectangular pit openings. We find that this complex QDM pattern results from the decomposition of the pit rim from a “quantum fortress” with four elongated QDs into four 1D arrays of multiple smaller QDs arranged along each side of the pit rim. Systematic parametric analysis indicates that varying the pit opening dimensions and the pit wall inclination directly impacts the number of QDs in the resulting QDM pattern, while varying the pit depth only affects the dimensions of the QDs in the nanostructure pattern. Therefore, the number, arrangement, and sizes of QDs in the resulting pattern of QDMs on the film surface can be engineered precisely by proper tuning of the pit design parameters. Our simulation results are supported by predictions of morphological stability analysis, which explains the pit rim decomposition into multiple QDs as the outcome of a tip-splitting instability and provides a fundamental characterization of the post-instability nanostructure pattern. Our theoretical findings can play a vital role in designing optimal semiconductor surface patterns toward enabling future nanofabrication technologies.

36 MATERIALS SCIENCE↗

Inhibition of Micro-pitting by Tribofilm-Forming ZrO 2 Nanocrystal Lubricant Additives: A Micro-pitting Rig and Transmission Electron Microscope Study

The drive to reduce fuel consumption in transportation has encouraged the emergence of low viscosity lubricants to reduce viscous losses in the engine, drivetrain, and other components. However, viscosity reduction increases the risk of surface damage, thus motivating the development of new anti-wear (AW) additives. Capped ZrO 2 nanocrystals (NCs) in base oils have been shown to form AW tribofilms within microscale sliding contacts. However, the potential of ZrO 2 NCs to protect surfaces subjected to rolling-sliding contact from macroscale damage, such as micro-pitting, remains unexplored. Here, we explore the ability of ZrO 2 NCs to form protective tribofilms under harsh conditions using a micro-pitting rig (MPR), consisting of a three ring-on-roller configuration. The experiments were conducted in polyalphaolephin (PAO) base oil, with and without 5 nm diameter ZrO 2 NCs, at two levels of slide-to-roll ratio (SRR) (30% and 0%) and at variable test durations up to long durations (119 h). MPR results showed the use of ZrO 2 NCs gives rise to the formation of a tribofilm covering the roller surfaces and decreases the initiation and propagation of micro-pits compared to tests in pure PAO base stock. Transmission electron microscopy (TEM) performed on focused ion beam (FIB) milled cross-sectional samples of the roller surfaces revealed the growth of dense and 50–100 nm thick ZrO 2 -based tribofilms independent of (SRR), indicating the potential for robust micro-pitting fatigue protection. Nevertheless, small cracks localized within the near surface region of the roller tested at the most severe conditions (30% SRR and 119 h) were observed. The initiation of these cracks was directly related to the presence of manganese sulphide (MnS) inclusions in the steel, revealed using TEM combined with energy dispersive spectroscopy (EDS). Furthermore, the results highlight the benefits of the protective tribofilms formed by ZrO 2 NCs and suggest approaches for further optimizing their use.

36 MATERIALS SCIENCE↗

Diesel Fuel Consumption in Prominent U.S. Open-Pit Mines: Site-Level Estimates

This report presents a comprehensive framework for estimating diesel fuel consumption and prices at open-pit mines in the United States. The framework includes transparent methods for calculating site-level diesel energy use when direct reporting is unavailable, and a structured confidence evaluation for each method. The framework is demonstrated to estimate current diesel consumption at 21 open-pit mines in the United States. Initial findings support ongoing efforts to strengthen the competitiveness and security of the U.S. industrial base by supporting data-driven supply chain analysis and decision-making, improved transparency in mining sector energy use, and targeted deployment of energy innovation and cost-reduction strategies. Future updates to the dataset—coupled with expanded data transparency and method validation—will help ensure that the findings remain relevant as the sector continues to evolve.

02 PETROLEUM↗

Pitting Corrosion in 316L Stainless Steel Fabricated by Laser Powder Bed Fusion Additive Manufacturing: A Review and Perspective

Abstract 316L stainless steel (316L SS) is a flagship material for structural applications in corrosive environments, having been extensively studied for decades for its favorable balance between mechanical and corrosion properties. More recently, 316L SS has also proven to have excellent printability when parts are produced with additive manufacturing techniques, notably laser powder bed fusion (LPBF). Because of the harsh thermo-mechanical cycles experienced during rapid solidification and cooling, LPBF processing tends to generate unique microstructures. Strong heterogeneities can be found inside grains, including trapped elements, nano-inclusions, and a high density of dislocations that form the so-called cellular structure. Interestingly, LPBF 316L SS not only exhibits better mechanical properties than its conventionally processed counterpart, but it also usually offers much higher resistance to pitting in chloride solutions. Unfortunately, the complexity of the LPBF microstructures, in addition to process-induced defects, such as porosity and surface roughness, have slowed progress toward linking specific microstructural features to corrosion susceptibility and complicated the development of calibrated simulations of pitting phenomena. The first part of this article is dedicated to an in-depth review of the microstructures found in LPBF 316L SS and their potential effects on the corrosion properties, with an emphasis on pitting resistance. The second part offers a perspective of some relevant modeling techniques available to simulate the corrosion of LPBF 316L SS, including current challenges that should be overcome.

Voisin, T. (ORCID:0000000287462659)↗

Pitting Propagation Behavior on Low Alloy AISI 4130 (UNS G41300) Steel Exposed to Various Alkali and Alkaline Earth Metal Chlorides

Pit propagation studies were conducted to elucidate whether alkali and alkali earth metal cations such as Na+ and Rb+ present in the form of metal chloride salts such as RbCl affect pitting behavior in distinctly different manner than NaCl. Pit propagation studies were conducted on a low alloy steel using one-dimensional (1-D) pit method over pit depths from 300-1000 µm. LSV and EIS of planar electrodes of 4130 in a range of Cl- solutions were conducted and revealed no detected differences in impedance, open circuit, corrosion potential (Ecorr), passive current density (ipass), and pitting potential (Epit) as a function of salt type. In the case of one-dimensional pits during fast downward scan rates, the saturation potential (Esat) varied as a function of cation identity when pit depths were shallow. Mass transported limited current density also differed with cations in shallow pits when various alkali metal and alkaline metal cations were present. The limiting current density was increased for RbCl relative to NaCl The pit surface potential (Esurf) of activated pit surfaces reached Ecorr prior to establishing a condition where the pit electrolyte surface concentration (Csurf) was less than the critical concentration for active acidified pitting (i.e. Csurf<Ccrit) in this marginally passivating steel. For various Esurf and pit current density (ipit) combinations at constant Csurf where Ccrit< Csurf < Csat, E-log(i) plots were constructed using the method of Tianshu to create IR ohmic voltage corrected Tafel plots for various fixed pit solution concentrations. Under these conditions, the influence of cation identity on charge transfer controlled kinetics indicated slight differences in Tafel behavior where RbCl was slightly more aggressive than NaCl for low alloy steel oxidation. Differences in metal cation identity exert no effect on passive or breakdown on planar electrodes and only effect pit propagation stage in shallow pits.

Demarest, Chalres↗

Understanding the Interactions of Multiple Pits Under Freely Corroding Conditions

The interactions of two propagating pits on a single cathode surface were evaluated across variations in chloride concentration, water layer (WL), pit sizes, separation distance (x 2 ), and cathode size (L Cath ) under freely corroding conditions using Finite Element Methods (FEM). Calculated FEM current was utilized to predict stability based on the Galvele pit stability product. FEM predictions were utilized to train a neural network machine learning model for rapid stability predictions. Pit one is in the center of a circular cathode while pit two moves radially from the center pit. With two pits, the overall current in each pit is decreased with respect to a single pit, however, the total current is increased. Increasing WL and L Cath generally increased overall current in each pit and increased predicted maximum pit sizes. Increasing x 2 decreased current in pit two due to less cathode being available to support dissolution in proximity to pit two. Increasing chloride concentration from 0.6 to 3 M NaCl increased current, while increasing from 3 to 5.3 M NaCl decreased current. An overall increase in predicted pit size with increase in chloride concentration is predicted. A machine learning model was created to predict current and maximum pit size and captured underlying physics and predicted stability across the multidimensional parameter space.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pit Stability Predictions of Additively Manufactured SS316 Surfaces Using Finite Element Analysis

Stainless steels are susceptible to localized forms of corrosion attack, such as pitting. The size and lifetime of a nucleated pit can vary, depending on a critical potential or current density criterion, which determines if the pit repassivates or continues growing. This work uses finite element method (FEM) modeling to compare the critical pit radii predicted by thermodynamic and kinetic repassivation criteria. Experimental electrochemical boundary conditions are used to capture the active pit kinetics. Geometric and environmental parameters, such as the pit shape and size (analogous to additively manufactured lack-of-fusion pores), solution concentration, and water layer thickness were considered to assess their impact on the pit repassivation criterion. The critical pit radius (the transition point from stable growth to repassivation) predicted for a hemispherical pit was larger when using the repassivation potential (E rp ) criteria, as opposed to the current density criteria (pit stability product). Including both the pit stability product and E rp into its calculations, the analytical maximum pit model predicted a critical radius two times more conservative than the FEA approach, under the conditions studied herein. The complex pits representing lack-of-fusion pores were shown to have minimal impact on the critical radius in atmospheric conditions.

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↗

Beneficial effect of copper on pitting resistance of Ni-Cr-Fe alloys

This study examines the effect of copper alloying on pitting resistance in a model solid solution FCC Ni-13%Cr-10%Fe alloy through potentiodynamic and potentiostatic polarization in 0.1 M NaCl in conjunction with an analysis using first-principles competitive electro-chemisorption modeling. The pitting potential increased with increasing Cu content in the alloy. Furthermore, the extent of metastable pit growth was suppressed and the incubation time for metastable to stable pit transition increased with Cu content. The first-principles competitive adsorption calculations suggested that Cu alloying suppresses chloride ion adsorption on the alloy surface in a simulated pit environment, which inhibits active dissolution at the pit bottom, enhances proton adsorption, and thereby increases the local pH at the pit bottom. In conclusion, we propose that these two effects of Cu in solid solution combine to reduce pit stability and may act in addition to the enrichment of Cu on the corroding pit surface.

36 MATERIALS SCIENCE↗

Predicting Pit Stability On Additively Manufactured SS316 Via Finite Element Modeling [Slides]

Pit growth and repassivation are complex, with many interconnecting geometric and environmental parameters to consider. Experimentally, it is difficult to isolate these individual parameters to study their effect on the stability of pits. To enable these studies, a finite element modeling approach has been developed to allow systematic testing of parameters that impact a pit’s stability. The specific parameters studied were the cathode diameter, the pit diameter and shape, and the water layer thickness. Hemispherical and rectangular-based pits were studied to determine the impact of the overall pit shape. Pit stability results were compared with mathematical calculations based on the Maximum Pit Model, for both 50% saturation and 100% saturated salt film coverage. Further studies expanded the range of pit geometry to those relevant to additively manufactured surfaces.

36 MATERIALS SCIENCE↗

Analysis of Pitting Corrosion on Wrought and Additively Manufactured 316L Stainless Steel in Atmospheric Environments

Additive manufacturing of metal components enables rapid fabrication of complex geometries. However, metal additive manufacturing also introduces new morphological and microstructural characteristics which might be detrimental to component performance. Here we report the pitting corrosion properties of wrought and additively manufactured 316L stainless steel after atmospheric exposure to coastal environments and laboratory-created environments. Qualitative visualization in combination with quantitative analysis of resulting pits provided an in-depth understanding of pitting differences between wrought and additively manufactured 316L stainless steel and between coastal and laboratory-based exposure. Optical and scanning electron microscopy were utilized for visualization, while white light interferometry measured pits across approximately 5mm x 5mm areas on each sample. Post-processing of the interferometry data enables quantification of pitting attack for each sample in terms of both pit depth and pit volume. The pitting analysis introduced herein offers a new technique to compare pitting attack between different manufacturing processes and materials.

36 MATERIALS SCIENCE↗

Geothermal Reserve Pits: Considerations for Installation on BLM-Administered Lands

Reserve pits, also known as sumps, are a common aspect of geothermal drilling operations. This paper describes the Bureau of Land Management's regulatory authorities and key environmental considerations associated with geothermal reserve pits. Reserve pit design, the need for environmental compliance measures, and reclamation approaches will vary depending on site-specific conditions. Groundwater and wildlife impacts are the most common environmental considerations related to reserve pits. In some cases, regulations or groundwater or soil conditions necessitate the use of a synthetic liner. However, the chemical composition of most geothermal drilling fluids and muds, completion fluids, and produced fluids that are discharged to reserve pits does not warrant pit liners. The potential for hazardous fluids, high water temperatures, and entrapment are concerns for wildlife. Common wildlife impact avoidance and mitigation measures include fencing, netting, and escape ramps. The need for these measures depends on localized site and environmental conditions. There are requirements to reclaim reserve pits following geothermal drilling operations. Reserve pits often remain in place to accommodate multiple phases of drilling and well testing. They are eventually backfilled and decommissioned.

BLM↗

Revealing the growth kinetics of atmospheric corrosion pitting in aluminum via in situ microtomography

Abstract Understanding the mechanistic relationship between the environment, microstructure, and local kinetics of atmospheric corrosion damage remains a central challenge. To address this challenge, this study used laboratory-based X-ray tomography to directly observe attack in-operando over an extended period, enabling insights into the evolving growth kinetics and morphology of individual pits over months of exposure. Damage progression associated with nine pits in a 99.9% pure aluminum wire exposed to chloride salts in humid air was characterized. Most pits grew at a nominally linear rate up until pit death, which occurred within 12–24 h of nucleation. Exceptions to this were observed, with three pits exhibiting bimodal growth kinetics and growing for 40 or more hours. This was explained by secondary droplets that formed near the pits, increasing the cathode area. A corrosion-driven drying mechanism likely contributed to pit death in both cases. Pits first grew into the material followed by lateral expansion.

36 MATERIALS SCIENCE↗

The evolution of pit morphology and growth kinetics in aluminum during atmospheric corrosion

Abstract Assessing the lifetimes of alloys in humid, corrosive environments requires growth kinetic information regarding individual instances of damage, e.g. pit growth rates. Corrosion rates measured at the continuum scale using mass change convolute the rate of pit nucleation and growth, providing limited information on local kinetics. The current study used in-situ X-ray computed tomography to measure growth rates of individual pits in aluminum over 100 h of exposure in a humid, chloride environment. While pits grew at relatively constant rates over the first hours after nucleation, significant growth-rate nonlinearities subsequently occurred. These were linked to both droplet spreading, which altered the cathode size, and changes in the mode of pit growth. Pit morphology appeared to influence the dominant growth mode and the duration of pit growth. Post-mortem serial sectioning revealed pits preferentially attacked grain-boundary triple junctions and dislocation boundaries.

Noell, Philip J. (ORCID:0000000346998999)↗