Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Heterogeneous materials”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,189 records · Page 66

Using block-copolymer nanolithography as a tool to sensitively evaluate variation in chemical dry etching rates of semiconductor materials with sub-5 nm resolution

Ion implantation is a robust and established method to customize the electronic properties of Si. However, fabricating doped, ultrafine semiconductor nanostructures can be challenging. Ion implantation has well-established effects on the dry etch rates of Si, which becomes increasingly consequential as the target dimension shrinks below a few tens of nanometers. While dry etching arrays of block copolymer-templated nanoscale holes (pitch = 37.5 nm, diameter ~25 nm) into p-type, n-type, and undoped Si, we observed that the lateral etch rate was notably larger for the n-type regions than p-type or undoped regions. By doing image analyses on high resolution electron micrographs of the nanostructured hole arrays, we were able to extract the porosity and average radii of the holes with subnanometer sensitivity and compare the relative etch rates between different doping conditions. We found that degenerately doped n-type silicon consistently etches between approximately 17% and 27% faster in the lateral direction than p-type Si, resulting in significantly larger porosity and, consequently, less mechanical stability. Here, we demonstrate that top-down dimensional analysis of a densely packed porous nanostructure is a robust method for assessing extremely small differences in the lateral, chemical etch rate of doped Si to a degree of sensitivity that was previously unachievable. The minute, dense-packed nature of block copolymer self-assembled nanostructures is shown to be ideal for this application. This proposed method could be useful for designing fabrication processes for heterogeneous nanostructures, as slight dry etch rate variations that may be within process tolerance at the micrometer-scale appear to have nontrivial consequences at the nanometer scale.

42 ENGINEERING↗

Modeling diffusion and types I-V sorption of water vapor in heterogeneous systems

Here, a sorption and diffusion model is developed using a mobile-immobile decomposition of the vapor concentration. Henry’s mode represents the mobile species which diffuses through the solid, while Langmuir and pooling modes represent possible immobilization processes that cause nonlinearities in sorption capacity. The model can simulate the five classical sorption types and can incorporate additional dynamics compared to models based on thermodynamic equilibrium. Additionally, the framework allows for discontinuities in material properties encountered in multi-material systems. The resulting non-linear coupled equations are solved by employing a finite element method to discretize in space, and a backward Euler method to discretize in time. The discretized system of equations is solved via a Newton-type iteration scheme at each time-step. Four different materials are parameterized for the model, which are then used in examples to demonstrate the model’s ability to capture complex sorption processes in multi-material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A predictive strain-gradient model with no undetermined constants or length scales

A general meso–scale (GM) crystal plasticity (CP) model was developed that accounts for lower-order (strain hardening) and higher-order (internal stress) effects of geometrically necessary dislocations (GNDs). It is predictive: no arbitrary parameters or length scales were invoked and no ad hoc numerical techniques were employed. It uses general stress field equations for GND content and a novel harmonization technique to enforce consistency of elastic long-range singular defect fields with applied elastic-plastic fields. The model facilitates implementation in commercial finite element programs without requiring special elements, special boundary conditions, or access to element shape functions. GM simulations confirmed, with improved accuracy, previously published predictions of the Hall-Petch effect, Bauschinger effect, and anelasticity. Previously unpredicted phenomena were also predicted: anelasticity and hysteresis for single Ta crystals and strain-hardening stagnation. The internal stresses (higher-order effect) dominate at large length scales, while at small length scales, the GND density hardening (lower-order effect) dominates. As a result, GM predicts that strain heterogeneity and consequent GND internal stresses are important factors in anelasticity.

36 MATERIALS SCIENCE↗

From solid surfactants to micromotors: An overview of the synthesis and applications of heterogeneous particles

Colloid science has classically concerned itself with the investigation of the properties of dispersed phases in a bulk medium. This has led to the development of a rich amount of chemistry, physics, and engineering that have facilitated the evolution and maturation of this field. One of the many developments made over the last 30 years is the introduction of particles that are heterogeneous in chemistry and shape. These heterogeneities can introduce behaviors that are not achievable in homogeneous systems and that are specific to the type and class of nonuniformity. This has led to the development of numerous technologies, two of which are Janus micromotors and solid surfactants. Here, this review aims to familiarize the reader with the field of heterogeneous particles. We begin with an overview of various synthetic methods to produce colloidal particles that are heterogeneous in chemistry and shape. We then discuss their use as solid surfactants and autonomous micromotors. We then close by summarizing and providing a future perspective on the field.

36 MATERIALS SCIENCE↗

Microstructural evolution and strengthening mechanisms in a heat-treated additively manufactured Al–Cu–Mn–Zr alloy

In this report the microstructural and strength evolution of an additively manufactured Al-8.6Cu-0.5Mn-0.9Zr alloy upon aging at 300, 350, and 400 °C is investigated. The strengthening phases of the alloy evolve significantly upon aging, with breakdown and spheroidization of the interconnected θ-Al 2 Cu network, dissolution of metastable θ'-Al 2 Cu precipitates, and precipitation of nanometric L1 2 -Al 3 Zr from a matrix supersaturated in Zr. In the peak-aged states, the alloy displays a favorable combination of strength and ductility, with a room-temperature yield strength of 314–341 MPa and ductility of 11–13%. The measured yield strengths for microstructures with different aging treatments are compared to predictions of yield strengths from grain boundary, solid solution, and particle strengthening contributions. The observed strain hardening behavior is related to fundamental precipitate and dislocation interactions. Comparison between predicted and measured strength values indicates a continued need for strengthening models specifically developed for the heterogeneous microstructures of additively manufactured alloys.

36 MATERIALS SCIENCE↗

Tuning Strong Metal–Support Interactions via Synergistic Alloying

The encapsulation phenomenon associated with strong metal-support interaction (SMSI) has been largely restricted to catalyst systems consisting of group VIII metals with high surface energy and reducible transition metal oxide supports with low surface energy. Here, we demonstrate an encapsulation phenomenon that, while sharing morphological similarities with conventional SMSI, follows a distinctive pathway. This is shown by the encapsulation of CuAu nanoparticles (NPs) supported on highly ordered pyrolytic graphite (HOPG). Through dynamic monitoring of Cu, Au, and Cu 50 Au 50 NPs in an oxidizing atmosphere using ambient-pressure X-ray photoelectron spectroscopy, we show that this spontaneous encapsulation is achieved through the synergistic effect of the alloying elements. Specifically, the surface segregation of Cu promotes dissociative O 2 adsorption, leading to the formation of atomic O species, while the subsurface enrichment of Au hinders O incorporation into the bulk of CuAu NPs. Consequently, O spillover onto the graphite support occurs, resulting in the oxidation of the HOPG surface into graphitic oxide species. The higher affinity of the graphitic oxide species toward the Cu-segregated surface prompts their migration from the HOPG support to encapsulate the CuAu NPs. Finally, these results transcend the conventional SMSI and bear practical implications for the design and development of heterogeneous catalysts, particularly in carbon-supported alloy systems.

36 MATERIALS SCIENCE↗

Real-time (nanoseconds) determination of liquid phase growth during shock-induced melting

Melting of solids is a fundamental natural phenomenon whose pressure dependence has been of interest for nearly a century. However, the temporal evolution of the molten phase under pressure has eluded measurements because of experimental challenges. By using the shock front as a fiducial, we investigated the time-dependent growth of the molten phase in shock-compressed germanium. In situ x-ray diffraction measurements at different times (1 to 6 nanoseconds) behind the shock front quantified the real-time growth of the liquid phase at several peak stresses. These results show that the characteristic time for melting in shock-compressed germanium decreases from ~7.2 nanoseconds at 35 gigapascals to less than 1 nanosecond at 42 gigapascals. Our melting kinetics results suggest the need to consider heterogeneous nucleation as a mechanism for shock-induced melting and provide an approach to measuring melting kinetics in shock-compressed solids.

36 MATERIALS SCIENCE↗

Resolving intragranular stress fields in plastically deformed titanium using point-focused high-energy diffraction microscopy

Abstract The response of a polycrystalline material to a mechanical load depends not only on the response of each individual grain, but also on the interaction with its neighbors. These interactions lead to local, intragranular stress concentrations that often dictate the initiation of plastic deformation and consequently the macroscopic stress–strain behavior. However, very few experimental studies have quantified intragranular stresses across bulk, three-dimensional volumes. In this work, a synchrotron X-ray diffraction technique called point-focused high-energy diffraction microscopy (pf-HEDM) is used to characterize intragranular deformation across a bulk, plastically deformed, polycrystalline titanium specimen. The results reveal the heterogenous stress distributions within individual grains and across grain boundaries, a stress concentration between a low and high Schmid factor grain pair, and a stress gradient near an extension twinning boundary. This work demonstrates the potential for the future use of pf-HEDM for understanding the local deformation associated with networks of grains and informing mesoscale models. Graphical abstract

36 MATERIALS SCIENCE↗

Understanding the Performance Gap between Polycrystalline and Single-Crystal Nickel-Rich Layered Oxide Cathodes

Singe-crystal (SC) nickel-rich layered oxide cathodes, composed of boundary-free particles with high tap density, offer significant advantages in volumetric energy density and mechanical strength compared with polycrystalline (PC) cathode materials. However, as the nickel content increases (≥80%), SC Ni-rich cathodes often suffer from faster performance degradation than PC cathodes of the same composition, and the underlying causes of this discrepancy remain poorly understood. Herein, we reveal the distinct Ni redox behaviors that govern the electrochemical performance of SC and PC Ni-rich cathodes using multiscale and operando characterization techniques. Our results indicate that the increasingly heterogeneous Ni oxidation process in SC cathodes leads to the additional irreversible oxygen redox activity that deteriorates both the mechanical and chemical structures. In contrast, PC cathodes, despite with more pronounced surface reconstruction, exhibit greater chemomechanical stability due to homogeneous redox reactions during charging. Consequently, we find that bulk degradation, more than surface reactions, ultimately leads to fast capacity decay of SC Ni-rich cathodes during cycling. In conclusion, this work offers a comprehensive view on the impact of Ni redox evolutions on the chemomechanical stability in Ni-rich layered oxide cathodes, providing new insights into the longstanding performance gap between SC and PC cathodes, and guiding the rational design of Ni-rich cathode architectures.

36 MATERIALS SCIENCE↗

Transformation of TiN to TiNO Films via In-Situ Temperature-Dependent Oxygen Diffusion Process and Their Electrochemical Behavior

Titanium oxynitride (TiNO) thin films represent a multifaceted material system applicable in diverse fields, including energy storage, solar cells, sensors, protective coatings, and electrocatalysis. This study reports the synthesis of TiNO thin films grown at different substrate temperatures using pulsed laser deposition. A comprehensive structural investigation was conducted by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Non-Rutherford backscattering spectrometry (N-RBS), and X-ray absorption spectroscopy (XAS), which facilitated a detailed analysis that determined the phase, composition, and crystallinity of the films. Structural control was achieved via temperature-dependent oxygen in-diffusion, nitrogen out-diffusion, and the nucleation growth process related to adatom mobility. The XPS analysis indicates that the TiNO films consist of heterogeneous mixtures of TiN, TiNO, and TiO2 phases with temperature-dependent relative abundances. The correlation between the structure and electrochemical behavior of the thin films was examined. The TiNO films with relatively higher N/O ratio, meaning less oxidized, were more electrochemically active than the films with lower N/O ratio, i.e., more oxidized films. Films with higher oxidation levels demonstrated enhanced crystallinity and greater stability under electrochemical polarization. These findings demonstrate the importance of substrate temperature control in tailoring the properties of TiNO film, which is a fundamental part of designing and optimizing an efficient electrode material.

Cherono, Sheilah↗

Revealing meso-structure dynamics in additive manufacturing of energy storage via operando coherent X-ray scattering

3D printing is an emerging technology for the fabrication of energy storage devices, offering advantages over traditional manufacturing methods. However, optimization and design of such devices requires an understanding of the meso-structure formation during the 3D printing process. This study utilizes operando coherent X-ray scattering, X-ray Photon Correlation Spectroscopy (XPCS), to study the spatiotemporally-resolved far-from-equilibrium dynamics during direct ink writing 3D printing. Here, Lithium Titanate (LTO) based ink is prepared and rheologically tested for its shear-thinning properties. Two-time intensity-intensity functions are calculated to be used in subsequent quantitative analysis, which allows for an overall characterization of the dynamics, description of an initial fast decorrelation and identification of sudden rearrangements of subdomains of the sample. The results show the dynamics to be anisotropic, spatiotemporally heterogenous and marked by distinct rearrangement events, all of which impact the electrochemical performance of energy storage devices. The studied 3D printing ink is used to fabricate electrodes which are then electrochemically tested, showing good performance in cycling and retaining structural integrity. This work furthers the understanding of the far-from-equilibrium material dynamics during 3D printing, giving quantitative characterization of this process, and highlights aspects of structure formation relevant to the electrochemical performance of the resultant energy storage device.

36 MATERIALS SCIENCE↗

Nanoscale chemical imaging with structured X-ray illumination

High-resolution imaging with compositional and chemical sensitivity is crucial for a wide range of scientific and engineering disciplines. Although synchrotron X-ray imaging through spectromicroscopy has been tremendously successful and broadly applied, it encounters challenges in achieving enhanced detection sensitivity, satisfactory spatial resolution, and high experimental throughput simultaneously. In this work, based on structured illumination, we develop a single-pixel X-ray imaging approach coupled with a generative image reconstruction model for mapping the compositional heterogeneity with nanoscale resolvability. This method integrates a full-field transmission X-ray microscope with an X-ray fluorescence detector and eliminates the need for nanoscale X-ray focusing and raster scanning. We experimentally demonstrate the effectiveness of our approach by imaging a battery sample composed of mixed cathode materials and successfully retrieving the compositional variations of the imaged cathode particles. Bridging the gap between structural and chemical characterizations using X-rays, this technique opens up vast opportunities in the fields of biology, environmental, and materials science, especially for radiation-sensitive samples.

Li, Jizhou↗

Characterizing the uppermost 100 m structure of the San Jacinto fault zone southeast of Anza, California, through joint analysis of geological, topographic, seismic and resistivity data

We present results from complementary geological, topographic, seismic and electrical resistivity surveys at the Sagebrush Flat (SGB) site along the Clark fault (CF) strand of the San Jacinto fault zone trifurcation area southeast of Anza, California. Joint interpretation of these data sets, each with unique spatiotemporal sensitivities, allow us to better characterize the shallow (<100 m) fault zone at this structurally complex site. Geological mapping at the surface shows the CF has three main subparallel strands within a <100 m zone with varying degrees of rock damage. These strands intersect units of banded gneiss and tonalite, and various sedimentary units. Near the surface, the weathered but more intact tonalite and gneiss to the southwest have relatively high VP. The low-lying flat sedimentary basins around the two southwestern-most CF strands and elevated damaged gneiss to the northeast have lowest VP <500 m s–1. The high relief of the northeast gneiss unit may in part be explained by its extensive damage and inferred increased relative rock uplift. Resistivity imaging shows the unconsolidated dry basin sediments (maximum >1300 Ohm.m) contrasted against the compacted fine-grained (potentially wet) materials within the CF core and the Bautista Formation (minimum <40 Ohm.m), which is slightly elevated above the flat basins. The inverse relationship between VP (increases) and resistivity (decreases) in the uppermost ~15 m can be characterized as log–log linear with slopes of –2.6 to –4. At depths >30 m, the velocity heterogeneity near the surface merges into larger-scale structures that are generally slower on the northeast side of the CF core compared to the southwest side (as much as ~40 per cent reduction in average VP). A previous study revealed a 20–37 per cent variability in peak ground velocities across the SGB site from local earthquakes. The upper end of that range is associated with the near-surface unconsolidated sedimentary basins and northeast damaged gneiss unit. Preliminary analysis of time-dependent topography mostly shows effects of changing vegetation and anthropogenic activity.

Geochemistry & Geophysics↗

AmeriFlux FLUXNET-1F US-Me2 Metolius mature ponderosa pine

This is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-Me2 Metolius mature ponderosa pine. This is the FLUXNET version of the carbon flux data for the site US-Me2 Metolius mature ponderosa pine produced by applying the standard ONEFlux (1F) software. Site Description - Site Description before Fire (January, 2002 - August, 2020): The mean stand age is 71 years old and the stand age of the oldest 10% of trees is about 108 years old. This site is one of the Metolius core cluster sites with different age and disturbance classes and part of the AmeriFlux network. The overstory is almost exclusively composed of ponderosa pine trees (Pinus ponderosa Doug. Ex P. Laws) with a few scattered incense cedars (Calocedrus decurrens (Torr.) Florin) and has a peak leaf area index (LAI) of 2.1 m2 m-2. Tree height is relatively homogeneous at about 18 m, and the mean tree density is approximately 339 trees ha-1 (Irvine et al., 2008). The understory is sparse with an LAI of 0.2 m2 m-2 and primarily composed of bitterbrush (Purshia tridentata (Push) DC.) and greenleaf manzanita (Arctostaphylos patula Greene). Soils at the site are sandy (69%/24%/7% sand/silt/clay at 0–0.2 m depth and 66%/27%/7% at 0.2–0.5 m depth, and 54%/ 35%/11% at 0.5–1.0 m depth), freely draining with a soil depth of approximately 1.5 m (Irvine et al., 2008; Law et al., 2001b; Schwarz et al., 2004). Green Ridge Fire: On August 20, 2020, the Green Ridge Fire burned through Us-Me2. The fire was ignited by lightning on August 16th, and grew rapidly to the east over the first few days driven by strong, downslope (westerly) afternoon winds. Fire behavior and observed fire effects were highly heterogeneous due to the localized wind pattern carrying the flaming head of the fire forward, and the efforts being made by suppression resources to contain the fire. The site experienced the full range of fire effects, from <1 m high surface fire that charred litter and duff and only consumed shrubs and herbaceous material to full tree (>15 m) crown fire that consumed 100% of needles, small limbs, and surface fuels at high intensity, leaving only ash and bare soil post-fire. Salvage Logging: From late March to late April 2021, salvage logging by the landowner occurred at the site. Almost all trees within the flux footprint were logged except a small area with lower burn severity, where sap flow and automatic soil respiration measurements are continued since the fire. In August 2022 the primary flux system was moved from the top of the damaged tall tower to a nearby shorter tower centering on the salvage/regenerating footprint.

Hanson, Chad↗

A versatile machine learning workflow for high-throughput analysis of supported metal catalyst particles

Accurate and efficient characterization of nanoparticles (NPs), particularly regarding particle size distribution, is essential for advancing our understanding of their structure-property relationship and facilitating their design for various applications. In this study, we introduce a novel two-stage artificial intelligence (AI)-driven workflow for NP analysis that leverages prompt engineering techniques from state-of-the-art single-stage object detection and large-scale vision transformer (ViT) architectures. This methodology is applied to transmission electron microscopy (TEM) and scanning TEM (STEM) images of heterogeneous catalysts, enabling high-resolution, high-throughput analysis of particle size distributions for supported metal catalyst NPs. The model's performance in detecting and segmenting NPs is validated across diverse heterogeneous catalyst systems, including various metals (Ru, Cu, PtCo, and Pt), supports (silica (SiO 2 ), γ-alumina (γ-Al 2 O 3 ), and carbon black), and particle diameter size distributions with mean and standard deviations ranging from 1.6 ± 0.2 nm to 9.7 ± 4.6 nm. The proposed machine learning (ML) methodology achieved an average F1 overlap score of 0.91 ± 0.01 and demonstrated the ability to disentangle overlapping NPs anchored on catalytic support materials. The segmentation accuracy is further validated using the Hausdorff distance and robust Hausdorff distance metrics, with the 90th percent of the robust Hausdorff distance showing errors within 0.4 ± 0.1 nm to 1.4 ± 0.6 nm. In conclusion, our AI-assisted NP analysis workflow demonstrates robust generalization across diverse datasets and can be readily applied to similar NP segmentation tasks without requiring costly model retraining.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal–organic framework (MOF) materials as polymerization catalysts: a review and recent advances

Synthetic polymers are ubiquitous across both the industrial and consumer segments of the world economy. Catalysts enable rapid, efficient, selective, and even stereoselective, formation of desired polymers from any of a host of candidate monomers. While numerous molecular catalysts have been shown to be effective for these reactions, separation of the catalysts from reaction products is typically difficult – a potentially problematic complication that suggests instead the use of heterogeneous catalysts. Many of the most effective heterogeneous catalysts, however, comprise supported collections of reaction centres that are decidedly nonuniform in their composition, siting, and activity. Nonuniformity complicates atomic-scale evaluation of the basis for catalytic activity and thus impedes scientific hypothesis-driven understanding and development of superior catalysts. In view of the fundamental desirability of structural and chemical uniformity at the meso, nano, and even atomic scale, crystallographically well-defined, high-porosity metal–organic frameworks (MOFs) have attracted attention as model catalysts and/or catalyst-supports for a wide variety of chemical transformations. In the realm of synthetic polymers, catalyst-functionalized MOFs have been studied for reactions ranging from coordination-mediated polymerization of ethylene to visible-light initiated radical polymerizations. Nevertheless, many polymerization reactions remain to be explored – and, no doubt, will be explored, given the remarkable structural and compositional diversity of attainable MOFs. Noteworthy emerging studies include work directed toward more sophisticated catalytic schemes such as polymer templating using MOF pore architectures and tandem copolymerizations using MOF-supported reaction centres. Finally, it is appropriate to recognize that MOFs themselves are synthetic polymers – albeit, uncoventional ones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying Boron Active Sites for the Oxidative Dehydrogenation of Propane

Oxidative dehydrogenation of propane (ODHP) to propylene could have a significant impact on the production of this critical chemical intermediate, if appropriate catalysts can be discovered. Recently, heterogeneous catalysts based on boron (oxides and nitrides) have been demonstrated to be promising for ODHP, but their active sites have not been conclusively identified. Here, we report that the deposition of differently sized boronic acids into the micropores of silica supports results in different distributions of surface borate species after calcination. Furthermore, these materials, in turn, display a wide range of rates in ODHP but similar selectivity, suggesting that they differ only in the numbers of active sites. Features identified by in situ Raman, IR, and magic-angle-spinning 11 B solid-state NMR spectroscopies are compared to catalyst activity. This correlation identifies the S2 borate species, a hydroxylated nonring boron, as the likely active site and provides a target for directed syntheses of future catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗