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At least 37 records · Page 2

Self-driving thin film laboratory: autonomous epitaxial atomic-layer synthesis via real-time computer vision analysis of electron diffraction

Emerging materials science platforms with the ability to make autonomous decisions on the fly are fundamentally changing the outlook and protocols for materials optimization and discovery. Because AI-driven self-navigating schemes can effectively reduce the total number of iterations needed to arrive at the "answer" (i.e. the best stochiometric composition for a desired physical property, optimum materials processing parameters, etc.) by significant margins, they have the potential to revolutionize materials and chemical manufacturing processes at large in research laboratory settings as well as in industrial plants. Here, we demonstrate a successful implementation of real-time closed-loop autonomous navigation of a multi-dimensional materials synthesis parameter space for fabricating phase-pure epitaxial films of a metastable phase of a functional oxide in a combinatorial pulsed laser deposition chamber. Sequential epitaxial growth iterations in search of the optimized recipe to stabilize the desired crystal phase were performed using frame-by-frame quantitative computer vision analysis of reflection high-energy electron diffraction (RHEED) images of the unit-cell level film being deposited. The autonomous scheme regularly resulted in > 30-fold reduction in the number of required experiments compared to a comprehensive mapping of the parameter space. The real-time workflow developed here can be readily extended to a variety of thin film synthesis platforms opening the door for self-driving atomic-level materials design as well as autonomous optimization of semiconductor manufacturing.

36 MATERIALS SCIENCE↗

Structural Complexities in Sodium Ion Conductive Antiperovskite Revealed by Cryogenic Transmission Electron Microscopy

Here we use low-dose cryogenic transmission electron microscopy (cryo-TEM) to investigate the atomic-scale structure of antiperovskite Na 2 NH 2 BH 4 crystals by preserving the room-temperature cubic phase and carefully monitoring the electron dose. Via quantitative analysis of electron beam damage using selected area electron diffraction, we find cryogenic imaging provides 6-fold improvement in beam stability for this solid electrolyte. Cryo-TEM images obtained from flat crystals revealed the presence of a new, long-range-ordered supercell with a cubic phase. The supercell exhibits doubled unit cell dimensions of 9.4 Å × 9.4 Å as compared to the cubic lattice structure revealed by X-ray crystallography of 4.7 Å × 4.7 Å. The comparison between the experimental image and simulated potential map indicates the origin of the supercell is a vacancy ordering of sodium atoms. This work demonstrates the potential of using cryo-TEM imaging to study the atomic-scale structure of air- and electron-beam-sensitive antiperovskite-type solid electrolytes.

36 MATERIALS SCIENCE↗

An orbital strategy for regulating the Jahn–Teller effect

ABSTRACT The Jahn–Teller effect (JTE) arising from lattice–electron coupling is a fascinating phenomenon that profoundly affects important physical properties in a number of transition-metal compounds. Controlling JT distortions and their corresponding electronic structures is highly desirable to tailor the functionalities of materials. Here, we propose a local coordinate strategy to regulate the JTE through quantifying occupancy in the ${{d}_{{{z}^2}}}$ and ${{d}_{{{x}^2} - {{y}^2}}}$ orbitals of Mn and scrutinizing the symmetries of the ligand oxygen atoms in MnO6 octahedra in LiMn2O4 and Li0.5Mn2O4. The effectiveness of such a strategy has been demonstrated by constructing P2-type NaLixMn1–xO2 oxides with different Li/Mn ordering schemes. In addition, this strategy is also tenable for most 3d transition-metal compounds in spinel and perovskite frameworks, indicating the universality of local coordinate strategy and the tunability of the lattice–orbital coupling in transition-metal oxides. This work demonstrates a useful strategy to regulate JT distortion and provides useful guidelines for future design of functional materials with specific physical properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

1D to 2D Transition in Tellurium Observed by 4D Electron Microscopy

A new microwave-enhanced synthesis method for the production of tellurium nanostructures is reported here—with control over products from the 1D regime (sub-5 nm diameter nanowires), to nanoribbons, to the 2D tellurene regime—along with a new methodology for local statistical quantification of the crystallographic parameters of these materials at the nanometer scale. Using a direct electron detector and image-corrected microscope, large and robust 4D scanning transmission electron microscopy datasets for accurate structural analysis are obtained. These datasets allow the adaptation of quantitative techniques originally developed for X-ray diffraction (XRD) refinement analyses to transmission electron microscopy, enabling the first demonstration of sub-picometer accuracy lattice parameter extraction while also obtaining both the size of the coherent crystallite domains and the nanostrain, which is observed to decrease as nanowires transition to tellurene. This new local analysis is commensurate with global powder XRD results, indicating the robustness of both the new synthesis approach and new structural analysis methodology for future scalable production of 2D tellurene and characterization of nanomaterials.

2D materials↗

Lattice Strain Measurement of Core@Shell Electrocatalysts with 4D Scanning Transmission Electron Microscopy Nanobeam Electron Diffraction

Strain engineering enables the direct modification of atomic bonding and is currently an active area of research aimed at improving electrocatalytic activity. However, directly measuring the lattice strain of individual catalyst nanoparticles is challenging, especially at the scale of a single unit cell. In this study, we quantitatively map the strain present in rhodium@platinum (core@shell) nanocube electrocatalysts using conventional aberration-corrected scanning transmission electron microscopy (STEM) and the recently developed technique of 4D-STEM nanobeam electron diffraction. We demonstrate that 4D-STEM combined with data preconditioning allows for quantitative lattice strain mapping with subpicometer precision and without the influence of scan distortions. When combined with multivariate curve resolution, 4D-STEM allows us to distinguish the nanocube core from the shell and to quantify the unit cell size as a function of distance from the core–shell interface. Our results demonstrate that 4D-STEM has significant precision and accuracy advantages in strain metrology of catalyst materials compared to aberration-corrected STEM imaging and is beneficial for extracting information about the evolution of strain in catalyst nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Electron‐Density Distribution of UCl 4 and Its Topology from X‐ray Diffraction

Abstract The chemistry of electrons in actinide complexes and materials is still poorly understood and represents a serious challenge and opportunity for experiment and theory. The study of the electron density distribution of the ground state of such systems through X‐ray diffraction represents a unique opportunity to quantitatively investigate different chemical bonding interactions at once, but was considered “almost impossible” on heavy‐atom systems, until very recently. Here, we present a combined experimental and theoretical investigation of the electron density distribution in UCl_ 4 crystals and comparison with the previously reported spin density distribution from polarized neutron diffraction. All approaches provide a consistent picture in terms of electron and spin density distribution, and chemical bond characterization. More importantly, the synergy between experiments and quantum‐mechanical calculations allows to highlight the remarkable sensitivity of X‐ray diffraction to electrons in materials.

Chemistry↗

Solid State Reduction Driven Synthesis of Mn Containing Multi-principal Component Alloys

In recent years, high entropy alloys (HEAs), also known as multi-principal component alloys (MPCAs) have emerged as a new and exciting class of materials. This paper reports on the solid state reduction synthesis of a series of CoFeNiMn-based MPCA compositions, starting from a mixture of the corresponding oxides. One of the aims of the study was to test whether the degree of reduction of MnO, a highly stable oxide, could be enhanced by tailoring the alloy composition. Specifically, the influence of Ni content was studied because Ni exhibits a significant negative enthalpy of mixing with Mn. High purity precursor powders of Co(OH) 2 , Fe 2 O 3 , MnO 2 , and NiO were milled and mixed using standard ceramic processing methods. Here, the nominal sample compositions (assuming complete oxide reduction) were (CoFeMn) x Ni (1-x) , for x = 0, 0.083, 0.166, and 0.25. The oxide samples were subjected to a series of isothermal reduction anneals in flowing 3 pct H 2 –Ar at 1100 °C. The resulting microstructures were characterized using scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The composition of the resulting MPCAs was determined quantitatively using wavelength dispersive spectroscopy (WDS) in the electron microprobe. The study revealed that for each of the initial oxide compositions studied, it was possible to achieve an MPCA with ~ 25 at. pct Mn. These results were found to be consistent with the predictions of a thermodynamic model whereby a negative enthalpy of mixing (ΔH mix ), combined with a contribution from configurational entropy, can offset a positive free energy of reduction (ΔG red ). The incorporation of vibrational entropy into first principles calculations was found to have a significant effect on the predicted crystal structure of the MPCAs.

36 MATERIALS SCIENCE↗

Characterizing defect structures in AM steel using direct electron detection EBSD

The mechanical properties of additive and traditionally manufactured alloys are largely dependent on the characteristics and distribution of dislocation cell networks that develop during the fabrication process. This work demonstrates the ability to quantitatively characterize these dislocation structures by high angular resolution electron backscatter diffraction analysis using a direct electron detector. The defect structures are characterized in terms of the geometrically necessary dislocation density and the associated Burgers vector and line direction. Furthermore, the results are discussed in terms of potential defect formation mechanisms.

36 MATERIALS SCIENCE↗

Multimodal analysis and characterization of the boehmite layer formed on AA6061 before and after alkaline etching

Low-enriched uranium (LEU) alloyed with 10% Mo (U-10Mo) is being considered as a promising alternative to oxide-based dispersion fuel with high-enriched uranium for use in research reactors. The configuration of this proposed LEU monolithic LEU fuel plate consists of a U-10Mo plate-type fuel foil with a 25 µm zirconium interlayer barrier clad with an aluminum alloy (AA6061). In certain research reactors, the clad AA6061 is coated with a boehmite layer to prevent corrosion. The boehmite layer has a high-pH passivation range, which makes it resistant to oxidation. Boehmite is usually formed on the AA6061 surface by autoclave processing. Before the boehmite layer is added, the surface of the AA6061 is cleaned using techniques such as polishing and wet etching. In this study, we use multimodal analysis to examine how pretreatment of AA6061 using polishing followed by alkaline etching affects the chemical composition of the boehmite layer. X-ray photoelectron microscopy (XPS), transmission electron microscopy (TEM), and x-ray diffraction (XRD) were used to study the chemical changes in the boehmite layer caused by alkaline etching pretreatment. XPS provides quantitative analysis for the Al:O ratio as well as oxidation states present on the surface, which suggests slight oxidation of the boehmite surface after alkaline etching of the AA6061 surface. We further explored this suggested oxidation of the boehmite surface using high-resolution transmission electron microscopy with selected area electron diffraction (SAED) and grazing incidence x-ray diffraction (GI-XRD), which suggested only a small amount of aluminum oxide at the surface. The multimodal analysis and imaging yielded new insights for optimizing boehmite growth on AA6061 for research reactors.

36 MATERIALS SCIENCE↗

Effect of Diel Cycling Temperature, Relative Humidity, and Synthetic Route on the Surface Morphology and Hydrolysis of α -U 3 O 8

The speciation and morphological changes of α-U 3 O 8 following aging under diel cycling temperature and relative humidity (RH) have been examined. This work advances the knowledge of U-oxide hydration as a result of synthetic route and environmental conditions, ultimately giving novel insight into nuclear material provenance. α-U 3 O 8 was synthesized via the washed uranyl peroxide (UO 4 ) and ammonium uranyl carbonate (AUC) synthetic routes to produce unaged starting materials with different morphologies. α-U 3 O 8 from UO 4 is comprised of subrounded particles, while α-U 3 O 8 from AUC contains blocky, porous particles approximately an order of magnitude larger than particles from UO 4 . For aging, a humidity chamber was programmed for continuous daily cycles of 12 “high” hours of 45 °C and 90% RH, and 12 “low” hours of 25 °C and 20% RH. Samples were analyzed at varying intervals of 14, 24, 36, 43, and 54 days. At each aging interval, crystallographic changes were measured via powder X-ray diffraction coupled with whole pattern fitting for quantitative analysis. Morphologic effects were studied via scanning electron microscopy and 12-way classification via machine learning. While all samples were found to have distinguishing morphologic characteristics (93.2% classification accuracy), α-U 3 O 8 from UO 4 had more apparent change with increasing aging time. Nonetheless, α-U 3 O 8 from AUC was found to hydrate more quickly than α-U 3 O 8 from UO 4 , which can likely be attributed to its larger surface area and porous starting material morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

LDRD 22A1059-068FP Tailoring the Properties of Multi-Phase Materials Through the Use of Correlative Microscopy and Machine Learning - Poster

High strength alloys with good ductility, hardness, and toughness are needed to meet stringent design requirements for extreme environments. One complication in this pursuit is the evidence that metals rarely exhibit both high strength and good fracture toughness as the underlying mechanisms work in opposition. An exception to this behavior is found in multiphase alloys that form complex microstructures of mixed phases with variable grain sizes and shapes that provide increased fracture toughness by the arrangement of their constituent elements. We propose to explore this phenomenon using state-of-the-art machine learning (ML) techniques in a new and novel manner to identify and correlate the critical microstructural features in a Titanium-10Vanadium-2Iron-3Aluminum (Ti-10V-2Fe-3Al) alloy that is reported to exhibit high strength and fracture toughness. Additionally, we will employ multiple, complementary characterization techniques such as optical microscopy, electron backscatter diffraction (EBSD), energy dispersive spectroscopy (EDS) and scanning electron microscopy to provide multi-layer, quantitative ground truth measures of the microstructures. This data will be used to train a Convolutional Neural Network (CNN) in a semi-supervised environment to identify key microstructural features such as ? platelet dimensions and locations and ?/? phase boundaries and correlate those features with the strength and toughness. Here the ? and ? nomenclature refers to hexagonal close pack (hcp) and body center cubic (bcc) crystal structures, respectively. Previous work has focused on popular alloys and typically used one characterization technique. This research is focused on a promising titanium alloy, uses multiple complimentary characterization tools to provide precise microstructural information and correlates to improved fracture toughness. The resulting ML tool can be trained for additional microstructural features, different alloy(s), and or target mechanical properties.

36 MATERIALS SCIENCE↗

Path integral molecular dynamics: A high-fidelity approach to quantum dynamics of electrons

We investigate electron transport in the uniform electron gas using ring-polymer molecular dynamics (RPMD). Working in the weakly coupled, non-degenerate regime, we use RPMD to probe how the onset of quantum diffraction effects at high temperature reshapes electron–electron collisions and leads to a classical-to-quantum crossover in macroscopic transport properties. Static thermodynamics obtained with RPMD are consistent with the weak-coupling equation of state, confirming correct quantum Boltzmann sampling. Real-time transport extracted from mean square displacements exhibits the expected ballistic-to-diffusive transition and a systematic reduction of the electronic self-diffusivity as quantum effects strengthen, due to quantum diffraction modifying electron–electron collisions. Direct ring-polymer scattering simulations reveal diffractive “softening” of binary deflections, providing a micro-to-macro link between collision physics and diffusion. The present study establishes RPMD as a quantitative, trajectory-based tool for electron transport across the classical–quantum crossover and furnishes benchmarks for improving Coulomb-log interpolation models. We outline extensions to multi-component plasmas and a path to incorporate Fermi–Dirac statistics within path-integral dynamics.

Electronic transport↗

Ptychography at all wavelengths

Ptychography is a computational imaging technique that operates across multiple wavelength regimes, from electron (picometres) to X-ray (~0.1 nm), extreme ultraviolet (~10 nm) and visible light (micrometres). By reconstructing both amplitude and phase from diffraction patterns, ptychography enables high-resolution, quantitative imaging without conventional limitations imposed by lens-based optics. Ptychography has enabled advances across a range of scales: achieving deep-sub-angstrom resolution with electron microscopy, becoming an indispensable tool at X-ray synchrotron facilities worldwide and overcoming the trade-offs between resolution and field-of-view in optical imaging. This Primer provides a unified treatment of ptychography across these wavelength regimes. First, we discuss theoretical foundations, reconstruction algorithms, experimental considerations and wavelength-specific challenges. We then give examples of raw and processed data from various configurations and wavelengths. Next, we highlight key applications of ptychography in life sciences, materials science and industry. We also discuss data standards, open-source software implementations and best practices for ensuring reproducibility across different wavelength regimes. Finally, we consider limitations and future opportunities for ptychography. Together with accompanying datasets and code implementations, this Primer aims to serve newcomers and experienced practitioners in the field, facilitating broader adoption of ptychography across different disciplines.

47 OTHER INSTRUMENTATION↗

Mudstone Baffles and Barriers in Lower Cretaceous Strata at a Proposed CO 2 Storage Hub in Kemper County, Mississippi, United States

The Cretaceous and Tertiary deposits in Mississippi, Alabama, and the adjacent continental shelf constitute a widespread succession of sandstone, mudstone, and carbonate that has proven to be an important target for geologic CO 2 storage in the onshore Gulf of Mexico basin. Integrated analysis of stratigraphy, sedimentology, and reservoir properties based on cores and geophysical well logs indicates that the Paluxy Formation and Washita- Fredericksburg interval present gigatonne-class storage opportunities. The distribution, geometry, and composition of the area is a direct reflection of the original depositional environments, and understanding these factors is essential for understanding the geologic storage potential of the Paluxy Formation and Washita-Fredericksburg interval at the Kemper County energy facility in Mississippi. Geologic characterization of the Mississippi Embayment at the energy facility focused primarily on characterizing the confinement potential of the storage complex. Integration of core analyses and geophysical well logs has yielded a high-resolution stratigraphic analysis of storage reservoirs, baffles, barriers, and seals. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS), and quantitative X-ray diffraction (XRD) was used to characterize microfabric, pore types, and mineralogy within mudstone of the east-central Mississippi Embayment at the Kemper County energy facility. Mudstone beds in the Paluxy Formation and Washita-Fredericksburg interval have variable thickness and continuity. High water saturation in the Cretaceous mudstone units influences swelling smectite clay and mudrock permeability based on pulse decay analysis is 1–96 nD. These low permeability values indicate that the mudstone units are effective baffles, barriers, and confining intervals that make significant migration of injected CO 2 out of the storage complex unlikely. The numerous baffles and barriers within the target reservoir intervals, moreover, favor the retention of multiple CO 2 in plumes within the abundant stacked sandstone bodies.

03 NATURAL GAS↗

In-situ quantification of the surface roughness for facile fabrications of atomically smooth thin films

Here in this work we present an in-situ technique to quantify the layer-by-layer roughness of thin films and heterostructures by measuring the spectral profile of the reflection high-energy electron diffraction (RHEED). The characteristic features of the diffraction spot, including the vertical to lateral size ratio c/b and the asymmetrical ratio c 1 /c 2 along the vertical direction, are found to be quantitatively dependent on the surface roughness. The quantitative relationships between them are established and discussed for different incident angles of high-energy electrons. As an example, the surface roughnesses of LaCoO 3 films grown at different temperatures are obtained using such an in-situ technique, which are confirmed by the ex-situ atomic force microscopy. Moreover, the in-situ measured layer-by-layer roughness oscillations of two LaCoO 3 films are demonstrated, revealing drastically different information from the intensity oscillations. The experiments assisted with the in-situ technique demonstrate an outstanding high resolution down to similar to ~0.1 Å. Therefore, the new quantitative RHEED technique with real-time feedbacks significantly escalates the thin film synthesis efficiency, especially for achieving atomically smooth surfaces and interfaces. It opens up new prospects for future generations of thin film growth, such as the artificial intelligence-assisted thin film growth.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Development of a silicon carbide ceramic based counter-flow heat exchanger by binder jetting and liquid silicon infiltration for concentrating solar power

A silicon carbide ceramic counter-flow heat exchanger with integrated headers was printed by binder jetting additive manufacturing process. Multiple phenolic binder infiltration cycles (3 or 5) followed by pyrolysis were conducted to increase the net carbon content of the printed SiC specimens. Subsequently, to attain full densification, silicon melt infiltration was used. The microstructure and mechanical properties were comprehensively characterized on the densified material. The chemical compositions and visual distribution of the various regions in the specimens were determined via scanning electron microscopy, while X-ray diffraction and synchrotron µ-computed tomography were used to provide a quantitative assessment of the volume fractions of the identified phase regions. Microhardness measurements showed dependence on the local microstructure. The fracture strength of the material was correlated with the specimen density and agreed with the reported values in the literature. High-temperature exposure at 750 °C for up to 200h did not degrade the strength for the specimens with three phenolic-binder infiltrations; however, the strengths degraded for ones with five phenolic-binder infiltrations. The associated fracture toughnesses of the specimens were ~3.4 MPam 1/2 at room temperature and 750°C, and the thermal conductivities varied from >150 W/mK at room temperature to ~45 W/mK at 750°C. Hence, this study validated the use of the binder-jetting printed SiC ceramic materials for high-temperature heat exchanges. Lastly, we also present in this work the first successful fabrication of a binder-jetting printed one-piece dense SiC ceramic heat exchanger body with unblocked channels that can be used for the flow of heat transfer fluids.

36 MATERIALS SCIENCE↗

Understanding of Active Sites and Interconversion of Pd and PdO during CH 4 Oxidation

Pd-based catalysts are widely used in the oxidation of CH 4 and have a significant impact on global warming. However, understanding their active sites remains controversial, because interconversion between Pd and PdO occurs consecutively during the reaction. Understanding the intrinsic active sites under reaction conditions is critical for developing highly active and selective catalysts. In this study, we demonstrated that partially oxidized palladium (PdO x ) on the surface plays an important role for CH 4 oxidation. Regardless of whether the initial state of Pd corresponds to oxides or metallic clusters, the topmost surface is PdO x , which is formed during CH4 oxidation. A quantitative analysis using CO titration, diffuse reflectance infrared Fourier-transform spectroscopy, X-ray diffraction, and scanning transmission electron microscopy demonstrated that a surface PdO layer was formed on top of the metallic Pd clusters during the CH 4 oxidation reaction. Furthermore, the time-on-stream test of CH 4 oxidation revealed that the presence of the PdO layer on top of the metallic Pd clusters improves the catalytic activity. Our periodic density functional theory (DFT) calculations with a PdO x slab and nanoparticle models aided the elucidation of the structure of the experimental PdO particles, as well as the experimental C-O bands. The DFT results also revealed the formation of a PdO layer on the metallic Pd clusters. This study helps achieve a fundamental understanding of the active sites of Pd and PdO for CH 4 oxidation and provides insights into the development of active and durable Pd-based catalysts through molecular-level design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Residual stress and microstructure in IN718-René41 graded superalloy fabricated by laser blown directed energy deposition

Additively printed Ni-based superalloy with a compositionally graded transition from IN718 to René41 was fabricated by laser blown-powder directed energy deposition (DED/LB-M), with the goals of meeting location-specific temperature capability and reducing component cost for hot gas path turbine components. Residual stress distribution in thin wall specimens with three sets of DED build parameters in the as-built and stress-relieved states was measured by neutron diffraction. For calculating residual stress, the calculated d0 method was found to be more appropriate as stress-free reference than using the lattice spacing measured from the stress-relief heat treated specimens. Longer dwell time (lower interpass temperature), higher energy input, smaller layer thickness resulted in a higher magnitude of tensile residual stresses at edges and compressive residual stresses at center of the specimens. The residual stress results did not show a strong dependence on graded compositions, indicating that the residual stress build-up was more geometry and process dependent. Non-destructive neutron imaging based on the attenuation coefficient qualitatively visualized the compositional variation in the bulk and showed good agreement with quantitative Electron Probe Micro-Analysis (EPMA) measurement. Grain structure, texture, and residual plastic strain along the build direction were characterized by Electron Backscatter Diffraction (EBSD). Long columnar grains with (001) preferred grain orientation were dominant along the build direction. Compositional change did not show an obvious effect on the epitaxial growth of dendrites and the continuation of the columnar grains. Residual plastic strain was relatively low in the as-built specimens.

36 MATERIALS SCIENCE↗