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1,567 records · Page 75

Improvements in the utilization of calcium carbonate in promoting sustainability and environmental health

Calcium carbonate (CaCO 3 ) is an incredibly abundant mineral on Earth, with over 90% of it being found in the lithosphere. To address the CO 2 crisis and combat ocean acidification, it is essential to produce more CaCO 3 using various synthetic methods. Additionally, this approach can serve as a substitute for energy-intensive processes like cement production. By doing so, we have the potential to not only reverse the damage caused by climate change but also protect biological ecosystems and the overall environment. The key lies in maximizing the utilization of CaCO 3 in various human activities, paving the way for a more sustainable future for our planet.

Chemistry

Ultrafast low-temperature metal–insulator interface phonon dynamics and heat transport in a Pt/Gd 3 Fe 5 O 12 heterostructure

Interfacial thermal and acoustic phenomena have an important role in quantum science and technology, including in spintronic and spincaloritronic materials and devices. Simultaneous measurements of the low-temperature thermal and acoustic properties of a metal/insulator heterostructure reveal distinct dynamics in the characteristic phonon frequency ranges of acoustic and thermal transport. The measurements probed a heterostructure consisting of a thin film of Pt on the ferrimagnetic insulator gadolinium iron garnet (Gd 3 Fe 5 O 12 , GdIG) grown epitaxially on a gadolinium gallium garnet substrate. Ultrafast structural dynamics within the Pt layer were tracked using time-resolved ultrafast x-ray diffraction and analyzed to probe interfacial acoustic and thermal properties. The rapid heating of the Pt layer by a 400 nm wavelength femtosecond-duration optical pulse produced transient structural changes that provided the stimulus for these measurements. Rapid heating produced a broadband acoustic pulse that was partially reflected by the Pt/GdIG interface. Temporal frequencies up to 740 GHz, corresponding to angular frequencies of several THz, were detected in a wavelet analysis of the acoustic oscillations of the strain in the Pt layer. The structural results were analyzed to determine (i) the acoustic damping coefficient and phonon mean free path in Pt at frequencies of hundreds of GHz and (ii) the Grüneisen anharmonicity parameter. The thermal conductance of the Pt/GdIG interface was tracked using the slower, tens-of-picosecond-scale, dynamics of the initial cooling of the heated Pt layer. Analysis using a model based on the Boltzmann transport equation shows that the phonon transmission is lower at the phonon frequencies relevant to thermal transport than for subterahertz regime acoustics.

Acoustic phenomena

Understanding Photovoltage Deficits in Electrochemically Grown Tin Sulfide (SnS) Thin-Film Photovoltaic Devices

Tin­(II) sulfide (SnS) is an earth-abundant semiconductor with a direct optical bandgap of ca. 1.1 eV, which makes it a promising absorber material for thin-film photovoltaic (PV) devices. However, existing devices have significant photovoltage deficits, which may be related to the anisotropic structure of the layered Herzenbergite SnS crystal structure. Here, we explore electrochemical deposition as a near room temperature path to oriented SnS crystal films on Mo and FTO substrates and employ vibrating Kelvin probe surface photovoltage (SPV) spectroscopy and J–V measurements to identify conversion losses in them. According to grazing-incidence X-ray diffraction and SEM, the SnS films consist of crystalline microplates with preferred orientation in the [111] and [001] directions. The bare SnS films produce only small and irreversible surface photovoltage signals, due charge trapping and recombination at the SnS surfaces, but addition of a CdS buffer layer lowers the charge recombination rate by 2 orders of magnitude and increases both the photovoltage and its reversibility due to the formation of a p-SnS/n-CdS junction. According to SPV, the FTO/SnS back interface (but not the Mo/SnS interface) forms a detrimental p–n junction that hinders hole transfer. Additional shunting through the relatively open microcrystal SnS layers and a lower conductivity of the FTO substrate explain the low power conversion efficiencies of the final devices (0.18 and 0.10% for the Mo and FTO substrates). Altogether, this work establishes a low-temperature path for the fabrication of crystalline SnS film-based solar cells and identifies the bottlenecks that limit high photoconversion efficiency.

deposition

Calibration of the Receiver Channel for the GOPEX Precursor Experiments

Calibration measurements for the cooled (253 K) photomultiplier tube (PMT) detector, used on the receiver channel of the transmit/receive (T/R) switch for GOPEX, were conducted in the laboratory. A pulsed frequency-doubled neodymium:yttrium-aluminum-garnet (Nd:YAG) laser was used to direct 532-mn light on the PMT. By monitoring the energy per pulse of the light incident on the PMT, the minimum number of photons detected could be determined. These results agreed with the photon flux back-calculated from the PMT output waveform. Approximately 700 incident photons arriving during a temporal pulse width of approximately 65 nsec were detected with a signal-to-noise ratio (SNR) of approximately 1. Other receiver channel characteristics, such as PMT dark currents, optical transmission, and interference filter sensitivity to angle of light incidence, were also measured.

A Biswas

Enhanced Recovery of Critical Minerals and Geological Hydrogen in The Mine of the Future

invited perspective article: The rapid demand for critical minerals (CMs) and hydrogen (H2) necessitates innovative solutions beyond conventional mining. This study explores enhanced mineral recovery (EMR) and geological hydrogen production (GeoH2) by leveraging the Earth’s subsurface as a reactive platform. Using ultramafic rocks and engineered fluids, the approach simultaneously mobilizes critical resources and produces H2 through natural processes like serpentinization. This paradigm offers a transformative pathway to secure essential materials and diversify energy resources, setting a foundation for the Terrestrial Mine of the Future

Yan, Keju

Enhancing 300 Degree Celsius Electronic Packaging with Ceramic PCBs and Advanced Interconnection Techniques

Geothermal energy development requires downhole tools that operate reliably at temperatures up to 320 °C. While MWD tools work without thermal protection and logging tools use vacuum flasks for limited high-temperature use, Sandia National Laboratories is developing durable electronics on ceramic PCBs with protective coatings to enable long-term operation of geothermal instruments at sustained temperatures up to 300 °C.

Wright, Andrew Alexander [Sandia National Laborato

Delamination recycling of multilayer plastic films: Solvent-assisted separation pathways and recovery of solid polyolefins

Multilayer plastic films are excellent packaging materials due to the bound layers of multiple polymers, with each different polymer contributing to the film properties. Desirable properties lead to continuously growing demand for multilayer films. Multilayer plastic films are typically single-use and, as such, their increased production and disposal have led to waste management problems. Multilayer films are not currently recyclable primarily due to the multiple bound polymers. This work advances delamination as a recycling process to separate and sequester valuable polymers from multilayer films, facilitating the incorporation of these polymers into the circular economy. We effect delamination in a physical process that preserves targeted polymers as solid film, hence retaining their embodied energy. This work documents three different pathways of inducing delamination of multilayer films, with appropriate solvents disrupting adhesion between adjacent layers or dissolving a minor component of the film in less than an hour and at temperatures below 90°C, and where all initial polyethylene is maintained in its solid form throughout the process and is recovered at high purity. Solvent-based delamination is exemplified on commercial multilayer films with majority polyethylene (PE), and polyethylene terephthalate (PET) or ethylene vinyl alcohol copolymer (EVOH) or nylon also present. Solvent-based delamination is an energy-efficient and environmentally friendly recycling process that improves upon dissolution-precipitation recycling, since delamination involves very little dissolution and no precipitation, and is superior to pyrolysis which breaks down the polymers, while delamination keeps polymer chains intact. Furthermore, delamination recycling can contribute to the sustainable use of multilayer films as they continue to protect our food and medicine.

Chemical Recycling

High Temperature Dielectric Properties and Differential Scanning Calorimetry of Lunar Simulants

To guide development of microwave process technology that could be used during in situ construction on the Moon, we measured the high-temperature basic dielectric properties (εʹ and εʺ) of 17 lunar simulants and related materials. In order to confidently use these data one needs to understand the data’s strengths and weaknesses. Therefore, a goal of this publication is to provide insights into the comparative effects of sample composition, pre-treatments, experimental variables, high temperatures, and other factors on the measured response. The dielectric measurements were performed using the cavity perturbation method over a temperature range between room temperature to 1000 °C, or higher, and provided the real and imaginary components of permittivity at six frequencies. The utility of the original values was limited by the varying density of the pellets used in the measurement. Therefore, all of the εʹ and εʺ measurements at the frequency of 2466 MHz have been scaled to a constant density, 1.75 g/cm 3 . Here the data are presented as graphs chosen to aid analysis within and across simulant groups. To gain additional insight into the processes happening at the elevated temperatures in the dielectric measurements, heat capacity data was obtained using differential scanning calorimetry (DSC) on several of the simulant materials. Our data show that over the frequency range 397 MHz – 2985 MHz a material’s behavior does not greatly change, as compared to the scale of differences observed between lunar mare and highland simulants at high temperatures. For example at 1000 °C, the mare simulant JSC-1A absorbs 10 times more power than the highland simulant NUW-LHT-5M. We observe that as melting temperatures are reached both permittivity and dielectric loss rise non-linearly, helping to explain thermal runaway during microware heating. Our data show that even less than a few weight % of many non-lunar minerals, and the use of mixtures in simulants can affect the dielectric behavior at higher temperatures. A comparison of our results with published dielectric data for Apollo samples and with remote sensing of the Moon supports the conclusion the simulants and lunar material at room temperature have very similar dielectric values.

Differential Scanning Calorimetry

Copacabana: a probabilistic membership assignment method for galaxy clusters

Cosmological analyses using galaxy clusters in optical/near-infrared photometric surveys require robust characterization of their galaxy content. Precisely determining which galaxies belong to a cluster is crucial. In this paper, we present the COlor Probabilistic Assignment of Clusters And BAyesiaN Analysis (Copacabana) algorithm. Copacabana computes membership probabilities for all galaxies within an aperture centred on the cluster using photometric redshifts, colours, and projected radial probability density functions. We use simulations to validate Copacabana and we show that it achieves up to 89 per cent membership accuracy with a mild dependence on photometric redshift uncertainties and choice of aperture size. We find that the precision of the photometric redshifts has the largest impact on the determination of the membership probabilities followed by the choice of the cluster aperture size. We also quantify how much these uncertainties in the membership probabilities affect the stellar mass–cluster mass scaling relation, a relation that directly impacts cosmology. Using the sum of the stellar masses weighted by membership probabilities (⁠μ * ⁠) as the observable, we find that Copacabana can reach an accuracy of 0.06 dex in the measurement of the scaling relation at low redshift for a Legacy Survey of Space and Time type survey. These results indicate the potential of Copacabana and μ * to be used in cosmological analyses of optically selected clusters in the future.

79 ASTRONOMY AND ASTROPHYSICS

First in operando transient grating spectroscopy measurements on tungsten during high flux plasma operation in PISCES-RF

This work details the construction and first in operando transient grating spectroscopy measurements conducted on PISCES-RF during plasma operation. A preliminary study on a tungsten sample with varied plasma species (Ar and D 2 ), ion flux (4 × 10 21 to 6 × 10 22 ion/m 2 /s), ion energy (5 to 80 eV), and surface temperature (20 to 200 °C) is presented. Prior to plasma exposure, the thermal diffusivity and surface acoustic wave (SAW) speed, (6.9 ± 0.2) × 10 −5 m 2 /s and (2.66 ± 0.02) km/s, were measured in situ with a thermal grating period of 12.5 μm. During Ar plasma exposure, these two quantities vary according to the sample surface temperature. At low flux and varied ion energy, D 2 plasma exposure also results in thermal diffusivity and SAW speed varying with surface temperature alone. At high flux, D 2 plasma exposure results in no convincing change to the thermal diffusivity, but the SAW speed is reduced. After returning to 20 °C, post plasma exposures, the thermal diffusivity and SAW speed almost recover to the initial value prior to exposure.

Surface acoustic wave SAW

RMCProfile7 : reverse Monte Carlo for multiphase systems

This work introduces a completely rewritten version of the programRMCProfile(version 7), big-box, reverse Monte Carlo modelling software for analysis of total scattering data. The major new feature ofRMCProfile7is the ability to refine multiple phases simultaneously, which is relevant for many current research areas such as energy materials, catalysis and engineering. Other new features include improved support for molecular potentials and rigid-body refinements, as well as multiple different data sets. An empirical resolution correction and calculation of the pair distribution function as a back-Fourier transform are now also available.RMCProfile7is freely available for download at https://rmcprofile.ornl.gov/.

Chemistry

Calibration of the Nonlinear Viscoelastic SPECtacular Model for 828-CTBN/DEA/GMB and 828/Z/AlOx

Nonlinear viscoelastic model calibrations are developed for two filled epoxies: an adduct of Epon 828 DGEBA and CTBN cross-linked with diethanolamine (DEA) filled with glass microballoons, called 828-CTBN/DEA/GMB, and Epon 828 DGEBA cross-linked with Ancamine Z and filled with alumina, called 828/Z/AlOx. The thermo-mechanical responses of these materials are represented using the SPECtacular constitutive model, an extension of the Simplified Potential Energy Clock (SPEC) model. The model couples

Cundiff, Kenneth Noel [Sandia National Laboratorie

Phonon-mediated ultrafast dynamics in self-assembled monolayers of 4-mercaptobenzoic acid on gold

Non-equilibrium interactions between plasmonic metals and adsorbed molecules lie at the heart of emerging applications such as plasmonic photocatalysis and sensing, though the ultrafast charge and energy transfer mechanisms arising from these interactions are not well understood. Herein, we investigate the ultrafast dynamics of Au nano-islands tethered with a self-assembled monolayer (SAM) of electron-withdrawing 4-mercaptobenzoic acid (4MBA) molecules. Ultrafast UV-visible transient absorption spectroscopy following excitation of the interband transition in Au reveals three well-known, characteristic time constants that quantify electron–electron (el–el), electron–phonon (el–ph) and phonon–phonon (ph–ph) scattering lifetimes. When comparing the dynamics of bare Au and 4MBA-Au, we find that the el–ph and ph–ph scattering lifetimes are notably longer in 4MBA-Au. Density functional perturbation theory calculations ascribe the elongation in el–ph lifetimes in 4MBA-Au to the significant coupling of acoustic phonon modes of Au with certain molecular vibrations of 4MBA, leading to decreased spatial overlap between carrier electronic states and the acoustic modes. We speculate that the elongation of ph–ph scattering lifetimes in 4MBA-Au arises due to poor thermal conductivity of the SAM which disrupts efficient energy dissipation from Au to the environment, thus slowing down the thermalization of phonons. This work provides a glimpse into how molecular adsorbates modify the charge carrier and phonon dynamics of Au and sets the stage for further systematic exploration of plasmonic metal–molecule interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Boundary Layer Analysis of Shock Tube Flows

Shock tubes offer a controlled environment to reproduce kinetic and radiative phenomena characteristic of atmospheric entry flows under ground-test conditions. The boundary layer developing behind the incident shock wave determines the available test time, influences particle residence times important for similarity scaling, and can affect radiative energy transport. In this study, we couple a quasi-1D space marcher with the compressible boundary-layer equations to numerically compute the post-shock flow in a shock frame of reference for various test gas mixtures representative of different planetary atmospheres. The solvers are individually verified against CFD simulations and analytical correlations available in the literature. Coupled solutions are computed for a finite-rate chemistry in the boundary layer and a non-catalytic isothermal wall. Results yield refined estimates of the maximum separation distance, as well as insights into concentration profiles of relevant species within the boundary layer.

Andrea Fagnani

Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors

The mesoscopic phase behavior of decylmethylimidazolium (C 10 mim) ionic liquids (ILs) bearing three monovalent anions—thiocyanate (SCN − ), nitrate (NO 3 − ), and chloride (Cl − )—mixed with water at relatively high IL contents (50–95 wt%) was investigated. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) were employed to follow the evolution of both local and mesoscale structures across this composition range. In the absence of water, C 10 mimSCN and C 10 mimCl behaved as disordered liquids, whereas C 10 mimNO 3 spontaneously formed a hexagonally ordered cylindrical mesophase and displayed a sticky-solid macroscopic appearance. Upon addition of water, C 10 mimSCN remained a viscous liquid and only weakly ordered lamellar domains were observed. This limited ordering is attributed to the lack of hydrogen bonding and weak interaction energy between SCN − anions and C 10 mim + cations. In contrast, the trigonal-planar NO 3 − and point-like Cl − anions promoted the formation of well-defined hexagonal mesophases up to 35–45 wt% water. The formation of hydrogen bonding of the two anions with imidazolium ring protons likely enabled the creation of compact ion clusters that effectively exclude water molecules from the immediate vicinity of the IL aggregates. These findings demonstrate that the interaction energy between ion pairs dictate IL-water interactions and therefore control the transition from disordered liquids to ordered mesophases in IL/water mixtures with high IL contents. In conclusion, the combined SAXS/WAXS analysis reveals a correlation between local intermolecular structure and the emergence of mesoscopic order, providing a systematic framework for tailoring mesoscale structures in alkylimidazolium-based IL/water systems.

36 MATERIALS SCIENCE

3D Printing of Polyelectrolyte Complex-Integrated Photocurable Hydrogel Resins

In this study, we developed a photocurable hydrogel resin incorporating a polyelectrolyte complex (PEC) for 3D printing. Acrylamide-based monomers were formulated with varying PEC contents (0–15 wt %) in an aqueous KBr medium to fabricate patterned porous hydrogel structures. The morphology of printed hydrogels was characterized by field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. Notably, the PEC5 and PEC10 formulations exhibited optimal thermal stability and compressive properties, attributed to the homogeneous distribution of PEC domains within the hydrogel matrix. Furthermore, dye adsorption experiments demonstrated excellent removal efficiency, highlighting the potential of PEC-containing hydrogels for environmental remediation applications, particularly in the treatment of dye-contaminated wastewater.

Yang, Jinchul [University of Tennesse Knoxville]

BISON analyses of TRISO fuel performance, its dependence on time-at-temperature, and possible implications for fuel design and qualification

The Advanced Gas Reactor Fuel Development and Qualification (AGR) program has established a substantial technical foundation to support private entry into the U.S. high-temperature gas-cooled reactor market. However, emerging tristructural isotropic (TRISO)-fueled reactor applications include small modular reactors and microreactors with longer fuel residence times, which may expose fuels to higher time-at-temperature (TAT) values than were explored by the AGR program. Increased TAT could affect diffusive and thermomechanical behaviors such as Pd penetration, fission gas release, creep, and fission product transport. In this work, we applied multiscale best-estimate BISON fuel performance modeling to assess these effects within a representative design space based on the AGR-5/6/7 experiment and analyzed trends in predicted particle and compact fuel performance metrics with possible implications for near-term fuel design and qualification. BISON unambiguously predicted that TRISO fuel performance is sensitive to TAT. Increasing TAT was not predicted to increase the magnitude of failure-inducing tangential stresses in particle coating layers. Predictions obtained using a mechanistic model for Pd penetration indicated that penetration depth does not depend strongly on TAT. While these observations suggest that AGR testing provides a conservative upper bound for the steady-state operation of TRISO particles at lower powers and higher residence times, BISON also predicted that the release of poorly retained Ag would increase with TAT. Because these analyses applied models to extrapolate beyond the available experimental data, the authors recommend performing targeted experiments to confirm these predictions. Nevertheless, these predictions may provide reactor developers with enough confidence to make near-term design decisions associated with the potential fuel performance trade-offs of increasing TAT.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Laboratory Investigations: Low Earth Orbit Environment Chemistry With Spacecraft Surfaces

Long-term space operations that require exposure of material to the low earth orbit (LEO) environment must take into account the effects of this highly oxidative atmosphere on material properties and the possible contamination of the spacecraft surroundings. Ground-based laboratory experiments at Los Alamos using a newly developed hyperthermal atomic oxygen (AO) source have shown that not only are hydrocarbon based materials effected but that inorganic materials such as MoS2 are also oxidized and that thin protective coatings such as Al2O3 can be breached, producing oxidation of the underlying substrate material. Gas-phase reaction products, such as SO2 from oxidation of MoS2 and CO and CO2 from hydrocarbon materials, have been detected and have consequences in terms of spacecraft contamination. Energy loss through gas-surface collisions causing spacecraft drag has been measured for a few select surfaces and has been found to be highly dependent on the surface reactivity.

Jon B Cross