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At least 1,639 records · Page 91

Chemical diffusion: Another factor affecting the magnetoresistance ratio in Ta/CoFeB/MgO/CoFeB/Ta magnetic tunnel junction

This letter investigates the microstructure and mean inner potential (MIP) profile of Ta/CoFeB/MgO/CoFeB/Ta magnetic tunnel junctions (MTJs) by high resolution transmission electron microscopy (HRTEM) and electron holography, respectively. The inconspicuous crystallization of MgO barrier is confirmed by HRTEM in the post-annealed sample at 250 Degree-Sign C. An obvious MIP difference is displayed in the Ta layers between the top and bottom of the MTJ, and elemental content difference of them is confirmed by energy dispersive spectroscopy. These results imply that the chemical diffusion can also give rise to a lower tunnel magnetoresistance ratio besides the inconspicuous crystallization of MgO barrier.

36 MATERIALS SCIENCE↗

Three-dimensional plastic response in polycrystalline copper via near-field high-energy X-ray diffraction microscopy

The evolution of the crystallographic orientation field in a polycrystalline sample of copper is mapped in three dimensions as tensile strain is applied. Here, using forward-modeling analysis of high-energy X-ray diffraction microscopy data collected at the Advanced Photon Source, the ability to track intragranular orientation variations is demonstrated on an ~2 µm length scale with ~0.1° orientation precision. Lattice rotations within grains are tracked between states with ~1° precision. Detailed analysis is presented for a sample cross section before and after ~6% strain. The voxel-based (0.625 µm triangular mesh) reconstructed structure is used to calculate kernel-averaged misorientation maps, which exhibit complex patterns. Simulated scattering from the reconstructed orientation field is shown to reproduce complex scattering patterns generated by the defected microstructure. Spatial variation of a goodness-of-fit or confidence metric associated with the optimized orientation field indicates regions of relatively high or low orientational disorder. An alignment procedure is used to match sample cross sections in the different strain states. The data and analysis methods point toward the ability to perform detailed comparisons between polycrystal plasticity computational model predictions and experimental observations of macroscopic volumes of material.

36 MATERIALS SCIENCE↗

Influence of rolling reduction and annealing on recrystallization and grain structure in Ta-2.5W alloys

The microstructural evolution of wrought Tantalum - 2.5 wt% Tungsten (Ta-2.5W) alloys during thermomechanical processing is critical for optimizing their mechanical reliability in demanding applications such as aerospace, chemical processing, and nuclear technology. Despite the widespread use of Ta-W alloys, a comprehensive understanding of how rolling reduction, annealing temperature, and elemental inhomogeneity interact to determine recrystallization behavior and grain refinement remains incomplete. Here, in this study, we systematically investigate the effects of cold rolling and subsequent annealing on the microstructure of Ta-2.5W, with particular attention to grain orientation, stored energy, and elemental banding. Our results demonstrate that higher rolling reduction rates lower the onset and completion temperatures for recrystallization, resulting in finer and more homogeneous grain structures. Electron backscatter diffraction (EBSD) analysis reveals that grains with a 〈111〉 parallel to the plate normal possess higher stored energy and nucleate recrystallization more readily than grains with a 〈001〉 parallel to the plate normal. Elemental mapping shows that tungsten inhomogeneity leads to localized bands of accelerated recrystallization and hardness variation. These findings provide new insights into the mechanisms of microstructure refinement in Ta-2.5W alloys, offering guidance for tailoring processing routes to achieve superior performance in demanding engineering environments.

Annealing↗

Homogeneous carbon doping of magnesium diboride by high-temperature, high-pressure synthesis

We have used high-pressure, high-temperature synthesis at 1500–1700 °C and 10 MPa to create homogeneously C-substituted MgB{sub 2} from a B{sub 4}C + Mg mixture. X-ray diffraction analysis showed large peak-shifts consistent with a decrease in the a lattice parameter for the B{sub 4}C-derived MgB{sub 2} as compared to an undoped sample (0.033–0.037 Å, depending on the sample). Microstructural investigation showed a three-phase mixture in the B{sub 4}C-derived ingots: MgB{sub 2−x}C{sub x} (with 0.178 < x < 0.195), MgB{sub 2}C{sub 2}, and Mg. The carbon concentration determined from the lattice parameter shift (5.95 at. %) matched well with the calorimetrically derived concentration of 5.3–5.8 at. % C. Furthermore, the carbon content measured by electron probe micro-analysis was shown to be 6.2 ± 1.3 at. %. Finally, we performed bulk specific heat measurements to determine the homogeneity of C-doping in the MgB{sub 2}. The width of the T{sub c} distribution for the C-doped MgB{sub 2} was only 3–6 K with a full-width half maximum (FWHM) of 1.4 K, compared to a width of 2.5 K and a FWHM of 0.65 for an undoped sample. The consistency of these three measurements on a large-grained homogeneous material is unambiguously supportive of C-substitution.

36 MATERIALS SCIENCE↗

Microstructural, optical and electrical properties of CdS thin films grown by spray pyrolysis technique as a function of substrate temperature

In this research, nanocrystalline cadmium sulfide thin films were produced by the spray pyrolysis technique on glass substrates. The effects of substrate temperature in the range 400–550 °C on the structural, morphological, optical, and electrical properties of the thin films were investigated. The thin films have been characterized by investigating their X-ray diffraction, field emission scanning electron microscope (FE-SEM), and optical absorption (UV–Vis) measurements. X-ray analysis revealed that thin films were a polycrystalline structure with the hexagonal phase in all cases and by increasing in substrate temperature, crystallite size decreases, and dislocation density increases. The FE-SEM images showed that the surface of the thin films is uniform, homogeneous and without cracks. The average sizes of the grains are at the range of 210–235 nm. The obtained values for optical band gap have been in the range of 2.18–2.41 eV, where the value of optical band gap for the thin films decreases by increasing substrate temperature. The Urbach energies of the thin films increase as the substrate temperature is increased. When substrate temperature increased from 400 to 550 °C, electrical resistivity increased from 531 to 2817 Ω cm, carrier concentration decreased from 15.96 × 10{sup 14} to 3.71 × 10{sup 14} cm{sup −3}, Hall mobility decreased from 7.37 to 5.98 cm{sup 2}/V s. Hall effect analysis indicated that the thin films exhibited n-type conductivity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Nanoscale Phase Separation and Large Refrigerant Capacity in Magnetocaloric Material LaFe 11.5 Si 1.5

Here, ferromagnetic transitions, the magnetocaloric effect, and the atomic-scale microstructure in an annealed bulk material of LaFe 11.5 Si 1.5 were investigated using magnetic measurements, Mössbauer spectroscopy, high-resolution X-ray diffraction analysis, and high-resolution transmission electron microscopy. The results provide evidence of the coexistence of two ferromagnetic phases with different Curie temperatures. The phase with a Curie temperature of 216 K corresponds to a Si-rich phase of a NaZn 13 -type structure with a small lattice volume, whereas the phase with a Curie temperature of 185 K corresponds to a Si-poor phase of a NaZn 13 -type structure with a large lattice volume. This phase coexistence is observed on a nanometer scale and it can account for inverse thermal hysteresis of the ferromagnetic transition in the Si-rich phase during warming. Furthermore, the phase coexistence helps the bulk material achieve a refrigeration capacity of 170 J kg -1 due to a combination of the magnetocaloric effect in each phase. It is determined that the magnetocaloric effect in the Si-rich and the Si-poor phase brings about a maximum of the total entropy change of -3.55 and -6.80 and J kg -1 K -1 at respective Curie temperatures, respectively. Fundamentally, the phase coexistence indicates coloring of Si atoms in the lattice of a NaZn 13 -type structure and can be attributed to nanoscale phase separation of a disordered precursor during annealing of the bulk material. The nanoscale phase separation may occur in other magnetocaloric materials, thus allowing for improvement of their refrigeration capacity.

36 MATERIALS SCIENCE↗

Chaotic behavior of light-assisted physical aging in arsenoselenide glasses

The theory of strange attractors is shown to be adequately applicable for analyzing the kinetics of light-assisted physical aging revealed in structural relaxation of Se-rich As-Se glasses below glass transition. Kinetics of enthalpy losses is used to determine the phase space reconstruction parameters. Observed chaotic behaviour (involving chaos and fractal consideration such as detrended fluctuation analysis, attractor identification using phase space representation, delay coordinates, mutual information, false nearest neighbours, etc.) reconstructed via the TISEAN program package is treated within a microstructure model describing multistage aging behaviour in arsenoselenide glasses. This simulation testifies that photoexposure acts as an initiating factor only at the beginning stage of physical aging, thus facilitating further atomic shrinkage of a glassy backbone.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Quantifying the Impacts of Grain-scale Heterogeneity on Mechanical Response

Driven by the exceedingly high computational demands of simulating mechanical response in complex engineered systems with finely resolved finite element models, there is a critical need to optimally reduce the fidelity of such simulations. The minimum required fidelity is constrained by error tolerances on the simulation results, but error bounds are often impossible to obtain a priori. One such source of error is the variability of material properties within a body due to spatially non-uniform processing conditions and inherent stochasticity in material microstructure. This study seeks to quantify the effects of microstructural heterogeneity on component- and system-scale performance to aid in the choice of an appropriate material model and spatial resolution for finite element analysis.

36 MATERIALS SCIENCE↗

Computer vision models and advanced TEM imaging for microstructures of irradiated AM316 stainless steels

Advancements were made in automating microscopy-based material characterization, particularly in studying irradiation effects on additively manufactured (AM) materials using machine learning (ML) and computer vision (CV). These automation efforts address the challenges of analyzing complex microstructures, accelerating the detection of irradiation-induced defects. Two CV models were developed at Argonne National Laboratory (ANL) to enhance transmission electron microscopy (TEM) analysis of irradiated AM 316 stainless steel. The first model focused on the detection of irradiation-induced dislocation loops, which contribute to material hardening and embrittlement. These loops, categorized as faulted or perfect, were automatically detected and classified using a Mask R-CNN model trained on TEM images from both in-situ and ex-situ ion irradiation experiments. The model achieved high accuracy, with precision, recall, and F1 scores of 0.839, 0.734, and 0.776, respectively, demonstrating its effectiveness in analyzing dislocation loops in irradiated AM materials. The second CV model was developed to analyze the size and wall thickness of dislocation cells in laser powder bed fusion (LPBF) 316 stainless steel. Using a U-Net++ architecture with EfficientNet as the encoder, the model was trained on TEM images to segment and measure cell size and wall thickness.

36 MATERIALS SCIENCE↗

Electronic and transport properties of polycrystalline Ba{sub 8}Ga{sub 15}Ge{sub 31} type I clathrate prepared by SPS method

Samples of germanium Ba{sub 8}Ga{sub 15}Ge{sub 31} clathrate of type I were prepared using standard metallurgy methods. The structure, microstructure and phase composition of the prepared samples were analyzed by powder X-ray diffraction XRD and scanning electron microscope SEM combined with energy dispersive X-ray analysis EDX. Scanning thermoelectric microprobe STMP was used to characterize uniformity of Seebeck coefficient distribution at different stages of the material synthesis in order to optimize the synthesis method. Electrical conductivity, Seebeck coefficient and thermal conductivity were measured in the temperature range 20-450 Degree-Sign C. Based on the measured electrical properties and Hall carrier concentration n=5-9{center_dot}10{sup 20} cm{sup -3} at room temperature, electron effective mass m{sup Low-Asterisk} was estimated to be between 2.1-3 m{sub 0}. Preliminary FP-LAPW DFT calculations were performed for two chosen high symmetry superstructures Ba{sub 8}Ga{sub 16}Ge{sub 30} and Ba{sub 8}Ga{sub 6}Ge{sub 40} by means of WIEN2K package. Additionally topological analysis of total electron density according to Bader's Quantum Theory of Atoms in Molecules was carried out. The energy band gaps were calculated to be 0.3 eV for Ba{sub 8}Ga{sub 16}Ge{sub 30} and 0.38 eV for Ba{sub 8}Ga{sub 6}Ge{sub 40} which was close to the experimental results for Ba{sub 8}Ga{sub 16}Ge{sub 30}. The observed electrical properties were compared with the electronic band structure calculations, showing good qualitative correlation between the measured transport properties and the theoretical predictions. - Graphical abstract: Scanning thermoelectric microprobe STMP was used to investigate uniformity of the prepared polycrystalline Ba{sub 8}Ga{sub 15}Ge{sub 31} clathrate samples at different synthesis stages. Maps and histograms of the Seebeck coefficient distribution (presented in the picture) for Ba{sub 8}Ga{sub 15}Ge{sub 31} ingot after the first synthesis stage showed it is not uniform. The Seebeck coefficient distribution in the ingot was bimodal. The same analysis for the sample after annealing and sintering showed that the Seebeck coefficient distribution is unimodal. Compared to the ingot from I synthesis stage a significant improvement of material uniformity was observed. Highlights: Black-Right-Pointing-Pointer Scanning thermoelectric microprobe STMP measurements show important uniformity change during sample annealing. Black-Right-Pointing-Pointer Calculated band gap E{sub g} values are close to the reported E{sub g}. Black-Right-Pointing-Pointer Ga/Ge ratio change doesn't affect significantly the bonding properties. Black-Right-Pointing-Pointer Band structure calculations show that bond's character agrees with the Zintl concept.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A quantitative study of the structure-activity relationship in hierarchical zeolites using liquid-phase reactions

Micro/meso/macroporous (hierarchical) zeolites show remarkable catalytic performance for reactions involving bulky reactants. However, quantitative assessment of the microstructural characteristics contributing to the observed performance remains elusive. Here, structure–activity relationships are established for a set of micro/mesoporous self-pillared pentasil (SPP) zeolites using two parallel liquid-phase reactions (benzyl alcohol alkylation and self-etherification) based on analysis of mass transport and reaction kinetics. A reaction–diffusion mathematical model is developed that quantitatively assigns the catalytic contributions of the external surface and micropores of SPP zeolites for these reactions. In addition, the effect of the zeolite external surface structure on the corresponding catalytic activity is quantitatively assessed by comparing SPP zeolites (with MFI structure) with MCM-22 (with MWW structure). This work demonstrates that reaction–diffusion modeling allows quantitative description of the catalytic performance of hierarchical zeolites and provides a model reaction to assess nm-sized characteristic diffusion lengths in MFI.

bio-inspired↗

Microstructure of Friction Stir Welded AlSi9Mg Cast with 5083 and 2017A Wrought Aluminum Alloys

Wrought aluminum alloys 5083 and 2017A were each joined with cast aluminum alloy AlSi9Mg through friction stir welding in butt weld configurations. For each material system, the wrought and cast alloy positions, i.e., the advancing side or the retreating side, were exchanged between welding trials. The produced weldments were free from cracks and discontinuities. For each alloy configuration, a well-defined nugget comprised of alternating bands of the welded alloys characterized the microstructure. The degree of mixing, however, strongly depended on which wrought alloy was present and on its position during processing. In all cases, the cast AlSi9Mg alloy dominated the weld center regardless of its position during welding. Electron backscattered diffraction analysis showed that the grain size in both alloys (bands) constituting the nugget was similar and that the majority of grain boundaries exhibited a high angle character (20°-60°). Regardless of the alloy, however, all grains were elongated along the direction of the material plastic flow during welding. A numerical simulation of the joining process visualized the material flow patterns and temperature distribution and helped to rationalize the microstructural observations. The hardness profiles across the weld reflected the microstructure formed during welding and correlated well with the temperature changes predicted by the numerical model. Tensile specimens consistently fractured in the cast alloy near the weld nugget.

36 MATERIALS SCIENCE↗

Microstructures and Microhardness Properties of CMSX-4{sup ®} Additively Fabricated Through Scanning Laser Epitaxy (SLE)

Epitaxial CMSX-4{sup ®} deposition is achieved on CMSX-4{sup ®} substrates through the scanning laser epitaxy (SLE) process. A thorough analysis is performed using various advanced material characterization techniques, namely high-resolution optical microscopy, scanning electron microscopy, energy-dispersive x-ray spectroscopy, x-ray diffraction, and Vickers microhardness measurements, to characterize and compare the quality of the SLE-fabricated CMSX-4{sup ®} deposits to the CMSX-4{sup ®} substrates. The results show that the CMSX-4{sup ®} deposits have smaller primary dendritic arm spacing, finer γ/γ′ size, weaker elemental segregation, and higher microhardness compared to the investment cast CMSX-4{sup ®} substrates. The results presented here demonstrate that CMSX-4{sup ®} is an attractive material for laser-based AM processing and, therefore, can be used in the fabrication of gas turbine hot-section components through AM processing.

36 MATERIALS SCIENCE↗

Microstructural Response of Variably Hydrated Ca-Rich Montmorillonite to Supercritical CO2

We report on ab initio molecular dynamics simulations of Ca-rich montmorillonite systems, in different hydration states in the presence of supercritical CO2. Analysis of the molecular trajectories provides estimates of the relative H2O:CO2 ratio per interspatial cation. The vibrational density of states in direct comparison with dipole moment derived IR spectra for these systems provide unique signatures that can used to follow molecular transformation. In a co-sequestration scenario, these signatures could be used to identify the chemical state and fate of Sulfur compounds. Interpretation of CO2 asymmetric stretch shift is given based on a detailed analysis of scCO2 structure and intermolecular interactions of the intercalated species. Based on our simulations, smectites with higher charge interlayer cations at sub-single to single hydration states should be more efficient in capturing CO2, while maintaining caprock integrity. This research would not have been possible without the support of the office of Fossil Energy, Department of Energy. The computational resources were made available through a user proposal of the EMSL User facility, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

AIMD↗

Regional Subsidence Analysis Through a Multi-Scale Modeling Framework Based on Breakage Mechanics

Although poroelastic models are often used to explain the delay between subsurface fluid depletion and ground subsidence, inelastic compaction involving permanent changes of rock microstructure may exacerbate hydro-mechanical coupling, thus influencing the interpretation of measurements and long-term forecasts. Here, a multi-scale modeling approach is discussed, which accounts for the inherent connection between rock microstructure, hydraulic conductivity, and pore compaction. A constitutive model built within the framework of breakage mechanics is proposed to link the hydraulic conductivity of granular rocks with inelastic deformations and changes in grading caused by injection-depletion cycles at stress levels far from yielding. The proposed model has been incorporated into large-scale simulation frameworks, thus enabling the spatiotemporal mapping of regional subsidence through a hybrid, semi-analytical approach. Numerical results based on this strategy show that the model allows isolating near-field and far-field effects into the computation of land subsidence and can generate forecasts for different modeling scenarios (e.g., elastic and inelastic compaction, constant permeability, and concurrent change of compressibility and permeability). In particular, examples of simulations for the case of the Groningen gas field are discussed, showing the model capabilities to use both field measurements and laboratory tests for the generation of reasonable subsidence maps, without expensive computational costs. Results indicate that ignoring coupled inelastic effects has major consequences on the predicted timescale of subsidence. Specifically, while all the model scenarios produced similar long-term ground settlements, those ignoring breakage-dependent permeability changes result in a variation of the temporal window of residual subsidence of the order of several decades.

58 GEOSCIENCES↗

Multiscale Analysis of Nonlinear Systems Using Computational Topology

Computational Homology in Fluids: M. Schatz, K. Mischaikow. This effort focused on characterizing both the structure and dynamics of complex spatio-temporal flows that arise in thermal convection. Microstructure Characterization: T. Wanner, K. Mischaikow. We extended our previous work on studying the time evolution of patterns associated with phase separation in conserved concentration fields. Probabilistic Homology Validation: W. Kalies, T. Wanner, K. Mischaikow. Our above mentioned work on microstructure characterization is based on numerically studying the homology of certain sublevel sets of a function, whose evolution is described by deterministic or stochastic evolution equations. Computational Homology and Dynamics: W. Kalies, T. Wanner, K. Mischaikow. Topological methods can be used to rigorously describe the dynamics of nonlinear systems. We are approaching this problem from several perspectives and through a variety of systems. Stress Networks in Polycrystals: T. Wanner. Together with E. Fuller (NIST) and D. Saylor (FDA) we have characterized stress networks in polycrystals. This part of the project is aimed at developing homological metrics which can aid in distinguishing not only microstructures, but also derived mechanical response fields. Microstructure-Controlled Drug Release: K. Mischaikow, T. Wanner. This part of the project is concerned with the development of topological metrics in the context of controlled drug delivery systems, such as drug-eluting stents. We are particularly interested in developing metrics which can be used to link the processing stage to the resulting microstructure, and ultimately to the achieved system response in terms of drug release profiles. Microstructure of Fuel Cells: W. Kalies, K. Mischaikow. In collaboration with P. Voorhees (Northwestern Univ.) and M. Gameiro (Rutgers) we have been using our computational homology software to analyze the topological structure of the void, metal and ceramic components of a Solid Oxide Fuel Cell.

97 MATHEMATICS AND COMPUTING↗

Dynamic Scaling Analysis of Accelerated Irradiation Testing on Additive Manufacturing Materials by Positron Annihilation

The timely applications of Additive Manufacturing (AM) materials in nuclear environments require accelerated irradiation tests, mainly ion irradiation to enable rapid prototyping. Low dose ion irradiation would cause sub-nanostructure changes by generation of lattice defects, vacancies, vacancy clusters and voids and void swelling caused by cellular dislocations. Positron Annihilation Lifetime (PAL), a novel technology, sensitive towards sub-nanostructure morphology with high accuracy (about 10-7 vacancy per atom), supported by Transition Electron Microscope (TEM) would be applied to identify the type and total size of the defects. The subsequent PAL measurements and TEM surface studies would be followed by PAL analysis that includes sophisticated trapping model. The PAS results would become an input to dynamic scaling analysis (that predicts radiation effects from low dose studies for high dose effects), which incorporate mean-field theory model. The final effect is an in-depth understanding of the microstructure evolution of AM materials under ion irradiation which can be extrapolated to the studies of neutron irradiation, since ion-irradiation takes less time and do not cause the irradiation hazard. The working hypothesis is that PAL technology, that have excellent sensitivity to low-defect concentration would help to identify ion-induced material damage on the atomic and nano-scale level, which then could be extrapolated to understand the neutron damage better.

accelerated irradiation testing↗