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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Impact of the optical parametric amplification phase on laser pulse compression

Optical parametric chirped-pulse amplification (OPCPA) is an effective way to generate ultrashort pulses that has been used extensively for a variety of applications requiring high peak intensities. Precise control and measurement of a system’s spectral and spatial phases are required for Fourier transform–limited pulse compression and diffraction-limited focusing. Phase accumulated during optical parametric amplification (OPA) can degrade the compressibility and focusability of the pulse, reducing peak intensity. We used analytic and numerical analysis of OPA to study the influence of crystal parameters, wavefront of the pump and signal, and their relative optical alignment on the accumulated phase. Here, we show that the accumulated signal phase is largely independent of amplifier saturation and, with significant local wavefront gradients in the signal or pump beam, the quality of the compressed pulses can be degraded. We use first-order expressions for the pump- and signal-angle sensitivity to evaluate an OPCPA system consisting of a highly deuterated potassium dihydrogen phosphate (DKDP) amplifier designed to support bandwidth for 15 fs pulses centered at 920 nm.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Nanoscale structural evolution and phase transformation of geopolymers: In situ SAXS/WAXS investigation under uniaxial tension at elevated temperatures

This investigation delves into the degradation mechanisms of high-density polyethylene geomembranes (PE GMXs) under a spectrum of conditions, replicating real-world scenarios within a rigorously controlled laboratory setting. The treatment protocols applied induced a notable increase in the crystallinity of the treated specimens relative to the untreated controls. Small-angle x-ray scattering (SAXS) analysis identified an initial long period (interlamellar distance) of 16.9 nm for the untreated polymer, which expanded by 19.5% at a strain of 16.7 percent. Conversely, the treated PE GMXs exhibited a more gradual elongation of the long period, with an increase of merely 10.6% at a strain of 23.3 percent. At an elevated temperature of 65°C, both samples exhibited pronounced strain hardening, with the treated PE GMXs demonstrating superior stability even at a strain of 150 percent. Wide-angle x-ray scattering (WAXS) experiments corroborated these observations, revealing that the diffraction patterns of the untreated PE remained stable up to a strain of 16.7%, whereas those of the treated PE remained distinct up to a strain of 46.1 percent. Scanning electron microscopy (SEM) images substantiated the formation of a shish–kebab structure in the treated samples. The study concludes that the geopolymer underwent oxidation and material degradation as a result of the chemical and mechanical treatments, transitioning to a more crystalline state and concomitantly losing its initial elasticity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

In Situ X-ray Scattering Reveals Coarsening Rates of Superlattices Self-Assembled from Electrostatically Stabilized Metal Nanocrystals Depend Nonmonotonically on Driving Force

Self-assembly of colloidal nanocrystals (NCs) into superlattices (SLs) is an appealing strategy to design hierarchically organized materials with promising functionalities. Mechanistic studies are still needed to uncover the design principles for SL self-assembly, but such studies have been difficult to perform due to the fast time and short length scales of NC systems. To address this challenge, we developed an apparatus to directly measure the evolving phases in situ and in real time of an electrostatically stabilized Au NC solution before, during, and after it is quenched to form SLs using small-angle X-ray scattering. By developing a quantitative model, we fit the time-dependent scattering patterns to obtain the phase diagram of the system and the kinetics of the colloidal and SL phases as a function of varying quench conditions. The extracted phase diagram is consistent with particles whose interactions are short in range relative to their diameter. We find the degree of SL order is primarily determined by fast (subsecond) initial nucleation and growth kinetics, while coarsening at later times depends nonmonotonically on the driving force for self-assembly. We validate these results by direct comparison with simulations and use them to suggest dynamic design principles to optimize the crystallinity within a finite time window. The combination of this measurement methodology, quantitative analysis, and simulation should be generalizable to elucidate and better control the microscopic self-assembly pathways of a wide range of bottom-up assembled systems and architectures.

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

Modeling Sequences of Earthquakes and Aseismic Slip (SEAS) in Elasto-Plastic Fault Zones With a Hybrid Finite Element Spectral Boundary Integral Scheme

We present a coupled finite element spectral boundary integral framework for modeling sequences of earthquakes and aseismic slip on a 2-D planar rate-and-state fault with off-fault visco-plastic response in the plane strain approximation. The model resolves both slow aseismic deformation and inertia effects during rapid slip. As an application, we perform two sets of simulations with different choices of cohesion to explore the co-evolution of fault slip, bulk plasticity and local stress fields. The first set implements a relatively large value of the cohesion parameter, which results in limiting inelastic strain accumulation to dynamic rupture phases. The second set implements a smaller cohesion, allowing for plastic strain to accumulate in both seismic and aseismic phases. For the first model, our results indicate that the extent and distribution of plastic strain depend on the angle of maximum compressive principal stress. At larger angles, inelastic strain accumulates on the extensional side of a dynamically propagating rupture. At smaller angles, the extent of plasticity is limited to the compressional side of the domain. At smaller cohesion values, off-fault plasticity may occur during aseismic slip, which alters the nucleation characteristics and earthquake sequence pattern. Furthermore, our results at lower cohesion values indicate that plastic strain accumulation may occur in both the extensional and compressional sides of the off-fault bulk even at higher angles of maximum compression. In conclusion, this produces damage patterns that deviate from the traditional off-fault fan-like distribution observed in dynamic rupture simulations and emphasizes the significance of long-term deformation in interpreting observations.

58 GEOSCIENCES↗
DOE OSTI2022

Effect of differently oriented interlayer phases on the radiation damage of Inconel-$\mathrm{Ni}$ multimetallic layered composite

Multimetallic layered composites (MMLCs) have shown an excellent potential for application under extreme environments, e.g., accident-tolerant fuel cladding, because of their low oxidation tendency and high corrosion resistance. Interfacial phases or complexions in nanocrystalline materials accelerate the annihilation of defects and enhance the radiation resistance of materials, making MMLCs with engineered interlayer phases compelling to deploy in extreme conditions. However, implementation of MMLCs in full capacity remained a challenge due to a lack of fundamental understanding of the underlying mechanisms governing the characteristics of the interface between the metallic layers. The precise role of interlayer phases in MMLCs and their interaction with defects, specifically under extreme conditions, is still unexplored. Pursuing atomistic simulations for various Inconel-Ni MMLCs model materials, we revealed accelerated defect mobility in interlayers with larger crystalline misorientation and the inverse relationship between the interface sink strength to the misorientation angle. Furthermore, we found a linear relation between interlayer misorientation angle with the density of radiation-induced defects and radiation enhanced displacements. So, our results indicate that radiation-induced material degradation is accelerated by the higher defect formation tendency of MMLCs with a high-angle interlayer interface.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

Beam modulation and bump-on-tail effects on Alfvén eigenmode stability in DIII-D

Beam modulation effects on Alfvén eigenmode stability have been investigated in a recent DIII-D experiment and show that variations in neutral beam modulation period can have an impact on the beam driven Alfvén eigenmode spectrum and resultant fast ion transport despite similar time-averaged input power. The experiment was carried out during the current ramp phase of L-mode discharges heated with sub-Alfvénic 50–80 kV deuterium neutral beams that drive a variety of Alfvén eigenmodes unstable. The modulation period of two interleaved beams with different tangency radii was varied from shot to shot in order to modify the relative time dependent mix of the beam pitch angle distribution as well as the persistence of a bump-on-tail feature near the injection energy (a feature confirmed by imaging neutral particle analyzer measurements). As the beam modulation period is varied from 7 ms to 30 ms on/off (typical full energy slowing down time of τ slow ≈ 50 ms at mid-radius), toroidicity-induced Alfvén eigenmodes (TAEs) located in the outer periphery of the plasma become intermittent and coincident with the more tangential beam. Core mode activity changes from reversed shear Alfvén eigenmodes (RSAEs) to a mix of RSAE and beta-induced Alfvén eigenmodes. Discharges with 30 ms on/off period do not have a persistent bump-on-tail feature, have the lowest average mode amplitude and least fast ion transport. Furthermore, detailed analysis of an individual TAE using TRANSP kick modeling (Monte Carlo evolution of the distribution function with probabilistic 'kicks' by the AEs) and the resistive MHD code with kinetic fast ions, MEGA, find no strong role of energy gradient drive due to bump-on-tail features. Instead, the observed TAE modulation with interleaved beams is likely a pitch angle dependent result combined with slowing down of the tangential beam between pulses. For the conditions investigated, bump-on-tail contributions to TAE drive were found to be 5% or less of the total drive at any given time.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Deformation-enhanced hierarchical multiscale structure heterogeneity in a Pd-Si bulk metallic glass

Here, the multiscale structures in a Pd 82 Si 18 binary bulk metallic glass before and after deformation were studied using electron microscopies, high-energy synchrotron X-ray diffraction, and small-angle scattering techniques. The experimental results revealed an enhancement of hierarchical structure heterogeneities on multiple length scales after deformation. Hierarchical multiple shear bands of high number density were observed after bending, introducing complex but periodically distributed residual strain. Pair distribution function analysis revealed that the connectivity of the short-range clusters on the medium-range scale determines the packing density difference between the tension side and the compression side in the sample after bending. In-situ synchrotron X-ray diffraction study also revealed a transformation of connection modes among short-range clusters under uniaxial tension and compression, which is consistent with those of triaxial tension/compression parts upon bending in Pd 82 Si 18 glassy alloys. The nanoscale heterogeneities for metallic glasses after deformation observed by small-angle scattering and transmission electron microscopy may be attributed to the nanoscale amorphous phase separation and interacting multiple shear bands enhanced by plastic deformation. Our findings suggested that the enhancement of hierarchical heterogeneous structure on multiple length scales may explain the excellent plasticity of Pd-Si glassy alloys, deepening the understanding of structure-property relation during plastic deformation in metallic glasses.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Anomalous U ( 1 ) A couplings and the Columbia plot

When the quark masses are lighter than those in QCD, the standard lore is that a chiral transition of first order must emerge for three light flavors. Recently, however, numerical simulations on the lattice suggest that the chiral transition is of second order in the chiral limit. Using an extended linear sigma model in the mean field approximation, we study the relation between terms which break the anomalous, U ( 1 ) A symmetry and the order of the chiral phase transition, especially how a chiral transition of second order can arise for three massless flavors. We note that in an (unphysical) region of the “Columbia” phase diagram, when the strange quark mass is light and negative, corresponding to topological angle θ = π , the C P symmetry is spontaneously broken. Published by the American Physical Society 2025

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Comparative study of crystallization kinetics and phase segregation of triple cation and methylammonium lead iodide perovskites on moisture probing using synchrotron X-ray based radiation

3D mixed perovskites have achieved substantial success in boosting solar cell efficiency, but the complicated perovskite crystal formation pathway remains mysterious. Here we present detailed crystallization kinetics of mixed perovskites FA 0.83 MA 0.17 Pb(I 0.83 Br 0.17 ) 3 , where FA is formamidinium and MA is methylammonium, with the addition of Cs + to form a triple cation perovskite (3-CAT), in a comparison with the perovskite building block MAPbI 3 (MAPI) via static grazing-incidence wide-angle X-ray scattering (GIWAXS) and micro-diffraction measurements. Spin-coated films produced α-perovskite peaks with no PbI 2 or δ-intermediate phases, which was a promising result for the 3-CAT perovskite from micro-diffraction measurements. However, the 3-CAT did not remain stable on probing with varied relative humidity (RH) conditions as segregation back to the δ-intermediate and PbI 2 phase after 10 s of exposure to an RH value of 11% was found to occur from the GIWAXS results. When RH levels were elevated to over 100%, segregation peaks of PbI 2 and δ-intermediate (2H, 4H and 6H) became conspicuous as the α-phase intensity diminished, unlike for MAPI that remains relatively stable. The possible cause of this is hydrophilic bonds that form between the 3-CAT crystals and the small annealing window of the best composition perovskite (5% Cs + ) film.

Shatsala, Miller (ORCID:0009000927230192)↗
DOE OSTI2020

Predicting Excitation Energies of Twisted Intramolecular Charge-Transfer States with the Time-Dependent Density Functional Theory: Comparison with Experimental Measurements in the Gas Phase and Solvents Ranging from Hexanes to Acetonitrile

Electronically excited states characterized by intramolecular charge transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work, we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and in solvents representing a broad range of polarities, which involve intramolecular charge transfer mediated by a nonzero, "twisted" dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the "optimally tuned" LRC-ωPBE functional, which utilizes a system-specific yet nonempirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 to >20 Debye, the mean signed and absolute errors are 0.02 and 0.18 eV, respectively (compared, e.g., to -0.30 and 0.30 for PBE0, 0.44 and 0.47 for LRC-ωPBEh, 0.83 and 0.83 for ωB97X-V). We analyze the performance of polarizable continuum solvation models available in Q-Chem that partition the solvent response into fast and slow time scales, and clear trends emerge when measurements corresponding to the four small 4-(dimethylamino)benzonitrile (DMABN)-like molecules and a charged species are excluded. We make the case that the large errors found only for small molecules in the gas phase and weak solvents cannot be expected to improve via the optimal tuning procedure, which enforces a condition that is exact only in the well-separated donor-acceptor limit, and present empirical evidence implicating the outsized importance for small donor-acceptor systems of relaxation effects that cannot be accounted for by the linear-response time-dependent density functional theory within the adiabatic approximation. Finally, we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Twisted bilayer graphene. IV. Exact insulator ground states and phase diagram

Here, we derive the exact insulator ground states of the projected Hamiltonian of magic-angle twisted bilayer graphene (TBG) flat bands with Coulomb interactions in various limits, and study the perturbations away from these limits. We define the (first) chiral limit where the AA stacking hopping is zero, and a flat limit with exactly flat bands. In the chiral-flat limit, the TBG Hamiltonian has a U(4) × U(4) symmetry, and we find that the exact ground states at integer filling – 4 ≤ $\textit{ν}$ ≤ 4 relative to charge neutrality are Chern insulators of Chern numbers $ν_C$ = 4 – |$\textit{ν}$ |, 2 – |$\textit{ν}$ |, $\cdots$, |$\textit{ν}$ | – 4, all of which are degenerate. This confirms recent experiments where Chern insulators are found to be competitive low-energy states of TBG. When the chiral-flat limit is reduced to the nonchiral-flat limit which has a U(4) symmetry, we find $\textit{ν}$ = 0 , ± 2 has exact ground states of Chern number 0, while $\textit{ν}$ = ±1, ± 3 has perturbative ground states of Chern number $ν_C$ = ± 1, which are U(4) ferromagnetic. In the chiral-nonflat limit with a different U(4) symmetry, different Chern number states are degenerate up to second-order perturbations. In the realistic nonchiral-nonflat case, we find that the perturbative insulator states with Chern number $ν_C$ = 0 (0 < |$ν_C$| < 4 – |$\textit{ν}$ |) at integer fillings $\textit{ν}$ are fully (partially) intervalley coherent, while the insulator states with Chern number |$ν_C$| = 4 – |$\textit{ν}$ | are valley polarized. However, for 0 < |$ν_C$| ≤ 4 – |$\textit{ν}$ |, the fully intervalley coherent states are highly competitive (0.005 meV/electron higher). At nonzero magnetic field |$\textit{B}$ | > 0, a first-order phase transition for $\textit{ν}$ = ± 1, ± 2 from Chern number $ν_C$ = sgn ($\textit{νB}$)(2 – |$\textit{ν}$ |) to $ν_C$ = sgn ($\textit{νB}$)(4 – |$\textit{ν}$ |) is expected, which agrees with recent experimental observations. Lastly, the TBG Hamiltonian reduces into an extended Hubbard model in the stabilizer code limit.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Decomposition of liquid-liquid extraction organic phase structure into critical and pre-peak contributions

Solution nanostructure induced by amphiphile self-association plays an important role in various chemical and physical processes, including liquid-liquid extraction (LLE). Small angle scattering techniques are an essential means of probing this structure, but, due to non-uniqueness of scattering patterns, their interpretation is not trivial. Here, in this study, we decompose small angle x-ray scattering (SAXS) patterns for a range of binary LLE organic phases into two components: Ornstein-Zernike and pre-peak contributions resulting from, respectively, critical concentration fluctuations and packing of the amphiphilic extractant molecules in the nonpolar aliphatic diluent. While we previously applied Ornstein-Zernike scattering models to similar organic phases, including the pre-peak explicitly in the fit allows us to measure weak fluctuations at high extractant concentration and simultaneously obtain information on the position and intensity of the correlation peak related to amphiphile packing. Scattering patterns and partial structure factors calculated from molecular dynamics simulations support this interpretation. We demonstrate how this minimal scattering model describes nanostructuring for a large number of extractant types over their entire extractant/diluent composition ranges, suggesting simple and universal behavior. The straightforward assignment of these structural contributions facilitates the comparison of these features between different classes of extractant molecules and will enable further studies of organic phase aggregation. Applicability to more complex, process-relevant organic phases is illustrated with post-contact organic phases containing significant quantities of extracted lanthanide nitrate salt, which we find are readily described by this model.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Measurement of the fractional radiation length of a pixel module for the CMS Phase-2 upgrade via the multiple scattering of positrons

High-luminosity particle collider experiments such as theones planned at the High-Luminosity Large Hadron Collider requireever-greater vertexing precision of the tracking detectors,necessitating reductions in the material budget of the detectors.Traditionally, the fractional radiation length (x/X$_{0}$) ofdetectors is either estimated using known properties of theconstituent materials, or measured in dedicated runs of the finaldetector. In this paper, we present a method of direct measurementof the material budget of a CMS prototype module designed for thePhase-2 upgrade of the CMS detector using a 40–65 MeV positronbeam. A total of 630 million events were collected at the PaulScherrer Institut PiE1 experimental area using a three-planetelescope consisting of the prototype module as the central plane,surrounded by two MALTA monolithic pixel detectors. Fractionalradiation lengths were extracted from scattering angle distributionsusing the Highland approximation for multiple scattering. Astatistical technique recovered runs suffering from triggerdesynchronisation, and several corrections were introduced tocompensate for local inefficiencies related to geometric and beamshape constraints. Two regions of the module were surveyed andyielded average x/X$_{0}$ values of (0.72 ± 0.05)% and(0.95 ± 0.09)%, which are compatible with empirical estimatesfor these regions computed from known material properties of 0.753%and 0.892%, respectively. Two types of higher-granularity maps ofthe fractional radiation length were produced, subdivided eitherinto rectangular regions of uniform size, or polygonal-shapedregions of uniform material composition. The results bode well forthe CMS Phase-2 upgrade modules, which will play a key role in theminimisation of the material of the upgraded detector.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2025

Kramers nodal lines in intercalated TaS 2 superconductors

Kramers degeneracy is one fundamental embodiment of the quantum mechanical nature of particles with half-integer spin under time reversal symmetry. Under the chiral and noncentrosymmetric achiral crystalline symmetries, Kramers degeneracy emerges respectively as topological quasiparticles of Weyl fermions and Kramers nodal lines (KNLs), anchoring the Berry phase-related physics of electrons. However, an experimental demonstration for ideal KNLs well isolated at the Fermi level is lacking. Here, we establish a class of noncentrosymmetric achiral intercalated transition metal dichalcogenide superconductors with large Ising-type spin-orbit coupling, represented by In x TaS 2 , to host an ideal KNL phase. We provide evidence from angle-resolved photoemission spectroscopy with spin resolution, angle-dependent quantum oscillation measurements, and ab-initio calculations. Our work not only provides a realistic platform for realizing and tuning KNLs in layered materials, but also paves the way for exploring the interplay between KNLs and superconductivity, as well as applications pertaining to spintronics, valleytronics, and nonlinear transport.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Testing Lepton Flavor Universality and CKM Unitarity with Rare Pion Decays in the PIONEER experiment

The physics motivation and the conceptual design of the PIONEER experiment, a next-generation rare pion decay experiment testing lepton flavor universality and CKM unitarity, are described. Phase I of the PIONEER experiment, which was proposed and approved at Paul Scherrer Institut, aims at measuring the charged-pion branching ratio to electrons vs. muons, $R_{e/\mu}$, 15 times more precisely than the current experimental result, reaching the precision of the Standard Model (SM) prediction at 1 part in $10^4$. Considering several inconsistencies between the SM predictions and data pointing towards the potential violation of lepton flavor universality, the PIONEER experiment will probe non-SM explanations of these anomalies through sensitivity to quantum effects of new particles up to the PeV mass scale. The later phases of the PIONEER experiment aim at improving the experimental precision of the branching ratio of pion beta decay (BRPB), $\pi^+\to \pi^0 e^+ \nu (\gamma)$, currently at $1.036(6)\times10^{-8}$, by a factor of three (Phase II) and an order of magnitude (Phase III). Such precise measurements of BRPB will allow for tests of CKM unitarity in light of the Cabibbo Angle Anomaly and the theoretically cleanest extraction of $|V_{ud}|$ at the 0.02% level, comparable to the deduction from superallowed beta decays.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Revealing intrinsic domains and fluctuations of moiré magnetism by a wide-field quantum microscope

Moiré magnetism featured by stacking engineered atomic registry and lattice interactions has recently emerged as an appealing quantum state of matter at the forefront of condensed matter physics research. Nanoscale imaging of moiré magnets is highly desirable and serves as a prerequisite to investigate a broad range of intriguing physics underlying the interplay between topology, electronic correlations, and unconventional nanomagnetism. Here we report spin defect-based wide-field imaging of magnetic domains and spin fluctuations in twisted double trilayer (tDT) chromium triiodide CrI 3 . We explicitly show that intrinsic moiré domains of opposite magnetizations appear over arrays of moiré supercells in low-twist-angle tDT CrI 3 . In contrast, spin fluctuations measured in tDT CrI 3 manifest little spatial variations on the same mesoscopic length scale due to the dominant driving force of intralayer exchange interaction. Our results enrich the current understanding of exotic magnetic phases sustained by moiré magnetism and highlight the opportunities provided by quantum spin sensors in probing microscopic spin related phenomena on two-dimensional flatland.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

High-Field One-Dimensional and Two-Dimensional 27Al Magic-Angle Spinning Nuclear Magnetic Resonance Study of ?-, d-, and ?-Al2O3 Dominated Aluminum Oxides: Toward Understanding the Al Sites in ?-Al2O3

Herein, a detailed analysis was carried out using high-field (19.9 T) 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) on three specially prepared aluminum oxide samples where the ?-, d-, and ?-Al2O3 phases are dominantly expressed through careful control of the synthesis conditions. Specifically, two-dimensional (2D) multiquantum (MQ) MAS 27Al was used to obtain high spectral resolution, which provided a guide for analyzing quantitative 1D 27Al NMR spectra. Six aluminum sites were resolved in the 2D MQ MAS NMR spectra, and seven aluminum sites were required to fit the 1D spectra. A set of octahedral and tetrahedral peaks with well-defined quadrupolar line shapes was observed in the ?-phase dominant sample and was unambiguously assigned to the ?-Al2O3 phase. The distinct line shapes related to the ?-Al2O3 phase provided an opportunity for effectively deconvoluting the more complex spectrum obtained from the d-Al2O3 dominant sample, allowing the peaks/quadrupolar parameters related to the d-Al2O3 phase to be extracted. The results show that the d-Al2O3 phase contains three distinct AlO sites and three distinct AlT sites. This detailed Al site structural information offers a powerful way of analyzing the most complex ?-Al2O3 spectrum. It is found that the ?-Al2O3 phase consists of Al sites with local structures similar to those found in the d-Al2O3 and ?-Al2O3 phases albeit with less ordering. Spin–lattice relaxation time measurement further confirms the disordering of the lattice. Collectively, this study uniquely assigns 27Al features in transition aluminas, offering a simplified method to quantify complex mixtures of aluminum sites in transition alumina samples.

Xu, Suochang↗
DOE OSTI2025

Extracted Water Induces Concentration Fluctuations in Model Ternary Liquid–Liquid Extraction System

Organic phase aggregation and phase splitting are two important (and connected) phenomena in liquid–liquid extraction of metal ions. Previously, we demonstrated how structure in binary mixtures of extractant and diluent originates from concentration fluctuations associated with the so-called “third-phase formation” liquid–liquid phase instability. For more complex systems, we sought to understand how extracted aqueous components affect these concentration fluctuations. Here, in this study, we use small-angle X-ray scattering and molecular dynamics simulations to investigate organic phase structural changes upon contact with water in a model ternary system of water/alkane/extractant. Critical exponents were determined from scattering with temperature variation and were consistent with mean field values. Then, by controlling the water content in the organic phase through direct dissolution of fixed quantities at constant temperature, we relate the observed increase in the fluctuation length scale to changes to the spinodal temperature of the third-phase formation phase boundary. We find a roughly linear relationship between water concentration and the spinodal temperature and a similar slope in that relationship for different linear alkane diluents. This suggests that the mechanism by which water extraction impacts the organic phase structure is to enhance concentration fluctuations through the introduction of additional polar extractant-water complexes, which increases the spinodal temperature and thereby decreases the reduced temperature, i.e., the distance to the instability. This explanation for how solutes induce aggregation in liquid–liquid extraction organic phases may extend to more complex systems, explaining the large increases in correlation lengths reported under high acid and metal loading.

Bonnett, Brittany L. [Argonne National Laboratory ↗