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At least 73 records · Page 4

Mitigation of Cu-Induced Grain Boundary Sensitization in Steel Wire Rods Through a Desensitization Heat Treatment

Steel wire rods are essential for manufacturing high-strength steel tire cords. Yet, the presence of residual copper (Cu) in recycled steel can cause grain-boundary sensitization, embrittlement, and deterioration of the mechanical performance of the final product. This study introduces a desensitization heat treatment step designed to redistribute Cu away from austenite grain boundaries after sensitization occurs. The treatment consists of a 10 min dwell at 1000 °C in a 5%H 2 -Ar reducing atmosphere followed by quench. The temperature and hold time were selected based on diffusion calculations to promote solid-state back diffusion of Cu without altering grain morphology. Experimental validation showed that the dwell step reduced the length of Cu-rich sensitized zones of steel wire rod samples containing 0.21 wt.% Cu by approximately 89% and restored the mechanical properties to nearly 95–98% relative to low-Cu baseline steel (0.01 wt.% Cu). Compared with sensitized and as-obtained samples, these results highlight the effectiveness of the proposed method in improving both the microstructure and tensile performance of recycled steel wire rods, enabling their potential application in tire manufacturing.

copper↗

A compartmentalized model of multiphase chemical kinetics

There are significant challenges in predicting multiphase chemical kinetics due to the complex coupling of reaction and mass transport across a phase boundary (i.e., interface). Here, we describe a framework for predicting multiphase kinetics that embeds the elementary kinetic steps of reaction, solvation, and diffusion into a coarse grain spatial description of two phases. The model is constructed to bridge the short-timescale interfacial dynamics observed in molecular simulations with the longer timescales observed in kinetic experiments. A simple set of governing differential equations is derived, which, when solved numerically or analytically, yield accurate predictions of multiphase kinetics in microdroplets. Although the equations are formulated for gas-liquid reactions, the underlying conceptual framework is general and can be applied to transformations in other two-phase systems (solid-liquid, liquid-liquid, etc.).

Chemical kinetics and dynamics↗

Defect Production and Microstructural Feature Impact for Radiation Damage in Additively Manufactured 316 Stainless Steel

This milestone presents multi-scale modeling research results for additively manufactured 316 stainless steel. A combination of phase field, cluster dynamics, molecular dynamics, and density functional theory with machine learning is used, allowing for predictions of radiation-driven microstructural evolution in additively manufactured 316 stainless steel over a range of temperatures, damage rates, neutron spectra, and microstructures, and supporting the development of combined ion and neutron irradiation for material qualification. Informed by ion irradiation and neutron irradiation results across the Advanced Materials and Manufacturing Technologies program, we investigate the unique aspects of radiation-driven microstructure evolution in additively manufactured 316 stainless steel. In particular, we focus on understanding the impact of carbon concentration (varying, for example, between the 316L and 316H standards) on void formation; radiation-induced segregation at dislocation cells and grain boundaries; and the evolution of dislocation loops and network dislocation populations. We find that the unique characteristics of the additively manufactured microstructures must be accounted for in understanding the evolution of dislocation populations under thermal and irradiation conditions, such as the variation in sink strengths arising due to the variation in dislocation density. We also find that the radiation-induced segregation of Cr and Ni to grain boundaries and cell walls differs due to the differences in their defect sink biases. We also find that increasing the Ni content can slow vacancy diffusion, which may provide a mechanism for the observed reduction in transient swelling rate for austenitic Fe-Cr-Ni alloys with increasing Ni content. In addition, ion irradiations have shown that increasing carbon content in 316 SS results in a larger population of smaller voids, suggesting reduced vacancy diffusion. Our results show that the carbon content of additively manufactured 316 SS has a significant impact on the migration rate of defect clusters. The presence of carbon atoms results in carbon-vacancy trapping, significantly reducing the diffusion rate of vacancies. Carbon atoms may also be trapped near the surface of a void, which may reduce void growth by trapping vacancies that diffuse toward the void.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Morphologies of dealloying corrosion attack at grain boundaries

Dealloying corrosion at grain boundaries severely compromises the performance of polycrystalline materials across a wide variety of technological applications. The impact of this phenomenon depends upon the morphology and rate of intergranular dealloying, which can range from planar to wormhole-like patterns that rapidly advance into the alloy. Using 2D and 3D multi-phase field simulations, we reveal how diverse microstructures result from a fundamental interplay between alloy composition and a grain boundary migration mechanism that alters diffusional pathways of dealloying. Inside intergranular dealloying channels, corrosion product buildup can spawn new channels that branch into grain interiors, such that alloys can be degraded from the inside out. These processes further lead to an atypical coarsening mode assisted by diffusion in the dealloying agent. We summarize a unifying explanation for dealloying morphology selection in polycrystalline alloys, which provides an important step towards their optimization for dealloying corrosion environments.

Corrosion↗

Molecular dynamics study of grain boundaries as defect sinks under irradiation in LiAlO 2 and LiAl 5 O 8

Lithium aluminate ceramics, LiAlO 2 and LiAl 5 O 8 , show promise in nuclear environments due to their excellent radiation tolerance. Molecular dynamics simulations investigate grain boundaries (GB) and their role in defect evolution. Results reveal that GBs act as efficient defect sinks, with Li and Al atoms exhibiting distinct behaviors during displacement cascades. Tritium migration in LiAlO 2 is also studied, showing rapid diffusion and stable configurations with oxygen, corroborated by ab initio simulations from the literature. The calculated tritium diffusion coefficient of 1.33 × 10 - ¹⁴ m²/s aligns with the literature, validating the model. LiAl 5 O 8 demonstrates superior defect healing compared to LiAlO 2 , attributed to enhanced atomic transfer between grains and GBs. These findings reveal key insights into defect dynamics, providing essential insights for their application in tritium-producing burnable absorber rods (TPBARs).

36 MATERIALS SCIENCE↗

Electro-carburization of mild steel through two-step reaction in molten-salt electrolyte

The rapid carburization of mild steel is demonstrated via the electrochemical deposition of solid carbon, followed by thermochemical iron-carbon (Fe-C) reaction using a molten lithium-potassium carbonate (LiKCO 3 ) salt electrolyte and carbon dioxide as the carbon source. Depth-dependent microstructural and compositional changes in the steel are shown to be controlled by the applied cell voltage and reaction temperatures. Reaction temperatures above the Fe-C eutectoid temperature promote faster carburization due to carbon dissolution into austenite. The carbon deposition rate is regulated by the applied cell voltage: At - 2.4 V, carbon deposition occurs much faster than its diffusion into the steel, resulting in the accumulation of a carbon-rich layer exceeding 1 mm, which does not diffuse into the steel. In contrast, at - 1.8 V, all deposited carbon effectively diffuses into the steel, leaving a minimal external deposit. In both cases, carbon ingress forms a carbide-rich surface layer and precipitates additional carbides along the grain boundaries within the steel electrode. This method offers a potential approach to increase the carbon content of mild or low-carbon steel feedstocks, such as scrap or direct reduced iron, for industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chromium-doped uranium dioxide fuels: A review

UO 2 doped with parts per million CR 2 O 3 powder is considered a potential near term accident tolerant fuel candidate. Here, the results of decades of industry and academic research into Cr-doped UO 2 are analyzed and their shortcomings are critiqued. Focusing on the incorporation mechanisms of Cr into the fuel matrix, we explore a mechanistic understanding of the characteristic properties of Cr-doped UO 2 , notably, enhanced fission gas retention attributed to enlarged grain sizes following sintering, along with marginal improvements in the thermophysical properties. The findings of recent X-ray Adsorption Near Edge Spectroscopy studies were compared and put into conversation with historic data regarding the incorporation of Cr in UO 2 . On the basis of defect mechanisms, the case is made for the substitutional incorporation of Cr governing the lattice solubility but not the enhanced U diffusivity. Instead, Cr/CR 2 O 3 redox chemistry in a well-defined oxygen potential explains the differences in the U diffusivity and O/M ratio. The primary mechanism of doping enhanced grain growth is found to be liquid assisted sintering due to a CRO (1) eutectic phase at the grain boundaries. The role of inhomogeneities in Cr concentration in UO 2 at various length scales across the materials microstructure is highlighted and connected to promising experimental and modeling work to fill in the gaps in the current understanding of Cr-doped UO 2 . The review considers both the open scientific questions and engineering applications to illustrate the deep connections between the practice and theory in the design of accident tolerant nuclear fuels. In conclusion, the review ends with an outline of future works that combine meticulous irradiation studies and high resolution experiments with next generation modeling and simulations techniques empowered by machine learning advances to accelerate the fabrication and adoption of Cr-doped UO 2 light water reactors.

Cleveland, Mack Wesley [Massachusetts Inst. of Tec↗

Exploring Local Ionic Motion in Perovskite Solar Cells at Nanoscale through Scanning Thermo-Ionic Microscopy

We investigate the local ionic motion in the absorber layer of perovskite solar cells using scanning thermo-ionic microscopy (STIM). STIM images of perovskite films show higher STIM amplitude at most of the grain boundaries due to higher ionic motion at those regions. The perovskite absorber layer of devices aged under blue (450 nm) light soaking shows higher amplitude in STIM signal compared to controls kept in dark storage. Such enhancement of STIM amplitude upon aging under light implies an increased concentration or diffusivity (or both) of mobile ionic species in stressed devices. Our results demonstrate the utilization of the STIM technique to assess and understand the intrinsic local ionic motion in perovskite absorbers for further advancement in device stability and functionality.

aging↗

Flux Synthesis of A-site Disordered Perovskite La 0.5 M 0.5 TiO 3 (M$=$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Inorganic fillers play an important role in improving the ionic conductivity of solid composite electrolytes (SCEs) for Li-ion batteries. Among inorganic fillers, perovskite-type lithium lanthanum titanate (LLTO) stands out for its high bulk Li + conductivity on the order of 10 -3 S cm -1 at room temperature. According to a literature survey, the optimal LLTO filler should possess the following characteristics: i) a single-crystal structure to minimize grain boundaries; ii) a small particle size to increase the filler/polymer interface area; iii) a 1D morphology for efficient interface channels; and iv) cubic symmetry to facilitate rapid bulk Li + diffusion within the filler. However, the synthesis of single crystal, 1D LLTO nanomaterials with cubic symmetry is challenging. Herein, a flux strategy is developed to synthesize La 0.5 M 0.5 TiO 3 (LMTO, M$=$Li, Na, and K) single-crystal nanorods with an A-site-disordered, cubic perovskite phase. The flux media promotes the oriented growth of nanorods, prevents nanorods from sintering, and provides multiple alkali metal ion doping at M sites to stabilize the cubic phase. SCEs compositing the Li + -conducting LMTO nanorods as fillers and poly[vinylene carbonate- co -lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] matrix exhibit more than twice the conductivity of the neat polymer electrolyte (30.6 vs 14.0 µS cm -1 at 303 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of thermal grooving effects on vortex penetration in vapor-diffused Nb 3 Sn

While Nb 3 Sn theoretically offers better superconducting radio-frequency (RF) cavity performance (Q 0 and E acc ) to Nb at any given temperature, peak RF magnetic fields consistently fall short of the ~400 mT prediction. The relatively rough topography of vapor-diffused Nb 3 Sn is widely conjectured to be one of the factors that limit the attainable performance of Nb 3 Sn-coated Nb cavities prepared via Sn vapor diffusion. Here we investigate the effect of coating duration on the topography of vapor-diffused Nb 3 Sn on Nb and calculate the associated magnetic field enhancement and superheating field suppression factors using atomic force microscopy topographies. It is shown that the thermally grooved grain boundaries are major defects which may contribute to a substantial decrease in the achievable accelerating field. Further, the severity of these grooves increases with total coating duration due to the deepening of thermal grooves during the coating process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Kinetic interplay between chemical short-range order and grain boundaries in NiCoCr alloys under irradiation

Chemical short-range order (CSRO) and grain boundary (GB) engineering are routes to enhance radiation damage tolerance in alloys. Here, we reveal that CSRO and GB interact in a sink-strength-dependent manner under irradiation in NiCoCr. Near a weak sink (Σ3 GB), CSRO reduces defect cluster growth by slowing interstitial diffusion and enhancing vacancy-interstitial recombinations. In contrast, near strong sinks such as Σ5 GBs, CSRO and GB act competitively for interstitial accumulation but synergistically to suppress large stacking-fault tetrahedra growth via enhanced recombination. Such mechanistic duality underscores the need for coordinated control of CSRO stability and GB sink strength to enhance radiation damage tolerance.

36 MATERIALS SCIENCE↗

Bayesian SegNet for Semantic Segmentation with Improved Interpretation of Microstructural Evolution During Irradiation of Materials

Understanding the relationship between the evolution of microstructures of irradiated LiAlO2pellets and tritium diffusion, retention and release could improve predictions of tritium performance. Given expert-labeled segmented images of irradiated and unirradiated pellets, we trained Deep Convolutional Neural Networks to segment images into defect, grain, and boundary classes. Qualitative microstructural information was calculated from these segmented images to facilitate the comparison of unirradiated and irradiated pellets. We tested modifications to improve the sensitivity of the model, including incorporating meta-data into the model and utilizing uncertainty quantification. The predicted segmentation was similar to the expert-labeled segmentation for most methods of microstructural qualification, including pixel proportion, defect area, and defect density. Overall, the high performance metrics for the best models for both irradiated and unirradiated images shows that utilizing neural network models is a viable alternative to expert-labeled images.

Oostrom, Marjolein T.↗

Hydrogen charging and desorption from microstructural viewpoint: A method for deconvoluting hydrogen desorption spectra and unveiling the hydrogen-microstructure interaction

Understanding the interaction of hydrogen with microstructural features in metallic materials is crucial for designing hydrogen-resistant alloys. Although thermal desorption spectroscopy (TDS) is widely used for investigating the hydrogen binding behavior of various microstructural features, its application to face-centered cubic (fcc) metals and alloys that exhibit low hydrogen diffusivity is limited due to the lumped TDS desorption signals. This paper shows that, by coupling a Sofronis–McMeeking type hydrogen transport model with a microstructure-informed finite-element model, TDS data can be deconvoluted to reveal the underlying adsorption–diffusion–desorption processes, hydrogen diffusivity, and trap-binding energies. In conclusion, the austenitic steel SS316L in solution-annealed condition is used as a demonstration material, and we focused on investigating the interaction of deuterium (hydrogen isotope) with grain boundaries, which is difficult to investigate from experiments alone but critical for design of alloys for hydrogen infrastructure.

Finite element simulation, Polycrystalline Microst↗

SEI Formation and Lithium-Ion Electrodeposition Dynamics in Lithium Metal Batteries via First-Principles Kinetic Monte Carlo Modeling

The stabilization and enhanced performance of lithium metal batteries (LMBs) depend on the formation and evolution of the Solid Electrolyte Interphase (SEI) layer as a critical component for regulating the Li metal electrodeposition processes. This study employs a first-principles kinetic Monte Carlo (kMC) model to simulate the SEI formation and Li + electrodeposition processes on a lithium metal anode, integrating both the electrochemical electrolyte reduction reactions and the diffusion events giving place to the SEI aggregation processes during battery charge and discharge processes. The model replicates the competitive interactions between organic and inorganic SEI components, emphasizing the influence of the cycling regime. Results indicate that grain boundaries within the SEI facilitate faster lithium-ion transport compared to crystalline regions, crucial for improving the performance and stability of LMBs. The findings underscore the importance of dynamic SEI modeling for further development of next-generation high-energy-density batteries.

25 ENERGY STORAGE↗

Probing Surface Hydration and Isotope Exchange Kinetics in Proton-Conducting Ceramics Using DRIFTS and EIS

This internship project investigates how water vapor partial pressure (pH2O) affects surface hydration and H/D isotope-exchange kinetics in BaZr0.4Ce0.4Y0.1Yb0.1O3?d (4411) proton-conducting ceramic electrolytes. Diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) is used to monitor surface hydroxyl and deuteroxyl species under controlled humidified atmospheres during gas-switching experiments. These surface kinetic trends are to be correlated with bulk, grain-boundary, and total electrolyte resistance measured by electrochemical impedance spectroscopy (EIS) under matching conditions. The future goals of this study are to clarify the relationship between surface hydration dynamics and proton conduction behavior, improving interpretation of EIS data and guiding the optimization of ceramic electrolytes for energy applications.

08 - HYDROGEN↗

Voltage-Dependent First-Principles Barriers to Li Transport within Li-Ion Battery Solid Electrolyte Interphases

Charging a Li-ion battery requires Li-ion transport between the cathode and the anode. This Li-ion transport is dependent on (among other factors) the electrostatic environment that the ion encounters within the solid electrolyte interphase (SEI), which separates the anode from the surrounding electrolyte. A previous first-principles work has illuminated the reaction barriers through likely atomistic SEI environments but has had difficulty accurately reflecting the larger electrostatic potential landscape that an ion encounters moving through the SEI. In this work, we apply the recently developed quantum continuum approximation (QCA) technique to provide an equilibrium electronic potentiostat for first-principles interface calculations. Using QCA, we calculate the potential barrier for Li-ion transport through LiF, Li 2 O, and Li 2 CO 3 SEIs along with LiF–LiF and LiF–Li 2 O grain boundaries, all paired with Li metal anodes. Here, we demonstrate that the SEI potential barrier is dependent on the electrochemical potentials of the anode in each system. Finally, we use these techniques to estimate the change in the diffusion barrier for a Li ion moving in a LiF SEI as a function of the anode potential. We find that properly accounting for interface and electronic voltage effects significantly lowers reaction barriers compared with previous literature results.

25 ENERGY STORAGE↗

Nanoscale Miscibility in In Situ Polymerized Hybrid Electrolytes Speeds Up Ion Dynamics and Enables Stable Cycling of Li Metal Batteries

While the potential use of copolymerized electrolytes in Li metal batteries is subject to intense investigation, the fundamental understanding of the nanoscale domain formation and its effect on Li + transport is still lacking. In this study, we investigated the correlation between the Li + transport mechanism and the miscibility of monomers in polymer blend electrolytes derived from the in situ copolymerization of methyl methacrylate (MMA) and vinylene carbonate (VC) in the presence of polyethylene glycol dimethyl ether (PEGDME) plasticizer and bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The addition of a polar short chain plasticizer reduced the dynamic and structural heterogeneities of the electrolyte. Small-angle X-ray scattering (SAXS) measurements and coarse-grained molecular dynamics (MD) simulations were used to investigate the nanoscale structure of the electrolytes. The distribution of relaxation times corresponding to the three distinct diffusion mechanisms of the free and interfacial Li + ions at the copolymer/plasticizer and electrolyte/SEI boundaries was analyzed in a broad temperature range to elucidate the Li + transport mechanism. Furthermore, the chemical composition of the SEI and the contribution of a ceramic lithium lanthanum zirconium oxide (LLZO, Li 7 La 3 Zr 2 O 12 ) phase on the interfacial resistance, salt degradation, and SEI stability were studied by X-ray photoelectron spectroscopy (XPS) depth profile analysis and electrochemical testing.

Li metal↗

Quasiaperiodic grain boundary phases of Σ⁢5 tilt grain boundaries in refractory metals

We report ground-state structures and phase transitions in Σ⁢5⁢[001] tilt grain boundaries (GBs) in body-centered-cubic (bcc) refractory metals Nb, Ta, Mo, and W. Σ⁢5 tilt GBs have been extensively investigated over the past several decades, with their ground-state structure—composed of kite-shaped structural units—previously thought to be well understood. By performing a rigorous GB structure search that optimizes the number of atoms in the boundary core, we predict different quasiaperiodic “split kite” phases analogous to those previously found in GBs in face-centered-cubic metals. Furthermore, our results suggest that complex aperiodic phases of GBs appear to be a general phenomenon, as validated through density functional theory calculations. Moreover, the atoms in the split kite phase demonstrate distinct collective diffusion dynamics. Phase-contrast image simulations of split kites show better agreement with experimental observations, offering an alternative explanation for previous microscopy results and motivating future atomically resolved imaging of the GB structure.

Body-centered cubic↗