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At least 487 records · Page 27

First Principle based Thermal Conductivity Modeling of Metal Alloys with Applications on Uranium Alloys

Thermal conductivity is an important materials property related to heat transport, which is essential to many applications, ranging from thermoelectrics to nuclear reactor materials. High- quality thermal conductivity data is critical to these materials and their associated technologies, including the nuclear fuel materials like traditional oxide fuels and metallic uranium (U) fuels, e.g. U-Zr and U-Mo alloys. And thermal conductivity modeling is widely used to interpolate or extrapolate experimental data, to obtain high-quality thermal conductivity data over wide temperature and composition range, and to understand the impacts of different factors including defects and microstructures. However, a general thermal conductivity model for metal alloys which can work regrading different phase components is still missing. Also, for U alloys, a thermal conductivity model working with different phases is needed. Therefore, in this work, we developed thermal conductivity models for metal alloys, based on ab-initio calculations, semi-classical physics rules, and limited experimental data. The goals of these models are to help obtain high- quality thermal conductivity data within a little experimental input as possible, have models that are extendable to varying microstructures, including different types of irradiation effects, and provide mechanistic understanding of heat transfer in the modeled alloys. In this work, our model solves several challenges in the development. The DFT-BTE approach is applied to decrease the reliance on experimental data and make the model extendable to composition changes and defects. A practical and efficient way to combine the DFT inputs with physics rules is pointed out in this work too. A staged approach, which starts from simple cases of elemental metals, then extends to solid solutions, different compound phases, and multi-phase mixtures, is presented to work with the metal alloys in different phase components. Our models are demonstrated respectively on aU for elemental metal model, on U-Zr and U-Mo alloys in aU temperature range for multi-phase mixture model, on high-temperature U-Zr, U-Nb, and U-Mo alloys in the body-centered cubic phase for concentrated solid solution model, and on irradiated U-Mo alloys for irradiated metal alloy model. All models show great agreement with experimental data. In these demonstrations, our model shows its advantages compared to previous empirical fitting model. Our model requires fewer experimental data, due to the inputs from DFT. The quantitative insights into the different physical factors are provided in our model, as it incorporates the electron and phonon scattering mechanisms. Our model also can be extended to incorporate the contributions of point defects, grain boundaries, and noble gas bubbles, to integrate their effects on heat transfer. This model can serve as both a foundation for understanding the more complex thermal conductivity of realistic U alloy fuels and a useful tool to guide further modeling of thermal conductivity to aid materials and device design.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermal transport in phase-stabilized lithium zirconate phosphates

The thermal properties of yttrium-stabilized lithium zirconate phosphate [LZP: Li 1+x+y Y x Zr 2-x (PO 4 ) 3 with x = 0.15, -0.2 ≤ y ≤ 0.4 and with x = 0.0, y = 0.0] are presented over a wide temperature range from 30 to 973 K, elucidating the interplay between structural phase transformations and thermal properties in a solid state superionic conducting material. At room temperature, the thermal conductivity decreases by more than 75% as the stoichiometry is changed from lithium deficient to excess and increases with increasing temperature, indicative of defect-mediated transport in the spark plasma sintered materials. The phase transformations and their stabilities are examined by x-ray diffraction and differential scanning calorimetry and indicate that the Y3 + substitution of Zr 4+ is effective in stabilizing the ionically conductive rhombohedral phase over the entire temperature range measured, the mechanism of which is found through ab initio theoretical calculations. Finally, these insights into thermal transport of LZP superionic conductors are valuable as they may be generally applicable for predicting material stability and thermal management in the ceramic electrolyte of future all-solid-state-battery devices.

36 MATERIALS SCIENCE↗

Spectro-Microscopic Analysis of Soot Particle Composition and Source Attribution

Ambient soot particles significantly impact Earth’s radiative balance, human health, and atmospheric visibility. Their microstructural properties depend on formation and aging mechanisms, which vary by emission source and atmospheric processes. Hence, accurately identifying sources of soot enhances our understanding of their physicochemical properties and atmospheric implications. This study used a multi-modal approach to characterize and attribute sources of submicron soot particles collected in Israel during new particle formation events, biomass burning episodes, and background atmospheric conditions. Synchrotron-based X-ray microscopy was used to map soot (elemental carbon), organic carbon, and inorganic species. Implemented atomic force microscopy showed highly diverse phase states, with soot consistently exhibiting a solid-like phase. Automated µ-Raman analysis was subsequently performed on ~690 particles, identifying three soot classes based on spectral features corresponding to the "Defect" (D) and "Graphite" (G) bands of soot. We applied two-peak and five-peak fitting approaches to deconvolute the “Defect” peaks (D1, D2, D3, and D4) and G band from average Raman, revealing varying degrees of graphitic order. The degree of graphitic order was determined from metrics such as the D3 peak area, often observed when soot was internally mixed with organic material. Raman spectral features, along with temporal variations in particle classes contributions, suggest that Particle Type 1 corresponds to traffic related soot and Particle Type 2 to less graphitic soot from biomass burning, while Particle Type 3 is associated with more heterogeneous particulate representative of soot-OC mixtures emitted during new particle formation and biomass burning episodes.

Rivera-Adorno, Felipe (ORCID:0000000273557999)↗

First-Principles Understanding of Optical Excitations within Low-Dimensional Materials

The objective of this project is to utilize first-principles computational approaches to understand optical excitations within two-dimensional monolayers and heterostructures, with the ultimate goal of designing new materials by modifying the chemical and physical structure on the nanoscale. In 2D heterostructures, the nature and movement of the exciton is determined to a large extent by the electron-electron and electron-phonon strengths within individual monolayers, as well as the coupling between layers, all of which in turn depend on chemistry, solid-state screening properties, and quantum confinement. Controlling the nature and migration properties of excitons requires an understanding of the complex relationship between electrons, phonons, defects, disorder, and dynamics. The aim of this project is to determine, by analysis of highly accurate density functional theory (DFT) and many-body perturbation theory (MBPT) calculations, how these complexities can be decomposed into simple, tunable parameters. The specific goals of this project are to 1) understand electron conductivity, absorption and transparency of monolayer semiconductors and metals; 2) develop a theory of excitons near defects in low dimensions; and 3) understand the influence of inter-layer interactions in heterostructures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ultrasonic Inspection Of Thick Sections

Ultrasonics used to inspect large, relatively thick vessels for hidden defects. Report based on experiments in through-the-thickness transmission of ultrasonic waves in both steel and filament-wound composite cases of solid-fuel rocket motors.

Friant, C. L.↗

Telecom-Luminescent and Room Temperature Coherent Tetrathiafulvalene-Based Qubits in Spin-Rich Solids

One of the main challenges facing quantum information science (QIS) is the development of robust qubits that can be op-erated under ambient conditions. Current state-of-the-art anionic nitrogen vacancy center (NV–) defect qubits are robust enough to be operated at room temperature but lack scalability and tunability. These are areas where molecular qubits excel, although they typically suffer from poor air stability and fast decoherence at elevated temperatures and in magneti-cally noisy environments. Organic-based systems offer advantages to this end, although examples retaining room tem-perature coherence are still rare. Furthermore, most organic-based systems lack optical transitions similar to NV– centers that could allow for optical initialization and readout. Here we report two new organic-based qubit candidates that demonstrate room temperature coherence in nuclear and electron spin-rich environments. These qubits luminesce far into the near-infrared (NIR, 700-1700 nm) and telecom (~1260-1625 nm) regions, ideal for biological sensing and com-munications applications, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Lithium dendrite intrusion in solid-state batteries limits fast charging and causes short-circuiting, yet the underlying regulating mechanisms are not well-understood. Here, in this work, we discover that heterogeneous Ag + doping dramatically affects lithium intrusion into Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 (LLZO), a brittle solid electrolyte. Nanoscale Ag + doping is achieved by thermally annealing a 3-nm-thick metallic coating on LLZO, inducing Ag–Li ion exchange and Ag diffusion into grains and grain boundaries. Density functional theory calculations and experimental characterization show negligible impact on the electronic properties and surface wettability from Ag + incorporation. Mechanically, nanoindentation experiments show a fivefold increase in the mechanical force required to fracture the surface Ag + -doped LLZO, indicating substantial doping-induced surface toughening. Operando microprobe scanning electron microscopy experiments show that the Ag + -doped LLZO surface exhibits improved lithium plating at >250 mA cm −2 and an electroplating diameter that is expanded by over fourfold, even under an extreme indentation stress of 3 GPa. This demonstrates enhanced defect tolerance in LLZO, rather than electronic or adhesion effects. Our study reveals a chemo-mechanical mechanism via surface heterogeneous doping, complementing present bulk design rules to minimize mechanical failures in solid-state batteries.

36 MATERIALS SCIENCE↗

Thermodynamics-guided alloy and process design for additive manufacturing

In conventional processing, metals go through multiple manufacturing steps including casting, plastic deformation, and heat treatment to achieve the desired property. In additive manufacturing (AM) the same target must be reached in one fabrication process, involving solidification and cyclic remelting. The thermodynamic and kinetic differences between the solid and liquid phases lead to constitutional undercooling, local variations in the solidification interval, and unexpected precipitation of secondary phases. These features may cause many undesired defects, one of which is the so-called hot cracking. The response of the thermodynamic and kinetic nature of these phenomena to high cooling rates provides access to the knowledge-based and tailored design of alloys for AM. Here, we illustrate such an approach by solving the hot cracking problem, using the commercially important IN738LC superalloy as a model material. The same approach could also be applied to adapt other hot-cracking susceptible alloy systems for AM.

36 MATERIALS SCIENCE↗

Growth of mercuric iodide (HgI2) for nuclear radiation detectors

Mercuric iodide is a material used for the fabrication of the sensing element in solid state X-ray and gamma ray detecting instruments. The operation of the devices is determined to a large degree by the density of structural defects in the single crystalline material used in the sensing element. Since there were strong indications that the quality of the material was degraded by the effects of gravity during the growth process, a research and engineering program was initiated to grow one or more crystals of mercuric iodide in the reduced gravity environment of space. A special furnace assembly was designed which could be accommodated in a Spacelab rack, and at the same time made it possible to use the same growth procedures and controls used when growing a crystal on the ground. The space crystal, after the flight, was subjected to the same evaluation methods used for earth-grown crystals, so that comparisons could be made.

Vandenberg, L.↗

Unraveling the Material Processing Conditions for Optimizing FSW Process

In friction stir welding (FSW), a rotating threaded pin tool is inserted into a weld seam and literally stirs the edges of the seam together. This environmentally friendly, solid-state technique has been successfully used in the joining of materials that are difficult to fusion weld. To determine optimal processing parameters for producing a defect free weld a better understanding of the resulting metal deformation flow path and velocity is required. In this study the metal flow fields are marked by the use of thin (0.001? tungsten) wires embedded in the weld seam at various locations. X-ray radiographs record the position and segmentation of the wire and are used to elucidate the flow field. Microstructures observed in a FSW cross-section in an aluminum alloy are related to their respective strain-strain rate-temperature histories along their respective flow trajectories. Two kinds of trajectories, each subjecting the weld metal to a distinct thermomechanical process and imparting a distinct microstructure, can be differentiated within the weld structure.

Schneider, Judy↗

Quantifying the Material Processing Conditions for an Optimized FSW Process

In friction stir welding (FSW), a rotating threaded pin tool is inserted into a weld seam and literally stirs the edgs of the seam together. This environmentally friendly, solid-state technique has been successfully used in the joining of materials that are difficult to fusion weld. To determine optimal processing parameters for producing a defect free weld, a better understanding of the resulting metal deformation flow path and velocity is required. In this study the metal flow fields are marked by the use of thin (0.001 in. tungsten) wires embedded in the weld seam at various locations. X-ray radiographs record the position and segmentation of the wire and are used to elucidate the flow field. Microstructures observed in a FSW cross-section in an aluminum alloy are related to their respective strain-strain rate-temperature histones along their respective flow trajectories. Two kinds of trajectories, each subjecting the weld metal to a distinct thermomechanical process and imparting a distinct microstructure, can be differentiated within the weld structure.

Schneider, Judy↗

Al 2 O 3 Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

Among the many emerging technologies under investigation as alternatives to the successful Lithium-ion battery, the magnesium battery is promising due to the wide availability of magnesium, its high volumetric capacity, and the possibility for safety improvements. One of the largest challenges facing rechargeable magnesium batteries is the formation of a passivation layer at the Mg metal anode interface when reactive species in the electrolyte are reduced at the electrode-electrolyte interface. To control the solid electrolyte interphase in Lithium batteries, protective layers called artificial solid electrolyte interphase (ASEI) layers have been successful in improving Li metal anode performance. The approach of protecting Mg metal anodes from electrolyte degradation has been demonstrated by fewer studies in the literature than Li systems. In this work, we discuss the properties of Al 2 O 3 thin films deposited using atomic layer deposition as an artificial solid electrolyte interphase at the Mg anode. Our results demonstrate that Al 2 O 3 does prevent electrolyte degradation due to the reductive nature of Mg. However, undesirable properties such as defects and layer breakdown lead to Mg growth that causes soft-shorting. The soft-shorting occurs with and without the protection layer, indicating the ALD layer does not prevent it and hinders Al 2 O 3 from being an ideal candidate for a protection layer. Crucial effects of this layer on Mg electrochemistry at the interface were observed, including growth of Mg deposits leading to soft-shorting of the cell whose morphology showed a dependence on the Al 2 O 3 layer. These results may provide guidelines for the future design and development of protective ASEI layers for Mg anodes.

25 ENERGY STORAGE↗

Mitigating Electronic Conduction in Ceria‐Based Electrolytes via External Structure Design

Doped ceria electrolytes are the state of the art low‐temperature solid oxide electrolytes because of their high ionic conductivity and good material compatibility. However, cerium tends to reduce once exposed to reducing environments, leading to an increase in electronic conduction and a decrease in efficiency. Here, the leakage current is mitigated in ceria‐based electrolytes by controlling the defect chemistry through an engineered cathode side microstructure. This functional layer effectively addresses the problematic electronic conduction issue in ceria‐based electrolytes without adding significant ohmic resistance and increases the ionic transference number to over 0.93 in a thin 20 µm ceria‐based electrolyte at 500 °C, compared to a of 0.8 for an unmodified one. Based on this design, solid oxide fuel cells (SOFCs) are further demonstrated with the remarkable peak power density of 550 mW at 500 °C and excellent stability for over 2000 h. This approach enables a potential breakthrough in the development of ceria‐based low‐temperature solid oxide electrolytes.

36 MATERIALS SCIENCE↗

Role of Wadsley Defects and Cation Disorder to Enhance MoNb 12 O 33 Diffusion

Wadsley-Roth (WR) niobates have emerged as high-rate anode materials that can combine rapid ionic diffusion with good electronic conductivity. WR compounds have been defect-enhanced by limited annealing, however, such materials often contain multiple types of defects. In particular, both Wadsley defects (variable block size) and transition metal disorder have the potential to modify transport rates, however the corresponding effects are not well understood mechanistically. Here, MoNb 12 O 33 (MNO) was calcined at two different temperatures to compare a defect-rich condition (MNO-800) with a proximal order-rich condition (MNO-900) as assessed through XRD, XANES, EXAFS, and STEM characterizations. Galvanostatically cycled lithium half cells of MNO-800 exhibited additional capacity (307 mAhg −1 at 0.1C, 4.66% higher) and improved high-rate capacity of 200 mAhg −1 at 10C. ICI-based overpotential analysis identified solid state diffusion as the dominant rate limiting process where MNO-800 correspondingly exhibited ∼3X faster capacity-weighted diffusivity. A machine-learning interatomic potential was trained to density functional theory and then applied with molecular dynamics (MLIP-MD) to examine the possible roles of Wadsley defects and transition metal disorder. For both defect-types, Li was found to populate and activate fast diffusion paths from window sites at lower extents of lithiation as compared to the order-rich model.

defect↗

Size dependent lattice pseudosymmetry for frustrated decahedral nanoparticles

Geometric frustration—where geometry prevents simultaneous satisfaction of local interactions—generates pseudosymmetry and emergent behaviors across physical and biological systems. At the nanoscale, pseudosymmetric features in crystalline materials manifest as local strain and distortion, but how they depend on particle size and control structural stability remains unclear. Here, we report the first study of a size-dependent crossover in pseudosymmetry in multi-twinned gold nanoparticles (NPs), combining four-dimensional scanning transmission electron microscopy with nanoscale strain mapping grounded in continuum solid mechanics. Analysis of more than 20 decahedral NPs (20–55 nm) reveals pronounced heterogeneity in multiple modes of in-plane strain and displacement field in small NPs as five tetrahedral grains close the geometric gap, without extended defects. With increasing particle size, strain fields homogenize across grains and local phases shift from predominantly low-symmetry body-centered tetragonal motifs at small sizes to face-centered cubic character approaching the bulk limit. We identify a crossover particle size of ~35 nm, well below bulk, correlating with a transition from modified-Wulff shapes to pentagonal bipyramids, consistent with finite element predictions. This quantitative framework for mapping size-dependent strain and pseudosymmetry enables precise design and control of functional crystalline solids and phase transformation for catalysis, photonics, electronics, and energy storage.

Lin, Oliver [University of Illinois at Urbana-Cham↗

Bulk Crystal Growth of Piezoelectric PMN-PT Crystals Using Gradient Freeze Technique for Improved SHM Sensors

There has been a growing interest in recent years in lead based perovskite ferroelectric and relaxor ferroelectric solid solutions because of their excellent dielectric, piezoelectric and electrostrictive properties that make them very attractive for various sensing, actuating and structural health monitoring (SHM) applications. We are interested in the development of highly sensitive and efficient PMN-PT sensors based on large single crystals for the structural health monitoring of composite materials that may be used in future spacecrafts. Highly sensitive sensors are needed for detection of defects in these materials because they often tend to fail by distributed and interacting damage modes and much of the damage occurs beneath the top surface of the laminate and not detectable by visual inspection. Research is being carried out for various combinations of solid solutions for PMN-PT piezoelectric materials and bigger size crystals are being sought for improved sensor applications. Single crystals of this material are of interest for sensor applications because of their high piezoelectric coefficient (d33 greater than 1700 pC/N) and electromechanical coefficients (k33 greater than 0.90). For comparison, the commonly used piezoelectric ceramic lead zirconate titanate (PZT) has a d33 of about 600 pC/N and electromechanical coefficients k33 of about 0.75. At the present time, these piezoelectric relaxor crystals are grown by high temperature flux growth method and the size of these crystals are rather small (~3x4x5 mm(exp 3). In the present paper, we have attempted to grow bulk single crystals of PMN-PT in a 2 inch diameter platinum crucible and successfully grown a large size crystal of 67%PMN-33%PT using the vertical gradient freeze technique with no flux. Piezoelectric properties of the grown crystals are investigated. PMN-PT plates show excellent piezoelectric properties. Samples were poled under an applied electric field of 5 kV/cm. Dielectric properties at a frequency of 1 kHz are examined. The grown PMN-PT crystals show typical relaxor dielectric properties. Additionally, the thermal properties of the sample are tested. The results are in good agreement with those found in the literature and some are reported for the first time.

Aggarwal, Mohan D.↗

Revealing Possible Coherence Limiting Sources in Superconducting Qubit with Advanced Electron Microscopy

Superconducting materials hold great potential for solid-state quantum computing. Their fabrication relies on established semiconductor fabrication techniques, such as thin film deposition and lithography, but the complex processing steps can result in defects at the qubits' interfaces and surfaces that can negatively impact coherence time. To improve superconducting qubit performance, it is essential to understand the structural features, at the atomic scale, that may act as sources of decoherence limiting factor in both the Josephson junction (JJ) and resonators, which are key components of superconducting qubit. This talk will present our recent studies on the microstructures in a 2D-transmon, with an emphasis on the JJ. For this research, a combination of advanced microscopy techniques, including high-resolution (S)TEM imaging, and spectroscopy (EDS and EELS) are used to identify possible coherence-limiting defects or structural features.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ternary Nitride Materials: Fundamentals and Emerging Device Applications

Interest in inorganic ternary nitride materials has grown rapidly over the past few decades, as their diverse chemistries and structures make them appealing for a variety of applications. Due to synthetic challenges posed by the stability of N 2 , the number of predicted nitride compounds dwarfs the number that have been synthesized, offering a breadth of opportunity for exploration. This review summarizes the fundamental properties and structural chemistry of ternary nitrides, leveraging metastability and the impact of nitrogen chemical potential. A discussion of prevalent defects, both detrimental and beneficial, is followed by a survey of synthesis techniques and their interplay with metastability. Throughout the review, we highlight applications (such as solid-state lighting, electrochemical energy storage, and electronic devices) in which ternary nitrides show particular promise.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗