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At least 55 records · Page 3

Dependence of Crystallographic Orientation on Pitting Corrosion Behavior of Ni-Fe-Cr Alloy 028

The influence of crystallographic orientation on the pitting corrosion behavior of Ni-Fe-Cr alloy 028 was studied using a combination of X-ray diffraction (XRD), electron backscatter diffraction (EBSD), potentiodynamic polarization technique, and atomic force microscopy (AFM). The results show that there is anisotropy of pitting corrosion that strongly depends on crystallographic orientation of the surface plane. The distribution of pit density in a standard stereographic triangle indicates that the crystallographic planes close to {100} are more prone to pitting corrosion compared to planes {110} and {111}. The surface energy calculation of (001) and (111) shows that the plane with a high atomic packing density has a low surface energy with concomitant strong resistance to pitting corrosion. A correlation function between crystallographic orientation and pitting corrosion susceptibility suggests a method that not only predicts the pitting resistance of known textured materials, but also could help to improve corrosion resistance by controlling material texture.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Pitting Corrosion of 10Ni8CrMoV High-Strength Steel Induced by a Potential Perturbation

Pitting corrosion of high-strength steel 10Ni8CrMoV under square wave polarization (SWP) in simulated deep-sea environment is investigated and the possible mechanism is proposed. The results show that potential perturbation generates periodic intensification effect on both anodic and cathodic processes by frequently breaking the electrode equilibrium state. The intensity of periodic intensification effect essentially depends on the concentration gradient of Fe{sup 2+} cations at the steel/solution interface which acts as the forced electrochemical oscillator. The concentration gradient and the resulting concentration polarization effect increase periodically with the increase in SWP potential range. The morphology observation of the pitting and electric charge calculation indicate that the periodic intensification effect can promote the initiation and growth of pits by enhancing the anodic dissolution even under cathodic protection, but it is ineffective below the hydrogen evolution potential. The decrease in either upper or lower potential can mitigate anodic dissolution. Through the statistical analysis of pitting size, it is found that the wide potential range tends to activate the metastable pitting formed under hydrostatic pressure, forming densely distributed pitting. Meanwhile, it is more favorable to the formation of fully grown pits with high size dispersion degree when the proportion of electric charge in the anodic process is higher.

36 MATERIALS SCIENCE↗

Heterogeneous nucleation of pits via step pinning during Si(100) homoepitaxy

Using scanning tunneling microscopy (STM), we investigate oxide-induced growth pits in Si thin films deposited by molecular beam epitaxy. In the transition temperature range from 2D adatom islanding to step-flow growth, systematic controlled air leaks into the growth chamber induce pits in the growth surface. We show that pits are also correlated with oxygen-contaminated flux from Si sublimation sources. From a thermodynamic standpoint, multilayer growth pits are unexpected in relaxed homoepitaxial growth, whereas oxidation is a known cause for step-pinning, roughening, and faceting on elemental surfaces, both with and without growth flux. Not surprisingly, pits are thermodynamically metastable and heal by annealing to recover a smooth periodic step arrangement. STM reveals new details about the pits' atomistic origins and growth dynamics. Here, we give a model for heterogeneous nucleation of pits by preferential adsorption of Å-sized oxide nuclei at intrinsic growth antiphase boundaries, and subsequent step pinning and bunching around the nuclei.

36 MATERIALS SCIENCE↗

Direct observation of pitting corrosion evolutions on carbon steel surfaces at the nano-to-micro- scales

The Cl¯-induced corrosion of metals and alloys is of relevance to a wide range of engineered materials, structures, and systems. Because of the challenges in studying pitting corrosion in a quantitative and statistically significant manner, its kinetics remain poorly understood. Herein, by direct, nano- to micro-scale observations using vertical scanning interferometry (VSI), we examine the temporal evolution of pitting corrosion on AISI 1045 carbon steel over large surface areas in Cl¯-free, and Cl¯-enriched solutions. Special focus is paid to examine the nucleation and growth of pits, and the associated formation of roughened regions on steel surfaces. By statistical analysis of hundreds of individual pits, three stages of pitting corrosion, namely, induction, propagation, and saturation, are quantitatively distinguished. By quantifying the kinetics of these processes, we contextualize our current understanding of electrochemical corrosion within a framework that considers spatial dynamics and morphology evolutions. In the presence of Cl¯ ions, corrosion is highly accelerated due to multiple autocatalytic factors including destabilization of protective surface oxide films and preservation of aggressive microenvironments within the pits, both of which promote continued pit nucleation and growth. Furthermore these findings offer new insights into predicting and modeling steel corrosion processes in mid-pH aqueous environments

36 MATERIALS SCIENCE↗

Effect of varying threading dislocation densities on the optical properties of InGaN/GaN quantum wells with intentionally created V-shaped pits

The effect of varying threading dislocation densities on the internal quantum efficiencies (IQEs) of InGaN quantum wells (QWs), with and without intentionally created “V-pits,” is reported here. InGaN QW samples grown on GaN-on-sapphire templates with threading dislocation densities of <1 × 108 and <1 × 109 cm−2 are compared, with and without GaN/InGaN superlattice (SL) layers incorporated to intentionally open up the threading dislocation cores and form large-size “V-pits.” The formation of “V-pits” is confirmed by cross-sectional transmission electron microscopy to initiate from threading dislocations in the SL layers. The densities of the pits are confirmed by plan-view SEM to agree with the substrate threading dislocation densities. The experimental room temperature IQEs of the “V-pit” QW samples are enhanced to 15% ± 1% compared to 6% ± 2% for conventional QW samples. Both conventional and “V-pit” samples show insensitivity to the magnitude of the dislocation densities with respect to IQE performance, while the “V-pit” samples show shifts in the peak emission wavelengths compared to the conventional samples, attributed to strain modulation. This study provides additional understanding of the causes of the observed insensitivity of the IQEs to different threading dislocation densities.

Engineering↗

Research on Deformation Law of Deep Foundation Pit of Station in Core Region of Saturated Soft Loess Based on Monitoring

Saturated soft loess has a large pore structure, high compressibility, low strength, fluid plastic state, and poor engineering properties. It is still one of the key problems that engineering needs to solve. In order to study the influence of deep foundation pit excavation in the saturated soft loess area on the deformation of foundation pits, the deformation laws of ground settlement, enclosure structure, and supporting axial force were clarified based on the field tests on the deformation characteristics of deep foundation pits in areas with the high-water level in saturated soft loess, combined with geological conditions and on-site construction procedures. The results indicate the following: water supply and construction process were found to be the main factor in changing the surface settlement curve of deep foundation pits in saturated soft loess; increasing the construction speed of the pit bottom floor, inverted braces, floor frame beams, and sidewall frame beams to close the structure, which is conducive to restraining the deformation of the continuous underground wall and foundation pits in similar areas. In the initial stage of support layout, the axial force of steel support tends to increase too fast or even exceed the standard control value. Therefore, a reasonable preadding axial force is an effective means to control the deformation of the continuous underground wall and the axial force of the steel support. The current research results may provide a reference for constructing deep foundation pits in similar areas.

Wang, Xueyan↗

Chemistry Envelope for Pitting and Stress Corrosion Cracking Mitigation

The present waste chemistry controls for the Hanford double-shell tanks (DSTs) were established in the 1980s in response to tank failures caused by stress corrosion cracking (SCC) at the DOE Savannah River Site (SRS). Portions of the SRS chemistry limits were coupled with corrosion testing results from Pacific Northwest Laboratory (PNL) and adopted for corrosion control of the DST waste at the Hanford Site. Since that time, the temperatures of many DST wastes have decreased to less than 50 °C as the radioactive material has decayed, the testing program in Argentina demonstrated that chloride ion in Hanford Site waste could cause pitting, and other work showed that dilute solutions could cause pitting at the liquid air interface (LAI). Moreover, future transfers from the single shell tanks and the waste treatment plant and process changes may shift the DST waste chemistries to a broader range of compositions with higher aggressive anion concentrations than the wastes that are presently stored. The decreasing temperatures led to the formulation of new chemistry controls for the minimization of SCC risks for operations below 50 °C in 2010, and these controls were partially adopted. The Tank Integrity Expert Panel (TIEP) Corrosion Subgroup (CSG) recommended that additional testing be performed to assess the potential for pitting and LAI corrosion. Since 2015, DNV-GL, SRNL, and the Hanford Site laboratory have investigated pitting and LAI corrosion at current and anticipated DST chemistries and Savannah River National Laboratory (SRNL) undertook a statistically based investigation of the role of nitrate and halide ion induced pitting corrosion. The objective was to develop a comprehensive waste chemistry envelope for the simultaneous minimization of the pitting and SCC risks caused by halide and nitrate ions. This report summarizes the technical basis for the new waste chemistry envelope to minimize the potential for both pitting and cracking corrosion induced by nitrate and halide ions, and the strategies used for the validation of the new controls.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Pit Technologies at a Glance

The National Nuclear Security Administration has tasked Los Alamos National Laboratory (LANL) with important national security work: to develop a plutonium pit manufacturing capability and deliver a minimum of 30 plutonium pits per year in the years ahead. A pit is a hollow sphere of plutonium that, when uniformly compressed by explosives inside a warhead or bomb, causes a nuclear explosion. New pits are needed to maintain the nation’s nuclear stockpile and are a key component of nuclear deterrence and world peace. LANL’s Pit Technologies (PT) division manufactures these pits safely and securely. The work takes place in the Plutonium Facility (PF-4), the nation’s most modern plutonium science and manufacturing facility. LANL is currently the only place in the country with the capability to manufacture plutonium pits.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Influence of Heat Input and Cold Wire Feeding Rate on Pitting Corrosion Resistance of Submerged Arc Welding Duplex Stainless Steel Welds

Welding thermal cycles may severely impair duplex stainless steel (DSS) performance, especially local pitting resistance and toughness. The restricted welding energy between 0.5 and 2.5 kJ mm{sup −1} represents a limiting factor for productivity increase in DSS welding, and the addition of cold wire is an interesting alternative to increase the welding deposition rate without adding extra heat. The aim of this work is to evaluate the influence of the cold wire feeding rate (CW) and heat input (HI) on pitting corrosion behavior of DSS UNS S32304 bead-on-plate welds obtained by submerged arc welding (SAW). Cyclic potentiodynamic polarization was carried out in transverse weld sections using 1 mol L{sup −1} NaCl solution at room temperature. Most pitting corrosion spots were located on the heat-affected zone (HAZ), and the pitting potentials were lower than the base metal due to higher ferrite fractions and the presence of chromium nitrides. Considering the same CW, the HI increasing reduced E{sub pit} for 1.6, 1.9, 2.2 kJ mm{sup −1}, but increased E{sub pit} for 2.7 kJ mm{sup −1}, due to a balance between the HAZ width and the austenite fraction.

36 MATERIALS SCIENCE↗

Refinement of Pitting Factor Basis to Evaluate Minimum Nitrite Requirement in Dilute Waste Chemistries

Considering that chloride concentrations are an order of magnitude lower at SRS than the maximum chloride previously tested to evaluate pitting susceptibility of carbon steel, it has been proposed that the Pitting Factor methodology be refined to determine if a reduction in the minimum nitrite requirement is warranted in more dilute solutions and those with chloride concentrations more indicative of waste tank chemistries at SRS. Through the use of cyclic potentiodynamic polarization, the susceptibility of A537 carbon steel to pitting corrosion was evaluated. The Pitting Factor was shown to accurately predict pitting susceptibility throughout the chemistry envelope evaluated. In addition, it was shown that nitrite is not required for inhibition of pitting corrosion in tank conditions with chloride concentrations observed at SRS and up to 4 M nitrate. Based upon these findings, new control limits were proposed that removed the minimum nitrite requirement within the chemistry envelope evaluated up to 50 °C.

36 MATERIALS SCIENCE↗

Waste Chemistry Envelope for the Determination of Pitting Corrosion Susceptibility - 19554

Liquid radioactive wastes at the Hanford and Savannah River sites are stored in large underground carbon steel tanks. The high-level wastes are processed in several of the tanks and then transferred by piping to other site facilities for further processing before they are stabilized in a vitrified or grout waste form. Based on waste removal and processing schedules, many of the tanks, will be required to be in service for times exceeding the initial intended life (i.e., greater than 60 years). Until the waste is removed from storage, transferred, and processed, the materials and structures of the tanks must maintain a confinement function by providing a barrier to the environment and by maintaining acceptable structural stability during design basis events, which include loadings from both normal service and abnormal (e.g., earthquake) conditions. Administrative programs are in place to mitigate potential corrosion mechanisms and thereby maintain the structural and leak integrity functions of these waste tanks throughout their intended service life. Waste chemistry and temperature control are the means by which corrosion degradation of the waste tanks is minimized. Chemistry controls are based on in-situ coupon tests, waste tank experience, and laboratory testing. These requirements comprise the technical standards for corrosion control. The standards are utilized then as guidelines for operational procedures. The present waste chemistry controls for the Hanford DSTs were established in the 1980's in response to tank failures caused by stress corrosion cracking (SCC) at the DOE Savannah River Site (SRS). Portions of the SRS chemistry limits, which were developed at the Savannah River National Laboratory (SRNL) were coupled with corrosion testing results from Pacific Northwest National Laboratories (PNNL) and adopted for corrosion control of the double-shell tank (DST) waste at the Hanford Site. Since that time, the temperatures of the waste in the DSTs have decreased to less than 50 deg. C in most cases as the radioactive material has decayed. As a consequence, new chemistry controls were formulated for SCC in 2010. This testing however, did not address that potential for pitting in the supernatant and at the liquid-air interface. Indeed, initial tests indicated that the inhibitor requirements for SCC would be insufficient for the prevention of pitting. In addition to lower waste temperatures, future retrieval and process changes may impact the DST waste chemistry. Initial projections suggest that the waste chemistry of the DSTs may shift to a broader range of pH and higher aggressive anion concentrations (e.g., chloride, sulfate, etc.) than the wastes that are presently stored. Additionally, processes within the vitrification facility may result in streams that are returned to the tank farm for evaporation. These streams may also contain high concentrations of aggressive species. SRNL investigated the propensity for pitting of the carbon steel waste tanks at current and projected DST waste chemistries. A statistically designed series of tests provided a pitting factor that relates the ratio of the inhibitor species to the aggressive species and the probability of observing pitting. An acceptable pitting factor was determined and was utilized for the development of a new chemistry envelope. The new chemistry envelope was compared to the envelope that was established for SCC and was determined to be bounding. Validation of the new chemistry envelope was performed via model simulations and comparison with historical experimental results and approaches to establishing chemistry envelopes. The new chemistry envelope will eventually be part of an overall assessment of the condition of the tanks and any changes made to the overall structural integrity program for the Hanford DSTs. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Repassivation underneath salt film on stainless steel pits

The repassivation temperature (Trp) of one-dimensional artificial pits made from 316L stainless steel was investigated in 3.5 wt.% NaCl by downward temperature scanning. For a given pit depth, T rp exhibited an unexpected “S” dependence on applied potential. Further analysis shows that this relationship is derived from repassivation underneath the salt film, which is different from repassivation that occurs when the concentration of metal cations at the pit surface decreases below a critical value. This indicates that there exists a reversal in the effect of the salt film on pit growth stability, which depends on temperature, applied potential, and pit depth.

36 MATERIALS SCIENCE↗

Pits 101: The four types of nuclear weapons modernization activities

We learned why we don’t need plutonium to make new pits in an earlier edition of Pits 101, but why do we need new pits from a national security standpoint? A plutonium pit, or the core of a nuclear weapon, is like a weapon’s battery. The pits that Los Alamos will make in coming years will be like new batteries for nuclear weapons in the existing stockpile. Pit production is mandated in order to meet Department of Defense (DOD) requirements by our primary customer, the National Nuclear Security Administration (NNSA), which is a semi-autonomous agency within the Department of Energy. NNSA’s mission is to “deliver safe, secure, reliable warheads for an effective nuclear deterrent.” As Marv Adams, head of NNSA Defense Programs, describes, it’s a mission that is simple to state, but challenging to deliver.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Evaluation of Applied Stress on Atmospheric Corrosion and Pitting Characteristics in 304L Stainless Steel

For this study, the effects of applied stress, ranging from tensile to compressive, on the atmospheric pitting corrosion behavior of 304L stainless steel (SS304L) were analyzed through accelerated atmospheric laboratory exposures and microelectrochemical cell analysis. After exposing the lateral surface of a SS304L four-point bend specimen to artificial seawater at 50°C and 35% relative humidity for 50 d, pitting characteristics were determined using optical profilometry and scanning electron microscopy. The SS304L microstructure was analyzed using electron backscatter diffraction. Additionally, localized electrochemical measurements were performed on a similar, unexposed, SS304L four-point bend bar to determine the effects of applied stress on corrosion susceptibility. Under the applied loads and the environment tested, the observed pitting characteristics showed no correlation with the applied stress (from 250 MPa to -250 MPa). Pitting depth, surface area, roundness, and distribution were found to be independent of location on the sample or applied stress. The lack of correlation between pitting statistics and applied stress was more likely due to the aggressive exposure environment, with a sea salt loading of 4 g/m 2 chloride. The pitting characteristics observed were instead governed by the available cathode current and salt distribution, which are a function of sea salt loading, as well as pre-existing underlying microstructure. In microelectrochemical cell experiments performed in Cl - environments comparable to the atmospheric exposure and in environments containing orders of magnitude lower Cl - concentrations, effects of the applied stress on corrosion susceptibility were only apparent in open-circuit potential in low Cl - concentration solutions. Cl - concentration governed the current density and transpassive dissolution potential.

36 MATERIALS SCIENCE↗

Perspective—Localized Corrosion: Passive Film Breakdown vs Pit Growth Stability

A debate about the critical step in localized corrosion has raged for decades. Some researchers focus on the composition and structure of the passive film associated with the initial breakdown of the film, whereas others consider that the susceptibility to pitting is controlled by the pit growth kinetics and the stabilization of pit growth. The basis for a unified theory of pitting is presented here in which pit stability considerations are controlling under aggressive conditions (harsh electrolytes and extreme environments and/or susceptible microstructures) and the passive film properties and protectiveness are the critical factors in less extreme environments and/or for less susceptible alloys.

36 MATERIALS SCIENCE↗

Correlation Between the Pitting Potential Evolution and σ Phase Precipitation Kinetics in the 2205 Duplex Stainless Steel

The aim of this work is to correlate the pitting potential (E{sub pit}) evolution with the kinetics of σ phase precipitation in the 2205 duplex stainless steel aged at 850 °C after solution treatment at 1150 °C. The potentiodynamic polarization curves indicate a reduction of the pitting corrosion resistance with the aging time, which is revealed by a decrease in the E{sub pit} values from 0.65 to 0.40 V{sub SCE}. Thus, E{sub pit} values are used to determine the kinetics parameters of the σ phase precipitation. The experimental transformed fraction agrees well with the one calculated by using the modified Kolmogorov–Johnson–Mehl–Avrami equation with an impingement parameter c = 0.6.

36 MATERIALS SCIENCE↗

Corrosion and repassivation of Super 13Cr stainless steel in artificial 1D pit electrodes at elevated temperature

Repassivation behavior of Super 13Cr martensitic stainless steel was investigated using a one-dimensional artificial pit electrode in deaerated NaCl solutions at 85 °C. Critical potentials for pit repassivation (E crit ) were measured by downward potential scans. E crit and the final current density (i f ) at the end of the scan can be correlated to the pit repassivation, showing that repassivation is more probable with smaller i f and higher E crit . Pit repassivation at a constant potential was correlated with if and average current density (i avg ). A combination of lower i f and i avg suggests a higher probability for pit repassivation.

36 MATERIALS SCIENCE↗

Efficient screening of rare large pit anomalies on polished surfaces using a minimalist sampling scheme

Lawrence Livermore National Laboratory (LLNL) has made significant strides in generating clean energy through its inertial confinement fusion (ICF) experiments. These experiments rely on high-density carbon (HDC) coated shells to encapsulate the fusion fuel. The success of these experiments is heavily dependent on the surface quality of these shells, as even minor imperfections, such as deep pits, can negatively impact fusion yield. Ensuring the required smoothness involves an extensive surface-finishing process that spans approximately 20 stages, making it both time-intensive and resource-demanding. A critical challenge in this process is the need for high-resolution scans to detect rare deep pits, which can be costly and impractical if performed on every shell. This highlights the necessity of developing more efficient scanning methods to optimize time and cost without compromising accuracy. To address these challenges, we introduce a novel approach that employs the multivariate Dvoretzky–Kiefer–Wolfowitz (DKW) inequality to provide a probabilistic upper bound on the error in estimating pit distribution characteristics via a Kernel Density Estimator (KDE). This error bound enables efficient and reliable estimation of pit distribution characteristics at a specified statistical confidence level using a minimal number of surface scans. The integrated DKW-KDE approach was validated through surface-finishing experiments across two batches of HDC-coated shells, demonstrating consistent and robust performance across multiple stages of the surface-finishing experiments. The validation studies suggest that the integrated DKW-KDE approach achieves comparable accuracy in estimating the risk of deleterious large pits with six scans, thus conserving time and resources. Further evaluations show that performance remains consistent across batches and over multiple polishing stages. In conclusion, based on these findings, one can leverage the minimal-scan insights to strategically improve the bottleneck inspection process, thus enhancing the productivity and quality of shell polishing and similar challenging manufacturing processes.

Inertial confinement fusion↗