Metal-Organic Framework- and Polyoxometalate-Based Sorbents for the Uptake and Destruction of Chemical Warfare Agents
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99 GENERAL AND MISCELLANEOUS↗
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Results for “phase control”
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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Alkali cation stabilization of defects in 2D MXenes at ambient and elevated temperatures
Transition metal carbides have been adopted in energy storage, conversion, and extreme environment applications. Advancements in their 2D counterparts, known as MXenes, enable the design of unique structures at the ~1 nm thickness scale. Alkali cations have been essential in MXenes manufacturing processing, storage, and applications, however, exact interactions of these cations with MXenes are not fully understood. In this study, using Ti 3 C 2 T x , Mo 2 TiC 2 T x , and Mo 2 Ti 2 C 3 T x MXenes, we present how transition metal vacancy sites are occupied by alkali cations, and their effect on MXene structure stabilization to control MXene’s phase transition. We examine this behavior using in situ high-temperature x-ray diffraction and scanning transmission electron microscopy, ex situ techniques such as atomic-layer resolution secondary ion mass spectrometry, and density functional theory simulations. In MXenes, this represents an advance in fundamentals of cation interactions on their 2D basal planes for MXenes stabilization and applications. Broadly, this study demonstrates a potential new tool for ideal phase-property relationships of ceramics at the atomic scale.
42 ENGINEERING↗
Magnetically confined surface and bulk excitons in a layered antiferromagnet
The discovery of two-dimensional van der Waals magnets has greatly expanded our ability to create and control nanoscale quantum phases. A unique capability emerges when a two-dimensional magnet is also a semiconductor that features tightly bound excitons with large oscillator strengths that fundamentally determine the optical response and are tunable with magnetic fields. Here, in this study, we report a previously unidentified type of optical excitation-a magnetic surface exciton-enabled by the antiferromagnetic spin correlations that confine excitons to the surface of CrSBr. Magnetic surface excitons exhibit stronger Coulomb attraction, leading to a higher binding energy than excitons confined in bulk layers, and profoundly alter the optical response of few-layer crystals. Distinct magnetic confinement of surface and bulk excitons is established by layer- and temperature-dependent exciton reflection spectroscopy and corroborated by ab initio many-body perturbation theory calculations. By quenching interlayer excitonic interactions, the antiferromagnetic order of CrSBr strictly confines the bound electron-hole pairs within the same layer, regardless of the total number of layers. Our work unveils unique confined excitons in a layered antiferromagnet, highlighting magnetic interactions as a vital approach for nanoscale quantum confinement, from few layers to the bulk limit.
36 MATERIALS SCIENCE↗
Light-induced ferromagnetism in moiré superlattices
Many-body interactions between carriers lie at the heart of correlated physics. The ability to tune such interactions would allow the possibility to access and control complex electronic phase diagrams. Recently, two-dimensional moiré superlattices have emerged as a promising platform for quantum engineering such phenomena. The power of the moiré system lies in the high tunability of its physical parameters by adjusting the layer twist angle, electrical field, moiré carrier filling and interlayer coupling. In this work, we report that optical excitation can highly tune the spin–spin interactions between moiré-trapped carriers, resulting in ferromagnetic order in WS 2 /WSe 2 moiré superlattices. Near the filling factor of v = 1/3 (that is, one hole per three moiré unit cells), as the excitation power at the exciton resonance increases, a well-developed hysteresis loop emerges in the reflective magnetic circular dichroism signal as a function of magnetic field, a hallmark of ferromagnetism. The hysteresis loop persists down to charge neutrality, and its shape evolves as the moiré superlattice is gradually filled, indicating changes of magnetic ground state properties. The observed phenomenon points to a mechanism in which itinerant photoexcited excitons mediate exchange coupling between moiré-trapped holes. This exciton-mediated interaction can be of longer range than direct coupling between moiré-trapped holes, and thus magnetic order arises even in the dilute hole regime. This discovery adds a dynamic tuning knob to the rich many-body Hamiltonian of moiré quantum matter.
36 MATERIALS SCIENCE↗
An automatically curated first-principles database of ferroelectrics
Ferroelectric materials have technological applications in information storage and electronic devices. The ferroelectric polar phase can be controlled with external fields, chemical substitution and size-effects in bulk and ultrathin film form, providing a platform for future technologies and for exploratory research. In this work, we integrate spin-polarized density functional theory (DFT) calculations, crystal structure databases, symmetry tools, workflow software, and a custom analysis toolkit to build a library of known, previously-proposed, and newly-proposed ferroelectric materials. With our automated workflow, we screen over 67,000 candidate materials from the Materials Project database to generate a dataset of 255 ferroelectric candidates, and propose 126 new ferroelectric materials. We benchmark our results against experimental data and previous first-principles results. The data provided includes atomic structures, output files, and DFT values of band gaps, energies, and the spontaneous polarization for each ferroelectric candidate. Finally, we contribute our workflow and analysis code to the open-source python packages atomate and pymatgen so others can conduct analogous symmetry driven searches for ferroelectrics and related phenomena.
36 MATERIALS SCIENCE↗
Controllable synthesis of environmentally stable vdW antiferromagnetic oxyhalide CrOCl
This work demonstrates APCVD synthesis of stable 2D CrOCl, a magnetic oxyhalide for spintronics and quantum devices. It reveals controllable gas-phase growth, with characterization confirming high-quality CrOCl free from Cr 2 O 3 and oxidation.
Banerjee, Rounak [Materials Science and Engineerin↗
Gyrotropy-induced symmetry breaking in RF-specific plasma wall interaction: Mechanisms and mitigation strategies
Ion cyclotron range of frequencies (ICRF) heating is essential for creating plasma in next-generation fusion devices. ICRF antennas often produce localized wall erosion, reducing reliability, material survivability, and overall plasma performance. We show that the wave physics' gyrotropy is among the causes of toroidal and poloidal asymmetries in these erosion spots, and that this source of asymmetry can be compensated for either by controlling the poloidal phasing or by modifying the limiter shapes.
Fusion reactors↗
Electric field reversals resulting from voltage waveform tailoring in Ar/O 2 capacitively coupled plasmas sustained in asymmetric systems
The etching of nanometer scale high-aspect-ratio (HAR) features into dielectric materials in low pressure radio frequency excited plasmas is often accompanied by charge accumulation inside the features which can slow etching rates and produce distortions such as twisting. The intra feature charging is at least partially produced by differences in electron and ion energy and angular distributions (EADs). Positive ions, accelerated to high energies having narrow angular spreads by the sheath electric field, can penetrate deeply into HAR features. Electrons typically arrive at the wafer with nearly thermal and isotropic distributions and do not penetrate deeply into HAR features. These disparities lead to differential charging of the inside of the feature, which can lead to reductions in etch rate and feature distortion due to ion deflection. With in-creasing aspect ratio of features, charging challenges are expected to continue for the foreseeable future. In this work, the use of tailored voltage waveforms in geometrically asymmetric capacitively coupled plasmas sustained in Ar/O 2 at 40 mTorr was computationally investigated with the goal of shaping the EAD of electrons incident onto the substrate to address differential charging. The tailored waveform consisted of a sinusoidal wave and its higher harmonics with a fundamental frequency of 1 MHz. Further, we found that electric field reversals in the sheath and presheath can occur during the anodic portion of the cycle. The electric field reversal increases the energy and decreases the angular spread of electrons incident onto the substrate. The magnitude of the electric field reversal can be controlled by the phase angle of the even harmonics and the gas composition. Due to its electronegative nature, increasing mole fractions of O 2 impedes electron transport to the surface which further increases the electric field reversal.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Entropic lens on stabilizer states
The n-qubit stabilizer states are those left invariant by a 2 n -element subset of the Pauli group. The Clifford group is the group of unitaries which take stabilizer states to stabilizer states; a physically motivated generating set, the Hadamard, phase, and controlled-not (cnot) gates which comprise the Clifford gates, impose a graph structure on the set of stabilizers. We explicitly construct these structures, the “reachability graphs,” at n ≤ 5. When we consider only a subset of the Clifford gates, the reachability graphs separate into multiple, often complicated, connected components. Seeking an understanding of the entropic structure of the stabilizer states, which is ultimately built up by cnot gate applications on two qubits, we are motivated to consider the restricted subgraphs built from the Hadamard and cnot gates acting on only two of the n qubits. We show how the two subgraphs already present at two qubits are embedded into more complicated subgraphs at three and four qubits. We argue that no additional types of subgraph appear beyond four qubits, but that the entropic structures within the subgraphs can grow progressively more complicated as the qubit number increases. Starting at four qubits, some of the stabilizer states have entropy vectors which are not allowed by holographic entropy inequalities. Here, we comment on the nature of the transition between holographic and nonholographic states within the stabilizer reachability graphs.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Self-assembled reconfigurable pump architectures via magnetic colloidal swarms
Self-assembled swarms of interactive active units, which are adaptive and dynamically reconfigurable to accommodate different functionalities, represent a promising platform for the development of next-generation robotics. Here, we utilize the emergent collective behavior of active magnetic colloids confined in quasi-two-dimensional arrays of overlapping wells to demonstrate the self-organization of a colloidal swarm into a dynamic pump architecture capable of controlled transport of passive cargo particles. This dynamic architecture provides a global unidirectional looping flow pattern along the entire length of the system. We show that the flow direction of the dynamic swarm-based pump can be externally controlled by a phase shift of a driving magnetic field energizing the swarm. The experimental observations are supported by computational modeling based on phenomenological coarse-grained particle dynamics coupled to shallow-water Navier-Stokes hydrodynamics. In conclusion, our findings demonstrate how the emergent collective behavior of a swarm can be orchestrated into a desired functionality by exploiting the interplay between activity and confinement potentials.
36 MATERIALS SCIENCE↗
Nonequilibrium renormalization group fixed points of the quantum clock chain and the quantum Potts chain
In this work, we derive an exact renormalization group recursion relation for the Loschmidt amplitude of the quantum Q-state clock model and the quantum Q-state Potts model in one dimension. The renormalization group flow is discussed in detail. The fixed points of the renormalization group flow are found to be complex in general. These fixed points control the dynamical phases of the two models, giving rise to nonanalyticities in its Loschmidt rate function, for both the pure and the disordered system. For the quench protocols studied, dynamical quantum phase transitions are found to occur in the clock model for all Qs considered, while in the Potts model, they only occur when Q < 4 .
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Resistivity phase diagram of cuprates revisited
The phase diagram of the cuprate superconductors has posed a formidable scientific challenge for more than three decades. This challenge is perhaps best exemplified by the need to understand the normal-state charge transport as the system evolves from Mott insulator to Fermi- liquid metal with doping. Here in this paper, we report a detailed analysis of the temperature (T) and doping (p) dependence of the planar resistivity of simple-tetragonal HgBa 2 CuO 4+δ (Hg1201), the single- CuO 2 -layer cuprate with the highest optimal superconducting transition temperature, T c . The data allow us to test a recently proposed phenomenological model for the cuprate phase diagram that combines a universal transport scattering rate with spatially inhomogeneous (de)localization of the Mott-localized hole. We find that the model provides a good description of the data. We then extend this analysis to prior transport results for several other cuprates, including the Hall number in the overdoped part of the phase diagram, and find little compound-to-compound variation in (de)localization gap scale. The results point to a robust, universal structural origin of the inherent gap inhomogeneity that is unrelated to doping-related disorder. They are inconsistent with the notion that much of the phase diagram is controlled by a quantum critical point, and instead indicate that the unusual electronic properties exhibited by the cuprates are fundamentally related to strong nonlinearities associated with subtle nanoscale inhomogeneity.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Laser pulse driven control of charge and spin order in the two-dimensional Kondo lattice
Fast and dynamical control of quantum phases is highly desired in the application of quantum phenomena in devices. On the experimental side, ultrafast laser pulses provide an ideal platform to induce femtosecond dynamics in a variety of materials. Here we show that a laser pulse driven heavy fermion system can be tuned to dynamically evolve into a phase, which is not present in equilibrium. Using the state-of-the-art time-dependent variational Monte Carlo method, we perform numerical simulations of realistic laser pulses applied to the Kondo lattice model. By tracking spin and charge degrees of freedom we identify a dynamical phase transition, within the partially Kondo screened phase, from a charge ordered into a metallic state, while preserving the spin order of the system. Furthermore, we propose using high-harmonic generation and nonequilibrium optical conductivity to identify the dynamical phase transition in an ultrafast experiment.
36 MATERIALS SCIENCE↗
In situ synchrotron diffraction of pressure-induced phase transition in DyPO 4 under variable hydrostaticity
In situ synchrotron x-ray diffraction was conducted on polycrystalline DyPO 4 to elucidate the details of the pressure-induced transition from the xenotime polymorph to the monazite polymorph. We used three different pressure-transmitting media (neon, a 16:3:1 methanol-ethanol-water mixture, and potassium chloride) to investigate the effect of hydrostaticity on the phase behavior. Specifically, our data clearly show a hydrostatic onset pressure of the xenotime-monazite transition of 9.1 GPa, considerably lower than the 15.3 GPa previously determined by Raman spectroscopy. Based on (quasi)hydrostatic data taken in a neon environment, third-order Birch-Murnaghan equation-of-state fits give a xenotime bulk modulus of 144 GPa and a monazite bulk modulus of 180 GPa (both with pressure derivatives of 4.0). Structural data and axial compressibilities show that DyPO 4 is sensitive to shear and has an anisotropic response to pressure. More highly deviatoric conditions cause the onset of the transition to shift to pressures at least as low as 7.0 GPa. We attribute early transition to shear-induced distortion of the PO4 tetrahedra. Finally, our characterization of the high-pressure behavior of DyPO 4 under variable hydrostaticity is critical for advancing rare earth orthophosphate fiber coating applications in ceramic matrix composites and may inform future tailoring of phase composition for controlled shear and pressure applications.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Formation kinetics and thermodynamic stability of the Aurivillius compounds in Bi 4 Ti 3 O 12 –BiFeO 3 system
Abstract The Aurivillius compounds in the Bi 2 O 3 –Fe 2 O 3 –TiO 2 system, combining ferroelectric, semiconducting, and ferromagnetic properties, have attracted particular interest. Formation kinetics and thermodynamic stability are the fundamental knowledge needed for modeling and predicting the temporal microstructure and property evolution during materials processing but have not yet been addressed by quantitative experimental measurement. This article focuses on the Bi n +1 Fe n –3 Ti 3 O 3 n +3 Aurivillius compounds on the Bi 4 Ti 3 O 12 –BiFeO 3 tie‐line to elucidate the mechanisms and thermodynamic controls responsible for phase formation of compounds with various perovskite‐like layers. Five high‐purity Aurivillius compounds Bi 4 Ti 3 O 12 , Bi 5 FeTi 3 O 15 , Bi 6 Fe 2 Ti 3 O 18 , Bi 7 Fe 3 Ti 3 O 21 , and Bi 8 Fe 4 Ti 3 O 24 with integer n = 3–7 values were synthesized and their phase transformation properties and enthalpies of formation were studied by X‐ray diffraction in situ, high temperature differential scanning calorimetry, and high temperature oxide melt solution calorimetry. Thermodynamic stability of the compounds decreases with increasing n , and formation kinetics gradually slow down, demonstrating the inherent difficulty to synthesize pure Aurivillius compounds with n larger than 8. This difficulty was confirmed by an impurity phase coexisting with Bi 9 Fe 5 Ti 3 O 27 .
Gong, Weiping↗
Experimental and Computational Studies of Crystal Nucleation in Composition Gradients (Final Report)
The major goals of this project were to develop and validate a predictive nucleation model that incorporates composition gradients and is applicable to a large range of metallic systems which form both stochiometric and non-stochiometric compounds. Computationally we planned to expand the extent of thermodynamics-based theories and lay the groundwork to improve the general understanding and predictive capabilities of the role that gradients play in phase formation, glass formability and stability, and nucleation and growth events. To address these goals, we used Molecular Dynamics (MD) simulations and both isothermal and isochronal nanocalorimetric experiments on amorphous phases with a controlled composition gradient with the hopes of validating and improving the classical nucleation model and its use in solid solutions. While the computations were successful and identified ways to improve the classical nucleation model, the in situ nanocalorimetry studies proved very challenging due to unexpected difficulties in fabricating effective calorimeters and samples. Thus, we could not experimentally validate our predicted influence of composition gradients on nucleation. Nonetheless, important insights were gained and modifications to the classical nucleation theory were suggested.
36 MATERIALS SCIENCE↗
Neptunium (V) Solubility in WIPP Brine: Presence and Absence of WIPP-Relevant Organic and Inorganic Ligands
The oxidation state and solubility of neptunium (Np) in 5 M NaCl and high ionic strength synthetic WIPP (Waste Isolation Pilot Plant) brines were systematically investigated as a function of pCH+ (7-11) in the presence and absence of WIPP-relevant organic ligands, including EDTA (Ethylenediaminetetraacetic acid), oxalate, citrate, and acetate, as well as inorganic ligands such as borate and carbonate at a temperature of 23 ± 2°C. This study was conducted through long-term batch solubility experiments spanning approximately 950 days, using an undersaturation approach. A comprehensive set of experimental and spectroscopic techniques, including UV-VIS-NIR spectroscopy and Np L III -edge X-ray Absorption Spectroscopy (XAS), was employed to identify the solubility-controlling Np solid phases and the predominant aqueous Np species present in the samples.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
CACTI CSAPR2 Taranis Retrievals
Taranis is an end-to-end processing chain for radar data written in Python with C extension for computation performance. Features include: masking for quality control, specific differential phase (Kdp), attenuation correction for reflectivity factor (Z) and differential reflectivity (Zdr) in rain, and additional geophysical retrievals. Retrievals are mostly drawn from literature or open-source software when appropriate, and have been tested, tuned, and modified to work with one another cohesively rather than using isolated off-the-shelf algorithms. Incorporated algorithms include hydrometeor (echo) identification, rain water content, raindrop mass-weighted mean diameter (gamma size distribution assumption), and rainfall rate (QPE). Taranis data sets exist for CSAPR2 PPI, HSRHI, and sector RHI scans. Cartesian-gridded data sets were also produced as well as a near-surface rain rate retrieval. More details can be found in the README.
54 ENVIRONMENTAL SCIENCES↗