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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.

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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Comprehensive two-dimensional gas chromatography under low-pressure conditions

The analysis of thermally labile and high-boiling point compounds by gas chromatography (GC) can be a challenge. One technique to overcome these challenges is low-pressure GC, which uses the vacuum produced from the mass spectrometer and wide-bore columns to elute compounds at significantly lower temperatures. While GC-MS is a powerful technique, comprehensive two-dimensional gas chromatography (GC × GC), allows for resolution of compounds that would typically coelute using GC. Here, in this study, a pesticide standard mixture (8270 MegaMix Standard) was analyzed using a conventional GC × GC-TOFMS configuration (0.25 mm inner diameter (i.d.) to a 0.18 mm i.d. column) and low-pressure GC × GC-TOFMS configuration (0.53 mm i.d. to a 0.53 mm i.d. column). Elution temperatures, sensitivity, and peak capacity were investigated for both configurations. Compounds eluted an average of 30 °C less on the low-pressure GC × GC-TOFMS configuration compared to the conventional GC × GC-TOFMS configuration. Moreover, the compounds were separated in ~13 min on the low-pressure GC × GC-TOFMS as opposed to 33 min for conventional GC × GC-TOFMS. However, due to the wide-bore columns and faster runtimes the low-pressure GC × GC-TOFMS had a lower, β corrected 2D peak capacity, n c,β,2D , of 1260 while the conventional GC × GC-TOFMS was 3588. Interestingly, both configurations yielded a similar peak capacity production of 93 peaks/min and 107 peaks/min for low-pressure and conventional GC × GC-TOFMS, respectively. A “real world” sample of diesel fuel was tested on the low-pressure and conventional GC × GC-TOFMS configurations and similar results were obtained compared to the pesticide standard mix except the peak capacity production of the low-pressure GC × GC-TOFMS configuration was higher than that of the conventional GC × GC-TOFMS method.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Performance and lifetime of intercalative water deionization cells for mono- and divalent ion removal

We report intercalative deionization (IDI) uses two cation intercalation electrodes separated by an anion exchange membrane in a symmetric cell design that has the potential to deliver electrochemically desalinated water in an energy- and water-efficient way. Here, we define and measure metrics to describe the performance and lifetime of IDI cells and compare them for NaCl and CaCl 2 feed solutions. With 20 mM NaCl, NiHCF/AEM/NiHCF flow cells achieve 10 mM average concentration change at a productivity of 20 l/h/m 2 and 5 mM average concentration change at 130 l/h/m 2 . In both cases the cells are operated at a 3C current rate and consume ~30 Wh/m 3 of energy. With 10 mM CaCl 2 , the specific capacity and salt removal of IDI flow cells is ~4 times lower. NiHCF/NiHCF beaker cells with CaCl 2 electrolyte suffer from strong capacity fade, while the same cells with NaCl electrolyte achieve 500 cycles without any capacity fade. Our post-mortem analysis using X-ray diffraction, secondary electron microscopy, energy dispersive X-ray spectroscopy, synchrotron-based X-ray absorption spectroscopy and micro X-ray fluorescence mapping reveals that NiHCF dissolves upon repeated intercalation with Ca 2+ , releasing residual K + , Ni 2+ and Fe(CN) 6 3 , which precipitates as a crystalline decomposition product on the electrodes. This side reaction deprives the active material NiHCF of charge compensating Fe, and thus accounts for the observed capacity fade.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Experimental performance of ejector heat pump operating in the sub-critical mode

Ejector heat pump (EHP) is an efficient-energy technology with a promising potential to replace the vapor compression cycle in heating and cooling applications. It can be powered by low-grade waste heat and uses environmentally friendly working fluids. EHP has also become a viable solution in research seeking cooling applications. However, little attention has been paid to using EHP for heating purposes. In order to investigate this, a steam EHP for domestic water heating was designed and built. The coefficient of performance (COP) is evaluated at various operating and design conditions in sub-critical operational modes to achieve higher condensation temperatures. Two primary nozzles with a throat diameter of 1.5 mm and 2.0 mm were investigated. The primary nozzle is movable along the ejector’s axis, allowing investigation of its positional effects on the EHP’s COP. Further, experimental measurements revealed that using a smaller throat diameter results in a high COP and low back pressure. The EHP COP and back pressure increase when the LTE temperature increases. Using a throat diameter of 1.5 mm, the EHP COP increases as the nozzle exit position (NXP) becomes closer to the constant area section. A COP of 2.42 and a back pressure of 4.28 kPa are achieved at a high-temperature evaporator (HTE) temperature of 130 °C and a low-temperature evaporator (LTE) temperature of 30 °C using a primary nozzle with 1.5 mm.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2023

Impacts of divalent cations (Mg 2+ and Ca 2+ ) on PFAS bioaccumulation in freshwater macroinvertebrates representing different foraging modes

Per- and polyfluoroalkyl substances (PFAS) have extensively contaminated freshwater aquatic ecosystems where they can be transported in water and partition to sediment and biota. In this paper, three freshwater benthic macroinvertebrates with different foraging modes were exposed to environmentally relevant concentrations of eight perfluoroalkyl carboxylates (PFCA), three perfluoroalkyl sulfonates (PFSA), and three fluorotelomer sulfonates (FTS) at varying divalent cation concentrations of magnesium (Mg 2+ ) and calcium (Ca 2+ ). Divalent cations can impact PFAS partitioning to solids, especially to sediments, at higher concentrations. Sediment dwelling worms (Lumbriculus variegatus), epibenthic grazing snails (Physella acuta), and sediment-dwelling filter-feeding bivalves (Elliptio complanata) were selected due to their unique foraging modes. Microcosms were composed of synthetic sediment, culture water, macroinvertebrates, and PFAS and consisted of a 28-day exposure period. L. variegatus had significantly higher PFAS bioaccumulation than P. acuta and E. complanata, likely due to higher levels of interactions with and ingestion of the contaminated sediment. “High Mg 2+ ” (7.5 mM Mg 2+ ) and “High Ca 2+ ” (7.5 mM Ca 2+ ) conditions generally had statistically higher bioaccumulation factors (BAF) than the “Reference Condition” (0.2 mM Ca 2+ and 0.2 mM Mg 2+ ) for PFAS with perfluorinated chain lengths greater than eight carbons. Long-chain PFAS dominated the PFAS profiles of the macroinvertebrates for all groups of compounds studied (PFCA, PFSA, and FTS). Furthermore, these results indicate that the study organism has the greatest impact on bioaccumulation, although divalent cation concentration had observable impacts between organisms depending on the environmental conditions. Elevated cation concentrations in the microcosms led to significantly greater bioaccumulation in the test organisms compared to the experimental reference conditions for long-chain PFAS.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Diesel fuel properties of renewable polyoxymethylene ethers with structural diversity

Polyoxymethylene ethers (POMEs) are a class of low-soot and high-cetane oxygenate oligomers of structure RO-(CH 2 O-) $n$ -R, with different chain lengths ($n$) and end-groups (R) that determine their diesel-like fuel properties. Commercial POMEs with methyl end-groups (MM-POME 3-6 ) exhibit undesirably low energy density and high-water solubility. A previous computational assessment indicated that the lower heating value (LHV) and water solubility for MM-POME 3-6 both improve upon end-group exchange with larger butyl, $iso$-butyl and $iso$-pentyl end-groups. Here, we expanded upon our initial trans-acetalization reaction that employed 1-butanol to install butyl end-groups to also include branched, higher carbon-number end-groups using $iso$-butanol and fusel oil as reagents. Additionally, these new products are termed $i$B*POME 1-6 , and FOil*POME 1-5 , respectively, and collectively referred to as R*POMEs. They possess the advantaged properties of the parent MM-POME 3-6 while exhibiting higher LHV (31 MJ kg -1 and 28 MJ kg -1 for $i$B*POME 1-6 , and FOil*POME 1-5 , respectively) and much reduced water solubility (2.7 g L -1 and 1 g L -1 for $i$B*POME 1-6 , and FOil*POME 1-5 , respectively). Additional fuel property analyses were performed using 20 vol% blends of the R*POMEs with a base diesel fuel. Overall, the greater energy density and decreased water solubility of the R*POMEs, as well as their synergistic blending with diesel at moderate blend levels, provide the greatest benefits to consumers and position this group of products as an environmentally friendlier blendstock alternative to the commercially available MM-POME 3-6 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Subsoil organo-mineral associations under contrasting climate conditions

Climate differences can induce profound changes in organo-mineral associations in soils. However, the magnitude of these modifications, whether as a direct effect of climate conditions or an indirect effect through changes in soil mineralogy, are still not fully understood. In this study, we aimed to improve understanding of how climate and resultant changes in soil mineralogy affect subsoil (i.e., 0.4–0.9 m) organo-mineral interactions at the macro- and microscale. A set of subsoil samples were collected throughout an elevation gradient (approximately 1800 to 2400 mm precipitation year –1 and 15 to 24ºC) on Kohala Mountain, Hawaii. We carried out a combined approach of bulk soil analyses with mineral extractions and spectroscopic and spectromicroscopic analyses. Significant positive correlations (p < 0.05) between soil organic carbon (SOC) with extracted Fe and Al (dithionite citrate bicarbonate – DCB and ammonium oxalate – OX) at the bulk soil scale supported prior research showing concurrent decline of subsoil Fe, Al and SOC above a precipitation level of ~2000 - ~2200 mm year -1 . However, divergence in microscale organo-mineral associations identified using NanoSIMS allowed us to discern the relative roles of Fe and Al in promoting organo-mineral associations. At the lower precipitation range (~1800 mm year -1 ), the clay fraction < 2 µm showed higher amounts of organic matter (OM) co-localized with Fe & Al compared with the higher precipitation level (~2300 mm year -1 ), where OM was mostly unassociated or only associated with Al. While Fe contributed to approximately 40% of the microscale organo-mineral associations in the lower precipitation site (quantified by co-localizations with OM segments), this contribution at the higher rainfall regime was only 5%. In contrast, the contribution of Al was approximately the same in both rainfall levels (approximately 30%). Therefore, associations with Al may be more important than Fe for OM stabilization under reducing climate conditions. The normalized CN:C ratio based on individual pixels was found to be higher when co-localized with Al, Fe, or both, especially under the high precipitation regime. This fact points towards the importance of Fe and Al to stabilize more N-rich OM, especially at high rainfall levels. In addition, subsoil from higher rainfall conditions exhibited more reduced forms of Fe (assessed by Fe K-edge XANES) and lower proportions of carboxyl-C (5% lower in the relative abundance) as well as higher alkyl/O-alkyl ratios determined by CP-MAS 13C NMR. Such differences in composition may directly influence the organo-mineral associations at both locations, as differences in Fe reduction and the presence of carboxyl-C groups are recognized to play a role in OM stabilization. We conclude that spatial relationships between Fe and Al with SOC at the microscale show a shift towards Al-dominated SOC associations at higher precipitation that could not be ascertained from bulk measurements alone. Therefore, they are of fundamental importance to understand the impact of climate change on SOC stabilization.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Mechanisms and kinetics of citrate-promoted dissolution of a uranyl phosphate mineral

The formation of uranyl phosphate precipitates is a remediation strategy to limit the mobility of uranium in contaminated soils. However, exposure to organic ligands, like the plant exudate citrate, can remobilize the uranium. The purpose of this study is to provide a more thorough comprehension of citrate-promoted dissolution of a uranyl phosphate mineral, chernikovite [(H 3 O)(UO 2 )(PO 4 )·3H 2 O], by determining the extent of uranium release from chernikovite at a wide range of citrate concentrations. Here we have quantified the kinetics of dissolution and proposed potential mechanisms of chernikovite dissolution to gain a better understanding of the fate of uranyl phosphate precipitates in the environment. Batch dissolution and continuously stirred tank reactor (CSTR) experiments indicate that increasing citrate concentrations from 0.1 mM to 50 mM increases the concentration of dissolved uranium. However, at citrate concentrations of 10 mM and greater, the effectiveness of the ligand to enhance the dissolution decreases. Density functional theory modeling and Raman spectroscopy indicate a strong interaction between citrate and the uranyl ions at the surface of the uranyl phosphate. The interaction between citrate and uranyl suggests the formation of an alteration layer of uranyl-citrate surface complexes, which could impede uranium release at citrate concentrations of 10 mM or higher. Together, these results indicate that the citrate-promoted dissolution of chernikovite is a fast reaction that is hindered by a combination of surface saturation and a secondary-phase precipitation reaction at higher concentrations of citrate and reaction times greater than or equal to 72 min based on the hydraulic residence time of CSTR experiments. These findings improve our understanding of the stability of uranyl phosphate for use in sequestration of uranium groundwater plumes at contaminated sites.

58 GEOSCIENCES↗
DOE OSTI2025

Phosphate-modulated transformation of Sb(V)-bearing ferrihydrite under microbial iron- and sulfate-reducing conditions

Antimony (Sb) is a toxic metalloid that poses environmental risks in terrestrial and aquatic systems. The fate of the Sb(V) oxyanion, Sb(OH) 6 − , is governed by complex biogeochemical processes, including immobilization by ferric (Fe(III)) oxides, reduction by sulfide, and the less-explored competitive adsorption with other anions such as phosphate (PO 4 3− ). Here, this study investigates the interplay between such mechanisms in controlling the behavior of Sb(V) associated with ferrihydrite (Fh) under Fe(III)- and sulfate-reducing conditions, with a particular emphasis on the role of phosphate in influencing Sb(V) mobility and transformation. Anoxic reactors that contained Sb(V)-coprecipitated Fh, varying PO 4 3− concentrations (0, 0.2, and 2 mM), and sulfate, were inoculated with a microbial community sourced from Sb-contaminated soil. Additionally, abiotic reactors with either Sb(V)-adsorbed or Sb(V)-coprecipitated Fh and different PO 4 3− loadings (0–100 mM) were created to investigate the competitive adsorption mechanisms in the absence of microbial activity. Results from the abiotic reactors suggest that Sb(V) is likely incorporated into the Fh structure, with only minor amounts remaining surface-bound and extractable by PO 4 3− . In the biotic reactors, microbial Fe(III) and sulfate reduction were more extensive in the presence of PO 4 3− . At 0.2 mM PO 4 3− , microbial activity transformed Fh into siderite and led to the complete reduction of Sb(V) to Sb(III) as stibnite (Sb 2 S 3 ). At 2 mM PO 4 3− , the greater coverage by PO 4 3− stabilized Fh and decreased the extent of both Fe(III) and Sb(V) reduction, and shifted the reduced products to mackinawite and Sb(III) adsorbed onto Fh, in addition to stibnite formation. This study demonstrates that while PO 4 3− may not directly compete with Sb(V) for sorption sites, it can influence Sb mobility in Fe(III)- and sulfate-reducing environments by enhancing microbial activity and altering the mineralization pathways.

Microbial Fe(III) and sulfate reduction↗
DOE OSTI2019

Advanced high-performance large diameter Cs 2 HfCl 6 (CHC) and mixed halides scintillator

This paper reports on successful growth and performance evaluation of two large diameter Cs 2 HfCl 6 (CHC) and Cs 2 HfCl 4 Br 2 (CHCB), both recently developed scintillator crystals. The discovery of Cs 2 HfCl 6 (CHC) as a scintillator has lately generated much interest in this material and its family, which belongs to the K 2 PtCl 6 cubic crystal structure. CHC is an intrinsic scintillator that is non-hygroscopic (slightly deliquescent, i.e., slightly moisture sensitive but does not deteriorate much when left in air), has no self-radioactivity, provides excellent energy resolution, and has excellent non-proportionality. CHC has a moderate density of 3.9 g/cm 3 and an effective atomic number of 58. Reported in this paper are transparent crack-free single crystal CHC and CHCB boules of one inch in diameter, both grown using the vertical Bridgman method. Samples retrieved from the boules, sized 23 mm × 30 mm and 23 mm × 26 mm, respectively, are characterized for their optical and scintillation properties. Energy resolutions of 3.5% and 3.7% (FWHM) at 662 keV, respectively, are reported. Light yields of 23,000 ph/MeV and 20,000 ph/MeV have been calculated for the large diameter CHC and CHCB crystals, respectively. Results comparable to previously reported results for smaller crystals have been obtained. Studies on decay time, non-proportionality, as well as detector characterization are also reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Synthesis of poly(3,4-ethylenedioxythuophene) derivatives using three-armed conjugated cross-linker and its thermoelectric properties

Conducting polymer based thermoelectric systems are very effective at harvesting electricity from waste heat with low-temperature gradients relative to environmental temperature. However, although various studies concerning the doping effect exist, there are insufficient reports on the effect of the change in polymer chain structure on the thermoelectric properties. Here we demonstrate different poly(3,4-ethylenedioxythiophene) (PEDOT)-derivative chain structures (such as linear, two-dimensional, co-polymer), by varying the amount of three-armed conjugated cross-linker (1,3,5-tri(2-thienyl)-benzene (TTB)). Further, at a small amount of TTB addition (until 0.5 mM), the electrochemical charge transport of the PEDOT films increased without shift of the UV–Vis absorbing property. However, from higher than 0.5 mM TTB, electrochemical charge transport decreased with blue shift of the UV–Vis absorbing curve. Moreover, the power factor of the PEDOT-derivative films without TTB to a small amount of TTB (0.5 mM) was improved from (27.03 to 49.43) µWm -1 K -2 , and at higher than 0.5 mM TTB concentration, was diminished, respectively, because a small amount of TTB enhanced the π–π interaction of the polymer chains without disrupting the conjugation, while excess TTB molecules blocked conjugation of the polymer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Enhanced joining strength in additive-manufactured polylactic-acid structures fused by embedded heated metallic meshes

Additively manufactured thermoplastic polymers, such as polylactic acid (PLA), hold significant promise for sustainable engineering structures, including wind turbine blades. Upscaling these structures beyond the limitations of 3D printer build volumes is a challenge; fusion joining presents a potential solution. This paper introduces a displacement-controlled resistance welding process for PLA, as an alternative to the typical force-controlled methods. Here, we investigated the bonding quality of resistance-welded and adhesive-bonded PLA beams through three-point bending and measured the surface deformations using digital image correlation. Different metal meshes (30%/0.11 mm Ni—Cu, 34%/0.07 mm Ni—Cu, and 36%/0.25 mm Co—Ni) served as heating elements. The process parameters were varied for the 34%/0.07 mm Ni—Cu mesh to identify an optimum set of parameters. Results showed that this optimized displacement-controlled welding achieved 94% of the original strength of monolithic samples. This indicates that the new welding process not only ensures high-quality bonding and fine surface finishing but also promotes sustainability, recyclability, and economic efficiency in various polymer and composite structural applications.

Additive manufacturing↗
DOE OSTI2025

Radiation-induced bowing of SiC/SiC composites under neutron flux gradients—integral experimental data for model validation

Here, the radiation-induced swelling of SiC and its composites, including strong dependencies on temperature and dose, can drive significant lateral bowing in the presence of temperature and/or dose gradients. In recent years, simulations have been performed to assess the extent of bowing in SiC composite light-water reactor (LWR) fuel cladding and boiling water reactor (BWR) channel boxes. However, to date, no integral experimental data exist to validate these models. This work provides the first experimental bowing evaluation of three ∼380 mm long SiC composite specimens irradiated under varying neutron dose gradients (∼50°C–60°C, 0.03–0.06 dpa): two tubes (∼9.8 mm diameter) and a miniature BWR channel box (∼30 mm square). The measured radiation-induced length swelling (∼0.3%–0.7% linear) was consistently 10%–21% higher than values obtained from 3D finite element structural analyses with inputs from 3D radiation transport calculations. This discrepancy could be at least partially explained by differences in dose rate (∼10 -8 dpa/s) compared to the literature data (∼10-6 dpa/s) used to establish the dose-to-swelling correlations in the model. Nevertheless, the modeled bowing magnitudes (<2 mm) obtained from finite element analyses and simple analytical equations were within the bounds of the experimental measurements for all specimens. With improved confidence in the ability to predict the structural response and measure the macroscopic deformations, future experiments will target transient bowing under neutron flux gradients at representative LWR temperatures and assess whether grid spacers can mitigate the tens of millimeters of bowing that would otherwise be expected in ∼4 m long LWR components.

bowing↗
DOE OSTI2020

Observation of a THz-sub-THz spontaneous coherent undulator radiation driven by a low energy electron beam from a thermionic RF electron gun

In this work, we report observations of an intense, multi-band, sub-THz and THz radiation extracted from a similar to 2-3 MeV electron beam with a flat transverse profile propagating in an oversized rectangular waveguide placed into a 3.25 mm gap of a planar undulator having 1.3 cm period and similar to 20 cm length. Radiation outcoupling is accomplished using a horn antenna and a miniature permanent in-vacuum magnet separating the mm-sub-mm-waves and electron beam. A table-top experiment utilizes a radio frequency thermionic electron gun delivering a thousand momentum-chirped microbunches per macropulse and an alpha-magnet producing microbunches of a sub-mm length. Total radiated energy of a sub-millijoule per a microsecond radio frequency macropulse is demonstrated with flux more than ten micro-Joules per centimeter squared. With 1 THz filter the energy measured is about 1 microjoule and flux of a few micro-Joules per centimeter squared.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Quantifying spatial resolution in a fast neutron radiography system

Neutron imaging is a powerful nondestructive examination modality that has been employed in various applications. Fast neutrons provide advantages over lower energy neutrons, such as examining thicker samples and inducing negligible activation and transmutations. However, fast neutrons interact mostly via elastic scattering with both the neutron detector and the object, causing degradation in spatial resolution. This study explores the quantification of spatial resolution caused by the testing target itself and suggests proper candidate materials for characterizing spatial resolution in terms of modulation transfer function. Knife-edge radiographs of 3 mm, 6 mm, and 5 cm thick Tantalum (Ta) foils, and a 2.54 cm Tungsten (W) cube were acquired using a CCD-based imaging system and a Polyvinyl Toluene (PVT) scintillator at the Ohio State Research Reactor (OSURR)’s fast neutron beam facility. The spatial resolutions calculated were 195 ± 20 μm, 224 ± 22 μm, 248 ± 25 μm, and 435 ± 44 μm for 3 mm, 6 mm, and 5 cm Ta foils, and 2.54 cm W cube, respectively. The results showed a worsening spatial resolution with increasing target thickness. Simulations and calculations estimate that elastic scattering kinematics between neutrons and protons in the PVT medium also limits spatial resolution, and it sets a lower limit of ~44 μm on the spatial resolution for 2 MeV neutrons.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2025

The effect on soot and its gas precursors of doping ethylene with 2,2,4,6,6-pentamethyl-heptane in the nitrogen-fuel stream of a laminar non-premixed Planar Mixing Layer Flame (PMLF)

Synthetic Aviation Turbine Fuels (SATFs) are promising for reducing soot emissions from the aviation sector and diversifying Jet Fuel (JF) sources. Accurately predicting the combustion and emissions behavior of SATFs (and other JFs) necessitates robust experimental databases to elucidate the chemistry of long-chain iso-paraffins, which can compose up to two-thirds of SATF blends and whose behavior is considered to be well-represented by that of iso-dodecane isomers. Here, this study characterizes two laminar non-premixed Planar Mixing Layer Flames (PMLFs) with mild soot loads fueled by nitrogen-diluted ethylene, pure and doped with 2,2,4,6,6-pentamethyl-heptane, respectively. The two PMLFs have the same stoichiometric mixture fraction and total hydrocarbon mole fraction in the fuel stream (X F,F =X C2H4,F +X C12H26,F = 0.260), resulting in nearly the same maximum temperature (T max ≈1800 K) and simple identification of the effects of doping. Importantly, any horizontal PMLF cross-section has a self-similar structure that can be modeled as an equivalent One-Dimensional Counterflow Flame (1D-CF) with vanishingly small strain rate (a). The cross-section at a Height Above the Burner (HAB) of 50 mm is characterized in terms of C 0 -C 18 gas species using capillary sampling followed by GC-MS analyses. Laser-Induced Emission Spectroscopy (LIES) quantifies the soot volume fraction (ƒ v ) profiles at HAB=25 and 50 mm where Elastic Laser Light Scattering (E-LLS) is performed to determine the a of the equivalent 1D-CFs and the profile of the E-LLS equivalent diameter ( d 6,3 ) of soot. The substitution of 1500 ppm of ethylene with 2,2,4,6,6-pentamethyl-heptane causes an increase of ≈1.5 in the concentrations of several polycyclic aromatic hydrocarbons and fv. Concurrently, the measured d 6,3 doubles in the oxidizer stream, yet remains the same in the fuel stream, at HAB=50 mm. Instead, at HAB= 25 mm, the iso-dodecane doping does not affect the d 6,3 profile in either stream. The experimental results partially validate the chemical reactions and soot formation kinetic model developed at Lawrence Livermore National Laboratory and provide directions to further improve its predictions.

Iso-dodecane (2,2,4,6,6-Pentamethyl-Heptane)↗
DOE OSTI2020

Capturing Deuteration Effects in a Molecular Mechanics Force Field: Deuterated THF and the THF–Water Miscibility Gap

Deuteration is a common chemical modification used in conjunction with experiments such as neutron scattering, NMR, and Fourier-transform infrared for the study of molecular systems. Under the Born–Oppenheimer (BO) approximation, while the underlying potential energy surface remains unchanged by isotopic substitutions, isotopic substitution still alters intramolecular vibrations, which in turn may alter intermolecular interactions. Molecular mechanics (MM) force fields used in classical molecular dynamics simulations are assumed to represent local approximations of the BO potential energy surfaces, and hence, MD simulations using simple isotopic mass substitutions should capture BO-compatible isotope effects. However, standard MM force-field parameterizations do not directly fit to the local harmonic quantum mechanical (QM) Hessian that describes the BO surface, but rather to QM normal-modes and/or mass-dependent internal-coordinate derived distortion energies. In this study, using tetrahydrofuran (THF)–water mixtures as our model system, we show that not only does a simple mass-substitution approach fail to capture an experimentally characterized deuteration effect (the loss of the closed-loop miscibility gap associated with the complete deuteration of THF) but also it is necessary to generate new MM force-field parameters that correctly describe isotopic dependent vibrations to capture the experimental deuteration effect. We show that the origin of this failure is a result of using mass-dependent features to fit the THF MM force field, which unintentionally biases the bonded terms of the force field to represent only the isotopologue used during the original force-field parameterization. In addition, we make use of our isotopologue-corrected force field for D 8 THF to examine the molecular origins of the isotope-dependent loss of the THF–water miscibility gap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electrostatic Gating of Ionic Conductance through Heterogeneous van der Waals Nanopores

Nanofluidic ionic transistors typically require gate voltages above 1 V and operate only at submillimolar ionic strengths, limiting their biocompatible applications. We demonstrate ionic transistors consisting of single sub-10 nm nanopores drilled in van der Waals (vdW) heterostructures with internal gate electrodes made of few-layer graphene. These devices deliver up to 10-fold current modulation at gate voltages as low as 0.3 V in 10 mM KCl, and ∼2-fold modulation at near-physiological 100 mM KCl. Baseline conductance with no gate shows surface-charge-dominated transport below 100 mM KCl, consistent with negatively charged hBN walls and ∼5 nm opening of the pores. The surface charge and the electrochemical asymmetry introduced by the three-electrode configuration govern the device’s behavior: negative gate voltage (V G ) enriches ionic concentrations and enhances current, whereas positive V G induces a local depletion zone that suppresses transport. The current modulation by V G is dependent on the polarity of the transmembrane potential and leads to ion current rectification. Molecular dynamics simulations of a nanopore in a hBN–graphene–hBN stack reveal confinement and surface charge-dependent suppression of the relative permittivity of interfacial water. Continuum modeling with radially varying interfacial water permittivity reproduces the asymmetric I–V characteristics and explains how the embedded gate sculpts local potential and ion concentrations. By enabling sub-0.5 V control of ionic transport at up to 100 mM salt concentrations, these devices address a key need in nanofluidics to create low-power ionic circuits and biosensing.

Materials science↗
DOE OSTI2022

Bedrock Vadose Zone Storage Dynamics Under Extreme Drought: Consequences for Plant Water Availability, Recharge, and Runoff

Bedrock vadose zone water storage (i.e., rock moisture) dynamics are rarely observed but potentially key to understanding drought responses. Exploiting a borehole network at a Mediterranean blue oak savanna site—Rancho Venada—we document how water storage capacity in deeply weathered bedrock profiles regulates woody plant water availability and groundwater recharge. The site is in the Northern California Coast Range within steeply dipping turbidites. In a wet year (water year 2019; 647 mm of precipitation), rock moisture was quickly replenished to a characteristic storage capacity, recharging groundwater that emerged at springs to generate streamflow. In the subsequent rainless summer growing season, rock moisture was depleted by about 93 mm. In two drought years that followed (212 and 121 mm of precipitation) the total amount of rock moisture gained each winter was about 54 and 20 mm, respectively, and declines were documented exceeding these amounts, resulting in progressively lower rock moisture content. Oaks, which are rooted into bedrock, demonstrated signs of water stress in drought, including reduced transpiration rates and extremely low water potentials. In the 2020–2021 drought, precipitation did not exceed storage capacity, resulting in variable belowground water storage, increased plant water stress, and no recharge or runoff. Rock moisture deficits (rather than soil moisture deficits) explain these responses.

54 ENVIRONMENTAL SCIENCES↗