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At least 289 records · Page 16

Recent progress in the synthesis of advanced biofuel and bioproducts

Energy is one of the most complex fields of study and an issue that influences nearly every aspect of modern life. Over the past century, combustion of fossil fuels, particularly in the transportation sector, has been the dominant form of energy release. Refining of petroleum and natural gas into liquid transportation fuels is also the centerpiece of the modern chemical industry used to produce materials, solvents, and other consumer goods. In the face of global climate change, the world is searching for alternative, sustainable means of producing energy carriers and chemical building blocks. The use of biofuels in engines predates modern refinery optimization and today represents a small but significant fraction of liquid transportation fuels burnt each year. Similarly, white biotechnology has been used to produce many natural products through fermentation. The evolution of recombinant DNA technology into modern synthetic biology has expanded the scope of biofuels and bioproducts that can be made by biocatalysts. Furthermore, this opinion examines the current trends in this research space, highlighting the substantial growth in computational tools and the growing influence of renewable electricity in the design of metabolic engineering strategies. In short, advanced biofuel and bioproduct synthesis remains a vibrant and critically important field of study whose focus is shifting away from the conversion of lignocellulosic biomass toward a broader consideration of how to reduce carbon dioxide to fuels and chemical products.

09 BIOMASS FUELS↗

Milligrams to kilograms: making microbes work at scale

Energy is one of the most complex fields of study and an issue that influences nearly every aspect of modern life. Over the past century, combustion of fossil fuels, particularly in the transportation sector, has been the dominant form of energy release. Refining of petroleum and natural gas into liquid transportation fuels is also the centerpiece of the modern chemical industry used to produce materials, solvents, and other consumer goods. In the face of global climate change, the world is searching for alternative, sustainable means of producing energy carriers and chemical building blocks. The use of biofuels in engines predates modern refinery optimization and today represents a small but significant fraction of liquid transportation fuels burnt each year. Similarly, white biotechnology has been used to produce many natural products through fermentation. The evolution of recombinant DNA technology into modern synthetic biology has expanded the scope of biofuels and bioproducts that can be made by biocatalysts. This opinion examines the current trends in this research space, highlighting the substantial growth in computational tools and the growing influence of renewable electricity in the design of metabolic engineering strategies. In short, advanced biofuel and bioproduct synthesis remains a vibrant and critically important field of study whose focus is shifting away from the conversion of lignocellulosic biomass towards a broader consideration of how to reduce carbon dioxide to fuels and chemical products.

59 BASIC BIOLOGICAL SCIENCES↗

Tritium Transport Phenomena in Molten-Salt Reactors: Molten Salt Tritium Transport Experiment Design

Tritium is produced from neutron interactions with both lithium and beryllium. Large quantities of tritium are generated in Molten Salt Reactors (MSRs) which use LiF/BeF2 (FLiBe) as the fuel salt. Tritium is unique among the radionuclide hazards as it readily permeates through metal structural materials at high temperatures. All metal surfaces are potential release paths for tritium. For adequate safety analysis and eventual licensing of new reactors, predictive models for tritium transport and release from MSRs must be developed. These models must account for the multiple transport phenomena involved with tritium: fuel salt phase mass transport, dissociation/recombination reactions on metal surfaces, interstitial diffusion through the metal structure, and salt or gas phase mass transport in the downstream fluid. These models also must also be validated with representative experiments. Our previous report outlined tritium transport phenomena involved in MSRs, made suggestions on gaps in the transport dataset, and proposed an experimental test stand to test combined transport effects – tritium transport through pipe walls in a convective salt flow. In this report, we summarize an updated analysis framework for tritium transport in MSRs, report our results on hydrogen and deuterium permeation through Hastelloy N, and describe the final design of the Molten Salt Tritium Transport Experiment (MSTTE, pronounced “misty”). The MSRE provides the only wholistic experimental data set for tritium transport in MSRs and understanding the transport phenomena involved in the MSRE is crucial for future model development. One set of parameters in our analysis framework was unknown for the MSRE—surface reaction rates for tritium on Hastelloy N. This warranted our hydrogen and deuterium permeation campaign to assess the permeability, diffusivity, and solubility of hydrogen isotopes in clean Hastelloy N. Surface reaction rate constants were probed by low pressure measurements, however, no surface effects were observed in the limits of our permeation apparatus. Permeation experiments on oxidized Hastelloy N were not performed for this report but are planned in future work. The experimental test stand, MSTTE, measures combined transport properties of the salt-metal system. MSTTE is a forced convection FLiBe loop with custom designed test section to measure tritium transport through candidate structural materials. We use MSRE relevant dimensionless numbers to design and scale the test section. Hastelloy N is a candidate loop and test section material due to the relevance for the MSRE and related designs, however, other metals are being considered (e.g. 316H SS) which may better align with current vendor concepts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The effect of interfacial phenomena on gas solubility measurements in molten salts

The behavior of fission gases in molten fuel salt reactors governs activity transport from the reactor and can also affect the performance of the reactor itself. The gas solubility can be described thermodynamically by Henry’s law. However, the coupling of the condensed and gas phases depends on the interfacial area, which is difficult to measure or even to estimate. Surfaces of materials in the reactor will include disperse phases in the salt and porosity within the structural materials, covering a range of compositions and sizes. These attributes can affect measurements of fundamental properties such as gas solubility. Methods to obtain gas solubility, surface tension, interfacial energies, and bubble gas transport are reviewed. Recent data from manometric experiments are interpreted based on xenon sorption onto salt-wetted quartz.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Commercially available Hydrogen Detection Systems for Corrosive, Oxygen-free Gas Streams: A Technical Summary

The growing use of hydrogen gas across energy, transportation, and chemical applications necessitates better hydrogen sensors and detectors. Few sensors exist for quantifying hydrogen gas in a corrosive, oxygen-free gas stream due to the challenging nature of the sampling environment and current technological status. Handheld, economic options include palladium-based, metal oxide, catalytic bead, and electrochemical sensors. More permanent and costly options include electrochemical sensors, thermal gas analyzers, mass spectrometers, gas chromatographs, and Raman spectrometers. In this technical report, a short review of current technology, along with the associated commercially available products, is provided. Raman spectroscopy is recommended as an ideal technology for on-line detection of hydrogen at low concentrations in a corrosive, oxygen-free gas stream.

08 HYDROGEN↗

SATS Transient Fission Gas Release Test with Irradiated Fuel under Loss of Coolant Accident Conditions

The transient fission gas release (tFGR) during the temperature ramp associated with a loss-of-coolant accident (LOCA) in light-water reactors (LWRs) is likely a significant contribution to the total pressure in a fuel rod and may cause an unexpected rod burst. The lack of data related to tFGR continues to be a key gap in understanding LWR cladding burst behavior under LOCA conditions. To fully characterize this behavior, tFGR data must be collected from several different systems that can capture all relevant testing conditions. Oak Ridge National Laboratory (ORNL) has developed a system to measure the integral tFGR from irradiated fuel segments. This system was designed to integrate with the existing Severe Accident Test Station (SATS) and to build upon decades of experience capturing fission gas to characterize fuel behavior. The tFGR system consists of a sweep gas system to transport gases from the in-cell SATS apparatus to an out-of-cell fission gas detection system composed of a series of cold traps to capture the off-gas from the heating tests and a gamma spectrometry system to detect and measure 85 Kr. Initial system testing operations were completed during which 85 Kr collection and measurement were verified along with the ability to detect stable inert gases. A tFGR test with a high-burnup fuel specimen was successfully conducted by the in-cell SATS-tFGR system at ORNL. The posttest examination is under way, the result of which will be reported in FY24.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

(Invited) Continuum Mathematical Modeling of Water Electrolysis: A Tutorial

Widespread use of hydrogen energy is contingent on the development of reliable and economical sources of hydrogen. Electrolysis from renewably-derived low-carbon electricity is a potentially viable method of hydrogen generation. Prime among the electrolysis technologies are those utilizing ion-conducting polymers (ionomers) including proton-exchange-membrane water electrolyzer (PEMWE). However, these technologies need to exhibit increased efficiency, performance, and durability to become commercially viable. Like most electrochemical devices, PEMWEs involve multiple components (e.g., catalyst, ionomer, transport layers, membrane, plates) and multiple phases, with phenomena occurring across different time and length scales. Furthermore, it is difficult to experimentally probe many of the species and phenomena during operation. Thus, mathematical modeling at the continuum level has been an invaluable aid in exploring, understanding, and optimizing PEMWE cell and components. Furthermore, this is especially true in the highly coupled and complex physics and chemistries that occur with the membrane-electrode assembly (MEA). The physics in a typical volume-averaged non-isothermal model include multiphase transport in porous media, concentrated-solution theory, Ohm's Law, and Butler-Volmer kinetics, and ion, gas, and water transport in the ionomer.

Dizon, Arthur↗

Electrical control of spin relaxation anisotropy during drift transport in a two-dimensional electron gas

Spin relaxation was studied in a two-dimensional electron gas confined in a wide GaAs quantum well. Recently, the control of the spin relaxation anisotropy by diffusive motion was first shown in D. Iizasa et al., arXiv:2006.08253. Here, we demonstrate electrical control by drift transport in a system with two subbands occupied. The combined effect of in-plane and gate voltages was investigated using time-resolved Kerr rotation. Furthermore, the measured relaxation time presents strong anisotropy with respect to the transport direction. For an in-plane accelerating electric field along [110], the lifetime was strongly suppressed irrespective of the applied gate voltage. Remarkably, for transport along [$1\bara{1}0$], the data shows spin lifetime that was gate dependent and longer than in the [110] direction regardless of the in-plane voltage. In agreement, independent results of anisotropic spin precession frequencies are also presented. Nevertheless, the long spin lifetime, strong anisotropy and drift response seen in the data are beyond the existing models for spin drift and diffusion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Upcycling waste PET into functional multiblock copolymers through controlled macromolecular design

Poly(ethylene terephthalate) (PET) oligomers derived from glycolysis depolymerization were converted into multiblock copolymers through diisocyanate-mediated coupling with dihydroxy-terminated oligomers, enabling precise control over copolymer sequence distribution, connectivity, and mechanical performance. Here, we demonstrate that telechelic PET oligomers isolated directly from depolymerized consumer waste can serve as reactive building blocks for the formation of segmented multiblock copolymers, eliminating the need to revert to monomeric feedstocks. Dihydroxy-terminated PET oligomers (Mw ≈ 8 kg mol−1) were coupled with poly(ethylene oxide) (PEO, Mw ≈ 4 kg mol−1) to form PET-PEO multiblock copolymers with high molar mass (Mw ≈ 160 kg mol−1). We further show that the timing of end-capping reactions provides a key control parameter that governs the competition between chain extension and termination, thereby dictating the resulting multiblock architecture and molecular-weight evolution. Evaluation of their mechanical properties reveals that virgin PET exhibits high modulus (∼3 GPa) and strength (43 MPa) but limited ductility (<10% elongation). In contrast, PET–PEO multiblock copolymers retain comparable tensile strength (44 MPa), albeit while exhibiting dramatically enhanced ductility (>90% elongation), forming tougher materials with efficient stress transfer between the rigid PET domains and the flexible PEO segments. When incorporated into PET/PEO blends at low loadings, the multiblock copolymers serve as effective compatibilizers, yielding materials with an intermediate modulus (1.1–1.2 GPa) and improved elongation compared to uncompatibilized blends. Furthermore, the presence of PEO blocks increases water uptake and gas permeability relative to virgin PET, reflecting the tunability of molecular transport through the copolymeric blocks. To our knowledge, this represents the first report of PET–PEO multiblock copolymers derived from post-consumer PET for gas transport applications. These results demonstrate that multiblock copolymer formation from telechelic PET oligomers provides a versatile platform for tailoring the mechanical and transport behavior of polyester-based materials through controlled macromolecular design and establishes a generalizable strategy for transforming consumer plastic waste into functional segmented polymers without requiring complete depolymerization to monomers.

Watson-Sanders, Shelby [Department of Chemistry, U↗

Experimental investigation of elemental and isotopic evaporation processes by laser heating in an aerodynamic levitation furnace

In this report we carried out evaporation experiments on a B-type calcium–aluminium-rich inclusion (CAI) melt in a gas-mixing aerodynamic levitation laser furnace, at 1873 K and an oxygen partial pressure of 10 -9.1 atm, for durations ranging from 60 to 600 s. Evaporation of SiO 2 and MgO follow the same trend as those observed in vacuum furnace experiments at the same temperature and starting composition, showing that their evaporation relative to one another from the melt is independent of pressure, oxygen fugacity, and hydrodynamical regime specific to the furnace. Isotopic ratios of Mg and Si in evaporation residues are used to derive fractionation factors of α 26/24 Mg vap-liq = 0.9906± 0.0004 and α 30/28 Si vap-lip = 0.9943±0.0003, which are both significantly closer to unity than those found for evaporation in a vacuum, which translates to less isotope fractionation. The residues are also less isotopically fractionated than expected for cases in which transport of the gas species away from the melt is diffusion-controlled at 1-atm. By analysing the flow regimes in our furnace, we find that advection by the levitating gas is the primary mode of mass transport away from the melt surface, as opposed to diffusion-limited transport in a vacuum or 1-atm tube furnace. A modified Hertz–Knudsen–Langmuir formulation accounts for this process, and shows that isotopic fractionation of both Si and Mg reflect a saturation factor (ratio of the pressure of the evaporating species to vapour saturation pressure) equal to 0.75. This is in perfect accord with recent measurements of Cu isotopic fractionation using a similar furnace. The fact that three elements (Mg, Si, Cu) with varying equilibrium vapour pressures, activity coefficients in the liquid, and diffusion coefficients in the gas have the same scaling behaviour to saturation pressure is a strong indication that the mechanism controlling evaporation is driven by the hydrodynamical regime imposed in the furnace. Therefore, this class of experiments can be used to constrain processes in which advection dominates over diffusion, such as (but not limited to) planetary ejecta, tektites, giant impacts, nebular condensation in a turbulent flow, or nuclear fallout material. Finally, the possibility to reach high temperatures (in excess of 3500 K) in this furnace allows it to be used to evaluate the activity coefficients of melt components in extreme conditions relevant to molten planetary interiors (i.e., magma oceans), with a specific focus on refractory elements.

58 GEOSCIENCES↗

Subsurface Redox Interactions Regulate Ebullitive Methane Flux in Heterogeneous Mississippi River Deltaic Wetland

Abstract As interfaces connecting terrestrial and ocean ecosystems, coastal wetlands develop temporally and spatially complex redox conditions, which drive uncertainties in greenhouse gas emission as well as the total carbon budget of the coastal ecosystem. To evaluate the role of complex redox reactions in methane emission from coastal wetlands, a coupled reactive‐transport model was configured to represent subsurface biogeochemical cycles of carbon, nitrogen, and sulfur, along with production and transport of multiple gas species through diffusion and ebullition. This model study was conducted at multiple sites along a salinity gradient in the Barataria Basin at the Mississippi River Deltaic Plain. Over a freshwater to saline gradient, simulated total flux of methane was primarily controlled by its subsurface production and consumption, which were determined by redox reactions directly (e.g., methanogenesis, methanotrophy) and indirectly (e.g., competition with sulfate reduction) under aerobic and/or anaerobic conditions. At fine spatiotemporal scales, surface methane fluxes were also strongly dependent on transport processes, with episodic ebullitive fluxes leading to higher spatial and temporal variability compared to the gradient‐driven diffusion flux. Ebullitive methane fluxes were determined by methane fraction in total ebullitive gas and the frequency of ebullitive events, both of which varied with subsurface methane concentrations and other gas species. Although ebullition thresholds are constrained by local physical factors, this study indicates that redox interactions not only determine gas composition in ebullitive fluxes but can also regulate ebullition frequency through gas production.

03 NATURAL GAS↗

Compositional Control on Shale Pore Structure Characteristics across a Maturation Gradient: Insights from the Devonian New Albany Shale and Marcellus Shale in the Eastern United States

The pore structure characteristics of shales are controlled by their mineralogical and organic matter (OM) composition. However, the contributions by different components in shales at varying thermal maturities remain poorly understood. In this study, Devonian New Albany Shale and Marcellus Shale samples spanning a thermal maturity from marginally mature (vitrinite reflectance R o 0.55%) to post-mature (R o 2.41 %) were selected to study the control of composition on the pore structure properties of shales at different stages of thermal maturation. Scanning electron microscope (SEM) imaging was used to examine pore types in shales, and low-pressure N 2 and CO 2 adsorption analyses were used to quantitatively characterize the mesopore and micropore characteristics of bulk shales and major components in shales. The results show that matrix-associated pores including interparticle pores between silt-sized mineral grains, phyllosilicate framework pores, and intraparticle pores within mineral grains exist in all samples but become less common with increasing maturity, which is likely caused by elevated compaction, cementation, and occlusion with bitumen. Secondary organic pores were not observed under SEM at marginal maturity but were detected in the condensate–wet gas and dry gas windows, with more organic pores in the dry gas window. At marginal maturity, OM has large amounts of mesopores and micropores as demonstrated by low-pressure N 2 and CO 2 adsorption analyses of OM isolated from shales, even though no OM-hosted pores were observed under SEM. With increasing thermal maturity, the mesopore and micropore specific surface area of OM increase and make greater contributions to the pore structure properties of bulk shales. The mesopore and micropore properties of shales are controlled by OM content and maturity as well as by clay mineral type and content, and they can be estimated from the contribution of each component at different stages of thermal maturation. In conclusion, accurate evaluation of the pore volume and SSA of shales will have important implications for assessing gas adsorption and transport in shales.

03 NATURAL GAS↗

Hydrogen Extremely Low Probability of Rupture Version 1

SAND2024-08511O The Hydrogen Extremely Low Probability of Rupture (HELPR) software toolkit provides probabilistic fracture assessments of natural gas infrastructure for transporting hydrogen. Using probabilistic sampling and sensitivity analysis—along with engineering fatigue and fracture mechanics— the software develops models that can predict structural integrity measures for natural gas pipelines under stress. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Schroeder, Benjamin↗

Computational analysis of flame initiation, quenching, and re-ignition in a prechamber natural gas engine under varying EGR-dilution levels

The on-road natural-gas (NG) fueled transportation relies on stoichiometric spark-ignition engines for the advantages of simple after-treatment system despite the efficiency penalty relative to lean-burn combustion strategies. Exhaust gas recirculation (EGR) has the potential to reduce this efficiency gap at low to moderate loads without the need for complex lean-exhaust aftertreatment systems. However, EGR dilution leads to reduced combustion stability and increased cycle-to-cycle variability. A promising technology that has the potential to achieve reliable operation under diluted conditions is the prechamber ignition (or turbulent jet ignition) which uses chemically active turbulent jets generated from combustion inside a prechamber to initiate, stabilize and accelerate combustion of the mixture inside the main chamber. The present work focusses on developing a RANS-based CFD approach to accurately reproduce in-cylinder phenomena in a stoichiometric NG prechamber-assisted heavy-duty engine without relying on complex combustion models that account for turbulence-chemistry interactions. This is necessary because reactive prechamber jets at high EGR dilution tend to extinguish while emerging into the main chamber, which is followed by a phase of re-ignition — a phenomenon that conventional G-equation or well-stirred reactor combustion models cannot reproduce. With addition of a damping multiplier to the well-stirred reactor model, the predictions are seen to show good agreement with experimental pressure evolution and combustion images acquired from a single cylinder Cummins N-14 optical diesel engine retrofitted with a prechamber ignition system. Model predictions of local heat release in the flame and temperature evolution inside the flame are used to investigate combustion dynamics in the prechamber and the main chamber. It is seen that the well-stirred reactor model with the inclusion of damping is able to reproduce the temporary reduction in heat release within the flame, which can be considered equivalent to quenching of jets, and the subsequent re-ignition of the flame inside the main chamber. The delay between quenching and re-ignition depends on the amount of dilution, as explained by an illustration of flame evolution in a Borghi diagram.

Prechamber ignition↗

Understanding Your Utility Bills: Natural Gas

As a fossil fuel NG is a colorless and odorless gas in its natural state and is one of the cleanest burning hydrocarbons. The factors that contribute to the popularity of natural gas in the US manufacturing sector include ease of availability, clean burning properties, market deregulation, and increased domestic production. Analyzing natural gas (NG) bills can sometimes pose unique problems. Learning to read your utility bills and understand why your utility charges different fees is critical in maximizing your cost savings through energy efficiency. A key to creating a baseline is collecting and analyzing natural gas utility data. Historical data from NG bills can identify trends and help to find the baseline usage for a manufacturing operation. This guide intends to help Better Plant Program partners in understanding natural gas bills and analyzing usage to reduce costs. The guide focuses on natural gas production and transportation, understanding key charges on bills, different rate structures, and saving opportunities. A fictitious worked out example in the final section demonstrates how readers could go about analyzing natural gas bills.

03 NATURAL GAS↗

Hierarchical triply periodic minimal surface structures as heat exchangers and reactors

The present disclosure relates to a transport mechanism apparatus for transporting at least one of a gas or a fluid. The transport mechanism may have an inlet, an outlet and a triply periodic minimal surface (TPMS) structure. The TPMS structure is formed in a layer-by-layer three dimensional (3D) printing operation to include cells propagating in three dimensions, where the cells include wall portions having openings, and where the cells form a plurality of flow paths throughout the transport mechanism from the inlet to the outlet, and where the cells form the inlet and the outlet.

Roy, Pratanu↗

Systems and methods for periodic nodal surface based reactors, distributors, contactors and heat exchangers

The present disclosure relates to a transport mechanism apparatus for transporting at least one of a gas or a fluid. The transport mechanism may have an inlet, an outlet and an engineered cellular structure forming a periodic nodal surface, which may include a triply periodic minimal surface (TPMS) structure. The structure is formed in a layer-by-layer three dimensional (3D) printing operation to include cells propagating in three dimensions, where the cells include non-intersecting, continuously curving wall portions having openings, and where the opening in the cells form a plurality of flow paths throughout the transport mechanism from the inlet to the outlet, and where portions of the cells form the inlet and the outlet.

Iyer, Jaisree Kannan↗

Along the Channel Gradients Impact on the Spatioactivity of Gas Diffusion Electrodes at High Conversions during CO 2 Electroreduction

Results of a 2-D transport model for a gas diffusion electrode performing CO 2 reduction to CO with a flowing catholyte are presented, including the concentration gradients along the flow cell, spatial distribution of the current density and local pH in the catalyst layer. The model predicts that both the concentration of CO 2 and the buffer electrolyte gradually diminish along the channels for a parallel flow of gas and electrolyte as a result of electrochemical conversion and nonelectrochemical consumption. At high single-pass conversions, significant concentration gradients exist along the flow channels leading to large local variations in the current density (>150 mA/cm 2 ), which becomes prominent when compared to ohmic losses. In addition, concentration overpotentials change dramatically with CO 2 flow rate, which results in significant differences in outlet concentrations at high conversions. The outlet concentration of CO attains a maximum of 80% along with 5% CO 2 and 15% H 2 , although the maximum single-pass conversion is limited to below 60% due to homogeneous consumption by the electrolyte. Fundamental and practical implications of our findings on electrochemical CO 2 reduction are discussed with a focus on the trade-off between high current density operation and high single-pass conversion efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗