Results for “heterogeneous processes” — Page 23

DOE OSTI2026

Solvent Stabilization of Protic Oxonium/Ammonium Intermediates in Cation Radical Cyclization Reactions Investigated via Computational Approaches

Anodic intramolecular cyclization reactions have substantial synthetic utility for formation of cyclic carbon–carbon or carbon–heteroatom bonds. For cases of intramolecular trapping of a cation radical by a protic nucleophile, the cyclization step coincides with a substantial increase in substrate acidity and thus may exhibit particularly pronounced solvent effects. In this computational work, we employ both quantum chemical (QM) and quantum mechanics/molecular mechanics (QM/MM) methods to compute solvent effects on free energy profiles for cyclization and deprotonation reaction steps for cation radical intermediates of substrates representative for anodic intramolecular cyclizations. We find substantial solvent contribution to the thermodynamic driving force for cation radical cyclization; for example, methanol and tetrahydrofuran solvents provide ∼30–35 kJ/mol driving force to form cyclic oxonium cation radicals and ∼15–25 kJ/mol driving force to form cyclic ammonium cation radicals, compared to baseline reactions in dichloromethane solvent. Given that these solvent shifts are on par with the innate cyclization reaction thermodynamics, the choice of solvent plays a crucial role in promoting/driving the cation radical cyclization step. Methanol is particularly effective at facilitating rapid deprotonation of the cyclic cation radical intermediate, which may lead to the full electrochemical process (e.g., second electron transfer) proceeding heterogeneously at the anode.

Khan, Shahriar [ORNL] (ORCID:0000000289138430)↗

DOE OSTI2026

Effects of Recovery Conditions and Aggregation Mechanisms on the Chemical and Physical Properties of Hybrid Poplar and Corn Stover Lignins

Heterogeneity in the physical properties and processing behavior of lignins recovered from biorefining process streams can hinder their effective utilization and industrial valorization. This work investigates lignin recovery by acidification from alkaline pretreatment liquors of varying sources (corn stover and hybrid poplar), compositions, solid contents, and incubation temperatures prior to filtration. Recovered lignins were characterized for filtration performance, mass yield, chemical composition, particle size and morphology, and color. A transition temperature was identified corresponding to marked shifts in lignin physical properties and was a function of the solid content and liquor source. Filtration below this temperature yielded slow-filtering, dark, brittle lignins with smoother particle surfaces, whereas precipitation above this threshold yielded fast-filtering, lighter, powdery lignins with rougher particle surfaces. The impact of temperature and concentration on universal cluster aggregation mechanisms was proposed to explain the differences between lignin particle properties and filtration behavior.

Aggregation↗

DOE OSTI2023

nmrrr : A Reproducible Workflow for Binning and Visualizing NMR Spectra From Environmental Samples

Nuclear magnetic resonance (NMR) spectroscopy is a useful tool for detection and identification of molecular structural information, with increasing applications in environmental sciences. NMR instrument outputs are however heterogeneous and require extensive post-processing, creating barriers to their use and application by non-specialists. Here, we report on a new open-source R package, nmrrr, that processes and visualizes spectral data obtained from one-dimensional solution-state and solid-state NMR experiments; the package also performs relevant calculations commonly applied in natural organic matter communities, such as computing the relative abundance of various functional groups. We document the package's installation, dependencies, and functions; and provide a standard workflow for processing NMR data. This package is currently available on CRAN and GitHub, and community contributions are welcome.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Time-domain thermoreflectance

Time-domain thermoreflectance (TDTR) has been instrumental in measuring the heat transfer properties of bulk and nanostructured materials over the past two decades. In this Primer, we describe the optical and thermal aspects of TDTR, with an in-depth discussion on the theory, apparatus design and implementation. We present examples that illustrate the ability of TDTR to measure thermal conductivity tensors, thermal conductance across material interfaces, and volumetric heat capacity of thin films, 2D materials and bulk materials. The ability of TDTR to spatially resolve thermal properties is useful for studying heterogeneous material systems, such as materials processed in or subjected to extreme environments. We consider current limitations of pump–probe metrologies and discuss recent advancements of TDTR, such as time-resolved magneto-optic Kerr effect (TR-MOKE), beam-offset TDTR/TR-MOKE, steady-state thermoreflectance, frequency-domain thermoreflectance and laser-flash TDTR. Lastly, we present an outlook on anticipated technological developments to further expand the ability of TDTR to measure nanoscale thermal properties.

42 ENGINEERING↗

DOE OSTI2024

EIC Software Overview

Development of the EIC project detector "ePIC" is now well underway and this includes the "single software stack" used for simulation and reconstruction. The stack combines several non-experiment-specific packages including ACTS, DD4hep, JANA2, and PODIO. The software stack aims to be forward looking in the era of AI/ML and heterogeneous hardware. A formal decision making process was implemented to choose the components that involved everyone in the collaboration that was interested. This talk will present an overview of the software stack currently used for development of the ePIC detector and on which we expect to execute the experiment.

Lawrence, David↗

DOE OSTI2023

Robust reconstruction of single-cell RNA-seq data with iterative gene weight updates

Single-cell RNA-sequencing technologies have greatly enhanced our understanding of heterogeneous cell populations and underlying regulatory processes. However, structural (spatial or temporal) relations between cells are lost during cell dissociation. These relations are crucial for identifying associated biological processes. Many existing tissue-reconstruction algorithms use prior information about subsets of genes that are informative with respect to the structure or process to be reconstructed. When such information is not available, and in the general case when the input genes code for multiple processes, including being susceptible to noise, biological reconstruction is often computationally challenging. We propose an algorithm that iteratively identifies manifold-informative genes using existing reconstruction algorithms for single-cell RNA-seq data as subroutine. We show that our algorithm improves the quality of tissue reconstruction for diverse synthetic and real scRNA-seq data, including data from the mammalian intestinal epithelium and liver lobules.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

1 kV Self-Aligned Vertical GaN Superjunction Diode

This work demonstrates vertical GaN superjunction (SJ) diodes fabricated via a novel self-aligned process. The SJ comprises n-GaN pillars wrapped by the charge-balanced p-type nickel oxide (NiO). After the NiO sputtering around GaN pillars, the self-aligned process exposes the top pillar surfaces without the need for additional lithography or a patterned NiO etching which is usually difficult. The GaN SJ diode shows a breakdown voltage (B V) of 1100 V, a specific on-resistance (R ON ) of 0.4 mΩ· cm2, and a SJ drift-region resistance ( R dr ) of 0.13 mΩ· cm2. Further, the device also exhibits good thermal stability with B V retained over 1 kV and R ON dropped to 0.3 mΩ· cm2 at 125°C. The trade-off between B V and R dr is superior to the 1D GaN limit. These results show the promise of vertical GaN SJ power devices. The self-aligned process is applicable for fabricating the heterogeneous SJ based on various wide- and ultra-wide bandgap semiconductors.

42 ENGINEERING↗

DOE OSTI2021

Monolithic Multigrid Methods for Magnetohydrodynamics

The magnetohydrodynamics equations model a wide range of plasma physics applications and are characterized by a nonlinear system of partial differential equations that strongly couples a charged fluid with the evolution of electromagnetic fields. After discretization and linearization, the resulting system of equations is generally difficult to solve due to the coupling between variables and the heterogeneous coefficients induced by the linearization process. In this paper, we investigate multigrid preconditioners for this system based on specialized relaxation schemes that properly address the system structure and coupling. Here, three extensions of Vanka relaxation are proposed and applied to problems with up to 170 million degrees of freedom and fluid and magnetic Reynolds numbers up to 400 for stationary problems and up to 20,000 for time-dependent problems.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2023

EIC Software Overview

Development of the EIC project detector "ePIC" is now well underway and this includes the "single software stack" used for simulation and reconstruction. The stack combines several non-experiment-specific packages including ACTS, DD4hep, JANA2, and PODIO. The software stack aims to be forward looking in the era of AI/ML and heterogeneous hardware. A formal decision making process was implemented to choose the components that involved everyone in the collaboration that was interested. This talk will present an overview of the software stack currently used for development of the ePIC detector and on which we expect to execute the experiment.

Lawrence, David↗

DOE OSTI2024

Evaluating Operators in Deep Neural Networks for Improving Performance Portability of SYCL

SYCL is a portable programming model for heterogeneous computing, so it is important to obtain reasonable performance portability of SYCL. Towards the goal of better understanding and improving performance portability of SYCL for machine learning workloads, we have been developing benchmarks for basic operators in deep neural networks (DNNs). These operators could be offloaded to heterogeneous computing devices such as graphics processing units (GPUs) to speed up computation. In this work, we introduce the benchmarks, evaluate the performance of the operators on GPU-based systems, and describe the causes of the performance gap between the SYCL and Compute Unified Device Architecture (CUDA) kernels. We find that the causes are related to the utilization of the texture cache for read-only data, optimization of the memory accesses with strength reduction, shared local memory accesses, and register usage per thread. We hope that the efforts of developing benchmarks for studying performance portability will stimulate discussion and interactions within the community.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2021

ParFlow

ParFlow is an open-source, modular, parallel watershed flow model. It includes fully-integrated overland flow, the ability to simulate complex topography, geology and heterogeneity and coupled land-surface processes including the land-energy budget, biogeochemistry and snow (via CLM). It is multi-platform and runs with a common I/O structure from laptop to supercomputer. ParFlow is the result of a long, multi-institutional development history and is now a collaborative effort between CSM, LLNL, UniBonn and UCB. ParFlow has been coupled to the mesoscale, meteorological code ARPS and the NCAR code WRF.

Smith, Steven↗

DOE OSTI2021

ParFlow

ParFlow is an open-source, modular, parallel watershed flow model. It includes fully-integrated overland flow, the ability to simulate complex topography, geology and heterogeneity and coupled land-surface processes including the land-energy budget, biogeochemistry and snow (via CLM). It is multi-platform and runs with a common I/O structure from laptop to supercomputer. ParFlow is the result of a long, multi-institutional development history and is now a collaborative effort between CSM, LLNL, UniBonn and UCB. ParFlow has been coupled to the mesoscale, meteorological code ARPS and the NCAR code WRF.

Smith, Steven↗

NASA NTRS1983

Fundamental combustion experiments in microgravity

Technical bases for microgravity combustion experimentation are identified for important areas of study. The analyses which underlie the need for microgravity experiments of single and two-phase autoignitions, explosions, thermokinetic oscillations, and kinetic oscillations are emphasized. It is shown that turbulent combustion experiments at microgravity are needed and that heterogeneous kinetics are a centrally important process in a number of classic experiments.

Berlad, A. L.↗

NASA NTRS1987

Translation and execution of distributed Ada programs - Is it still Ada?

Some of the fundamental issues and tradeoffs for distributed execution systems for the Ada language are examined. Steps that need to be taken to deal with heterogeneity of addressing program objects, of processing resources, and of the individual processor environment are considered. The ways in which program elements can be assigned are examined in the context of four issues: implied remote object access, object visibility and recursive execution, task termination problems, and distributed types.

Volz, Richard A.↗

NASA NTRS1990

A distinct variant of high-titanium mare basalt from the Van Serg core, Apollo 17 landing site

A fragment of basalt picked from the drive tube collected at Van Serg crater at the Apollo 17 landing site has a bulk chemistry more primitive than that of other high-titanium mare basalt groups collected at the site. The sample has a fine-grained olivine phyric, subophitic texture that is distinct from that of other high-titanium basalt samples. The grain size and texture suggest that the sample has a composition close to that of a magma. The crystallization sequence, with appearance of oxide minerals later than in other groups, and other petrographic features such as more-calcic plagioclase and early pigeonite rather than augite, are consistent with this sample representing a distinct variant of Apollo 17 high-titanium basalts. It is not related through closed-system igneous processes to any of the other mare basalt groups identified among Apollo 17 samples. Its characters emphasize the complexity of contemporaneous magma processes on the moon and the heterogeneity of that part of the mantle that was melted.

Ryder, Graham↗

NASA NTRS1993

Tectonic resurfacing of Venus

Impact crater distributions and morphologies have traditionally played an important role in unraveling the geologic histories of terrestrial objects, and Venus has proved no exception. The key observations are: mean crater retention age about 500 Ma; apparently random spatial distribution; modest proportion (17 percent) of modified craters; and preferential association of modified craters with areas of low crater density. The simplest interpretation of these data alone is that Venus experienced global resurfacing (assumed to be largely volcanic) prior to 500 Ma, after which time resurfacing rates decreased dramatically. This scenario does not totally exclude present geological activity: some resurfacing and crater obliteration is occurring on part of the planet, but at rates much smaller than on Earth. An alternative endmember model holds that resurfacing is also spatially randomly distributed. Resurfacing of about 1 sq km/yr eliminates craters such that a typical portion of the surface has an age of 500 Ma, but actual ages range from zero to about 1000 Ma. Monte Carlo simulation indicates that the typical resurfacing 'patch' cannot exceed about 500 km in diameter without producing a crater distribution more heterogeneous than observed. Volcanic or tectonic processes within these patches must be locally intense to be able to obliterate craters completely and leave few modified. In this abstract, we describe how global geologic mapping may be used to test resurfacing hypotheses. We present preliminary evidence that the dominant mode of resurfacing on Venus is tectonism, not volcanism, and that this process must be ongoing today. Lastly, we outline a conceptual model in which to understand the relationship between global tectonics and crater distribution and preservation.

Malin, Michael C.↗

NASA NTRS2011

Characterization of Catalyst Materials for Production of Aerospace Fuels

Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

DeLaRee, Ana B.↗

NASA NTRS2012

Characterization of Catalyst Materials for Production of Aerospace Fuels

Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

Best, Lauren M.↗