Study and Prediction of Chlorine-Induced Stress Corrosion Cracking
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Localized deformation has emerged as a key factor in the crack initiation process for irradiated steels, as cracks are observed to nucleate preferentially at these sites. Using high resolution electron backscatter diffraction (HREBSD), the local stress tensor surrounding the dislocation channel-grain boundary interaction sites was quantified and coupled with fully determined grain boundary plane orientation information to determine, for the first time, the relationship between grain boundary normal stress and intergranular crack initiation in irradiated austenitic stainless steel. A Fe-13Cr-15Ni alloy was strained in simulated boiling water reactor, normal water chemistry after quantifying the residual stress tensor at discontinuous dislocation channel – grain boundary interaction sites where grain boundaries were determined to be well oriented with respect to the loading axis. Local stresses at the grain boundary were observed to reach magnitudes greater than 1.5 GPa at a distance of 200 nm from the intersection between the dislocation channel and the grain boundary. A pseudo-threshold stress of 0.9 GPa was measured, below which no cracking was observed. As the stress acting normal to the grain boundary increased above this value, the susceptibility to cracking increased with the cracking fraction reaching 100% at the high end of the stress range. This study shows for the first time that not only does intersection between discontinuous dislocation channels and grain boundaries result in peak local stresses, while the magnitude of the local tensile stress drives the crack initiation process.
The influence of the external cathodic area, stress intensity, and electrochemical polarization level on the resultant crack growth rate and crack tip pH and potential was studied for stainless steel 304L in a sodium chloride environment. Before testing, the validity of in situ crack tip property measurements using microprobes and drilled holes was supported through modeling efforts and confirmed with experimental observations. Here, it was found that increasing the R-ratio during corrosion fatigue increased the crack growth rate and decreased the measured crack tip pH of the 304L sample. Decreasing the electrochemical potential (i.e., cathodic polarization) of the bulk sample increased the crack tip pH and stopped measured crack extension under constant K conditions. Conversely, increasing the potential of the bulk sample decreased the crack tip pH and induced cracking under constant K conditions. Decreasing the cathodic area external to the crack increased the measured pH at the crack tip and decreased the crack growth rate under fatigue conditions. For the given configuration, environment, and alloy studied, fatigue crack growth is not sustained by cathodic reactions solely occurring in the crack wake and notch. These results have implications for the ability to predict atmospheric crack growth rates from laboratory, full immersion experiments.
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This letter report presents a probabilistic performance assessment model to evaluate the probability of canister failure (through-wall penetration) by SCC. The model first assesses whether environmental conditions for SCC – the presence of an aqueous film – are present at canister weld locations (where tensile stresses are likely to occur) on the canister surface. Geometry-specific storage system thermal models and weather data sets representative of U.S. spent nuclear fuel (SNF) storage sites are implemented to evaluate location-specific canister surface temperature and relative humidity (RH). As the canister cools and aqueous conditions become possible, the occurrence of corrosion is evaluated. Corrosion is modeled as a two-step process: first, pitting is initiated, and the extent and depth of pitting is a function of the chloride surface load and the environmental conditions (temperature and RH). Second, as corrosion penetration increases, the pit eventually transitions to a SCC crack, with crack initiation becoming more likely with increasing pit depth. Once pits convert to cracks, a crack growth model is implemented. The SCC growth model includes rate dependencies on both temperature and crack tip stress intensity factor, and crack growth only occurs in time steps when aqueous conditions are predicted. The model suggests that SCC is likely to occur over potential SNF interim storage intervals; however, this result is based on many modeling assumptions. Sensitivity analyses provide information on the model assumptions and parameter values that have the greatest impact on predicted storage canister performance, and provide guidance for further research to reduce uncertainties.
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Reaction Dynamics in Energetic Materials: Detonation is a prototype of mechanochemistry, in which mechanically and thermally induced chemical reactions far from equilibrium exhibit vastly different behaviors. It is also one of the hardest multiscale physics problems, in which diverse length and time scales play important roles. The CACS group has performed multimillion-atom reactive MD simulations to reveal a novel two-stage reaction mechanism during the detonation of cyclotrimethylenetrinitramine (RDX) crystal. Rapid production of N2 and H2O within ~10 ps is followed by delayed production of CO molecules within ~ 1 ns. They found that further decomposition towards the final products is inhibited by the formation of large metastable C- and O-rich clusters with fractal geometry. The CACS group has also simulated the oxidation dynamics of close-packed aggregates of aluminum nanoparticles passivated by oxide shells. Their simulation results suggest an unexpectedly active role of the oxide shell as a nanoreactor.
The objective of this work was to obtain SCC growth data in Alloy 152 weld butter near the interface with Low Alloy Steel (LAS), which is a region where some dilution of Cr was expected to have occurred, thus presumably exhibiting an increased SCC-susceptibility vs. the bulk of the weld. The LAS piece used in this application was Alloy 533-Gr B from the Midland reactor lower head, and the Alloy 152 weld butter received a prototypical Post Weld Heat Treatment (PWHT) prior to joining by Alloy 152 to an Alloy 690 piece according to a procedure qualified to ASME IX. The compact tension specimens for SCC testing were aligned in the first layer of the Alloy 152 butter. The experimental approach based on tracking environmental enhancement vs. location was successful in identifying SCC-susceptible locations, and SCC rates ranging from 10-12 m/s to as high as 10-10 m/s were measured. The post-test examination of the specimens found that the fracture had the intergranular/interdendritic appearance typical of welds, and that the propagation was arrested wherever an intersection with the LAS occurred. The large range of SCC rates measured does not appear to correlate well with the local concentration of Cr (approx. 25% at the SCC locations), and, in fact, low Cr (20%) – high Fe “streaks” seemed to slow/arrest crack propagation. In short, simple “Cr dilution” does not seem to fully account for the “SCC-susceptible” microstructure that yielded the 10-10 m/s growth rate in this weld.
Acoustic Emission monitoring is a technique that detects and records phenomena related to the elastic waves generated by the release of strain energy during crack propagation events. The sensors used for this method are highly sensitive and do not typically need to be in relatively close proximity to the indication when compared to methods such as ultrasonic or eddy current testing. This characteristic makes acoustic emission an attractive method for monitoring locations that are not readily accessible to active inspection methods, such as with in-situ examination of dry cask storage system canisters. Acoustic emission is unique among nondestructive evaluation (NDE) methods as emission is caused by the energy released from the object inspected. Most NDE methods require that energy be introduced to the part from an external source; which is not necessary with acoustic emission. Acoustic emission signals are created during crack growth and plastic deformation. EPRI has been investigating the feasibility of using acoustic emission as a complementary NDE method for monitoring the structural condition of dry fuel storage canisters. To assess this feasibility three first of a kind field trials were conducted over a one year period. The goals of the field trials were to determine the potential path forward for the method and to assess needs for further research and development. Why this matters: The study evaluated the efficacy of structural health monitoring methods to support ISFSI license renewal commitments to support aging management of welded stainless steel canisters. (authors)
Several experimental techniques were utilized to understand the corrosion and SCC performance of possible techniques for repairing cracks and pits in SS304 utilized for dry cask storage of spent nuclear fuel. The repairs examined included cold spray, FSW, soldering, and VFAW. The corrosion and SCC assessment techniques utilized for comparing repairs against the base material were 4-pt bending SCC testing in boiling MgCl 2 at stress levels between 0 MPa and 350 MPa, immersion testing in 40% RH brine solution meant to mimic a service-like environment, SSRT SCC testing in 40% RH brine solution. For FSW alone, scanning electrochemical cell microscopy and microelectrochemical syringe cell were utilized to understand the corrosion performance across the weld, in the retreating/advancing sides, and base material. Based on the results of this study, the FSW and cold spray repair techniques proved most viable for SCC repair in SS304 dry cask storage applications and continuing research is highly recommended to understand and quantify in further detail their SCC performance compared to unrepaired SS304. Additionally, solder and VFAW (patch or incline) would not be recommended based on the corrosion and SCC findings in this study.
Oxide phases such as α-Fe2O3 (hematite) and α-Al2O3 (corundum) are highly insoluble in water; however, subcritical crack growth has been observed in humidity nonetheless. Chemically induced bond breaking at the crack tip appears unlikely due to sterically hindered molecular transport. The molecular mechanics of a crack in corundum with a reactive force field reveal minimal lattice trapping, leading to bond breaking before sufficient space opens for water transport. To address this, we model a pre-built blunt crack with space for H2O molecule adsorption at the tip and show that it reduces fracture toughness by lowering the critical J-integral. Then, we explore stress-enhanced dissolution to understand the mechanism of crack tip blunting in the oxide/water system. Density functional theory combined with metadynamics was employed to describe atomic dissolution from flat hematite and corundum surfaces in pure water. Strain accelerates dissolution, stabilizing intermediate states with broken bonds before full atom detachment, while the free energy profile of unstrained surfaces is almost monotonic. The atomistic calculations provided input for a kinetic model, predicting the shape evolution of a blunt crack tip, which displays three distinct regimes: (i) dissolution primarily away from the tip, (ii) enhanced blunting near but not at the apex, and (iii) sharpening near the apex. The transition between regimes occurs at a low strain, highlighting the critical role of water in the subcritical crack growth of oxide scales, with dissolution as the fundamental microscopic mechanism behind this process.
The objective of this project, which includes close collaboration with scientists from INL and ANL, is to investigate and demonstrate the use of advanced mechanical surface treatments like laser shock peening (LSP) and ultrasonic nanocrystal surface modification (UNSM) and establish baseline parameters for enhancing the fatigue properties and SCC resistance of nuclear materials like nickel-based alloy 600 and 304 stainless steel. The research program includes the following key elements/tasks: 1) Procurement of Alloy 600 and 304 SS, heat treatment studies; 2) LSP and UNSM processing of base metal and welds/HAZ of alloys 600 and 304; (3) measurement and mapping of surface and sub-surface residual strains/stresses and microstructural changes as a function of process parameters using novel methods; (4) determination of thermal relaxation of residual stresses (macro and micro) and microstructure evolution with time at high temperatures typical of service conditions and modeling of the kinetics of relaxation; (5) evaluation of the effects of residual stress, near surface microstructure and temperature on SCC and fatigue resistance and associated microstructural mechanisms; and (6) studies of the effects of bulk and surface grain boundary engineering on improvements in the SCC resistance and associated microstructural and cracking mechanisms
A number of major accomplishments resulted from the project. These include: • Data Structures, Algorithms, and Numerical Methods for Reactive Molecular Dynamics. We have developed a range of novel data structures, algorithms, and solvers (amortized ILU, Spike) for use with ReaxFF and charge equilibration. • Parallel Formulations of ReactiveMD (Purdue ReactiveMolecular Dynamics Package, PuReMD, PuReMD-GPU, and PG-PuReMD) for Messaging, GPU, and GPU Cluster Platforms. We have developed efficient serial, parallel (MPI), GPU (Cuda), and GPU Cluster (MPI/Cuda) implementations. Our implementations have been demonstrated to be significantly better than the state of the art, both in terms of performance and scalability. • Comprehensive Validation in the Context of Diverse Applications. We have demonstrated the use of our software in diverse systems, including silica-water, silicon-germanium nanorods, and as part of other projects, extended it to applications ranging from explosives (RDX) to lipid bilayers (biomembranes under oxidative stress). • Open Source Software Packages for Reactive Molecular Dynamics. All versions of our soft- ware have been released over the public domain. There are over 100 major research groups worldwide using our software. • Implementation into the Department of Energy LAMMPS Software Package. We have also integrated our software into the Department of Energy LAMMPS software package.
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