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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Anionic redox induced anomalous structural transition in Ni-rich cathodes

Ni-rich cathodes have emerged as one of the most promising candidates for power next generation electric vehicles. However, they often suffer from poor capacity retention when charged to high voltages and the origin of this degradation remains elusive. Here, by using high throughput operando neutron diffraction, a universal four-stage structural evolution of Ni-rich cathodes is revealed during the initial cycle for the first time. Particularly, we discovered a universal structural transition in Ni-rich cathodes at ~75% delithiation irrespective of Ni or substituent contents. This transition is hallmarked by the anomalous increase of average TM–O bond lengths, contradicting the conventional wisdom that TM–O bond lengths decrease during charge (oxidation). This anomaly is induced by the direct oxidation of lattice oxygen ions, which is rooted in the drastic decrease of oxygen-to-TM charge transfer gap at high degrees of delithiation. The onset of this anomalous transition matches very well with the onset of oxygen gas release and severe decline of capacity retention in Ni-rich cathodes, suggesting that this bulk structural transition plays an indispensable role in the degradation process. These findings shed light on the elusive degradation mechanism of Ni-rich cathodes, providing valuable clues to stabilize oxidized oxygen ions for stable cycling of layered oxide cathodes at high voltages.

25 ENERGY STORAGE↗
DOE OSTI2022

Transient reshaping of intraband transitions by hot electrons

Hot electrons, far above the lattice temperature of a material, present opportunities for enhanced solar energy harvesting or performance of otherwise unfavorable chemistry. The spectroscopic signatures and dynamics of hot carrier absorption and emission have been extensively studied in bulk and nanoscopic semiconductors, but the effects on intraband transitions are largely unexplored. In this work, the effect of hot electrons on the properties of colloidal quantum wells made of cadmium selenide is examined using ultrafast spectroscopy. Similar to expitaxial quantum wells, these atomically precise materials support intersubband transitions (a class of intraband transitions in 1D and 2D materials) in the near-infrared spectral window. Using energy-dependent photoexcitation, it is shown that electrons reach effective temperatures of 2000 K or greater. This results in a substantial transient shift in the oscillator strength of the instersubband transition to lower energies on a sub-picosecond time-scale. Similar heating of electrons is achieved under mid-infrared re-excitation, which permits ultrafast transmittance modulation throughout the near-infrared.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Ce stabilized Ni–SrO as a catalytic phase transition sorbent for integrated CO 2 capture and CH 4 reforming

Integration of carbon dioxide capture from flue gas with dry reforming of CH 4 represents an attractive approach for CO 2 utilization. The selection of a suitable bifunctional material serving as a catalyst/sorbent is the key. This paper reports Ni decorated and CeO x -stabilized SrO (SrCe 0.5 Ni 0.5 ) as a multi-functional, phase transition catalytic sorbent material. The effect of CeO x on the morphology, structure, decarbonation reactivity, and cycling stability of the catalytic sorbent was determined with TEM-EDX, XRD, in situ XRD, CH 4 -TPR and TGA. Here, cyclic process tests were conducted in a packed bed reactor. The results indicate that large Ni clusters were present on the surface of the SrNi sorbent, and the addition of CeO 2 promoted even distribution of Ni on the surface. Moreover, the Ce–Sr interaction promoted a complex carbonation/decarbonation phase-transition, i.e. SrCO 3 + CeO 2 ↔ Sr 2 CeO 4 + CO 2 as opposed to the conventional, simple carbonation/decarbonation cycles (e.g. SrCO 3 ↔ SrO + CO 2 ). This double replacement crystalline phase transition mechanism not only adjusts the carbonation/calcination thermodynamics to facilitate SrCO 3 decomposition at relatively low temperatures but also inhibits sorbent sintering. As a result, excellent activity and stability were observed with up to 91% CH 4 conversion, >72% CO 2 capture efficiency and ~100% residual O 2 capture efficiency from flue gas by utilizing the CeO 2 ↔ Ce 2 O 3 redox transition. This renders an intensified process with zero coke deposition. Moreover, the SLDRM with SrCe 0.5 Ni 0.5 has the flexibility to produce concentrated CO via CO 2 -splitting while co-producing a syngas with tunable H 2 /CO ratios.

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

The fate of liquid crystal topological defects on chemically patterned surfaces during phase transitions

Controlling topological defects in liquid crystals (LCs) is an essential element in the development of areas such as directed self-assembly and micropatterning materials. However, during the phase transition on confined patterned surfaces, how the morphologies in one liquid crystalline phase change from deformations or defects into another phase is much less known. Here, we examine the fate of defects in a LC confined on a patterned surface during smectic-A–nematic and nematic–isotropic phase transitions, using experiments and simulation analyses. Upon heating from smectic-A to nematic, a Toric focal conical domain (TFCD) melts into a +1 converging boojum defect, which then transitioned into a concentric configuration as temperature increases, attributed to a steeper decrease of the bend and twist modulus compared to splay modulus. During cooling, TFCDs are developed from two distinct pathways depending on the cooling rates. Our continuum simulation recapitulates these transformations and provides elastic constant-based explanations for the two pathways. Although the phase transition pathways of defects are independent of the geometry of the confined patterns, the arrangement of FCDs is highly dependent on the size and shape of the patterns. Finally, taken together, this simple approach offers promising opportunities for tuning the micro- or nano-patterning of topological defects in liquid crystals.

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

Polymorphism and phase transitions in Na 2 U 2 O 7 from density functional perturbation theory

Polymorphism and phase transitions in sodium diuranate, Na 2 U 2 O 7 , are investigated with density functional perturbation theory (DFPT). Thermal properties of crystalline α-, β- and γ-Na 2 U 2 O 7 polymorphs are predicted from DFPT phonon calculations, i.e., the first time for the high-temperature γ-Na 2 U 2 O 7 phase (R$\bar{3}$ with combining macron]m symmetry). The standard molar isochoric heat capacities predicted within the quasi-harmonic approximation are C p (298.15K)= 219.4 and 220.9 J K -1 mol -1 mfor P21/a α-Na 2 U 2 O 7 and C2/m β-Na 2 U 2 O 7 , respectively. Gibbs free energy calculations reveal that α-Na 2 U 2 O 7 (P2 1 /a) and β-Na 2 U 2 O 7 (C2/m) are almost energetically degenerate at low temperature, with β-Na 2 U 2 O 7 becoming slightly more stable than α-Na 2 U 2 O 7 as temperature increases. Here these findings are consistent with XRD data showing a mixture of α and β phases after cooling of γ-Na 2 U 2 O 7 to room temperature and the observation of a sluggish α → β phase transition above ca. 600 K. A recently observed α-Na 2 U 2 O 7 structure with P21 symmetry is also shown to be metastable at low temperature. Based on Gibbs free energy, no direct β → γ solid-solid phase transition is predicted at high temperature, although some experiments reported the existence of such phase transition around 1348 K. This, along with recent experiments, suggests the occurrence of a multi-step process consisting of initial β-phase decomposition, followed by recrystallization into γ-phase as temperature increases.

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

Percolative phase transition in few-layered MoSe 2 field-effect transistors using Co and Cr contacts

The metal-to-insulator phase transition (MIT) in two-dimensional (2D) materials under the influence of a gating electric field has revealed interesting electronic behavior and the need for a deeper fundamental understanding of electron transport processes, while attracting much interest in the development of next-generation electronic and optoelectronic devices. Although the mechanism of the MIT in 2D semiconductors is a topic under debate in condensed matter physics, our work demonstrates the tunable percolative phase transition in few-layered MoSe 2 field-effect transistors (FETs) using different metallic contact materials. Here, we attempted to understand the MIT through temperature-dependent electronic transport measurements by tuning the carrier density in a MoSe 2 channel under the influence of an applied gate voltage. In particular, we have examined this phenomenon using the conventional chromium (Cr) and ferromagnetic cobalt (Co) as two metal contacts. For both Cr and Co, our devices demonstrated n-type behavior with a room-temperature field-effect mobility of 16 cm 2 V −1 s −1 for the device with Cr-contacts and 92 cm 2 V −1 s −1 for the device with Co-contacts, respectively. Further, with low temperature measurements at 50 K, the mobilities increased significantly to 65 cm 2 V −1 s −1 for the device with Cr and 394 cm 2 V −1 s −1 for the device with Co-contacts. By fitting our experimental data to the percolative phase transition theory, the temperature-dependent conductivity data show a transition from an insulating-to-metallic behavior at a bias of ∼28 V for Cr-contacts and ∼20 V for Co-contacts. This cross-over of the conductivity can be attributed to an increase in carrier density as a function of the gate bias in temperature-dependent transfer characteristics. By extracting the critical exponents, we find that the transport behavior in the device with Co-contacts aligns closely with the 2D percolation theory. In contrast, the devices with Cr-contacts deviate significantly from the 2D limit at low temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Surface engineering of Pt nanocatalysts with transition metal oleates for selective catalysis: a case study on the hydrogenation of α,β-unsaturated aldehydes

Selective and active catalysts enable effective use of feedstocks, reduced energy consumption and waste generation. Tuning the electronic structure of heterogeneous metal nanocatalysts via their surface modifications is a promising strategy to design highly selective and active catalysts for the synthesis of harder to make and more cost-efficient products. Here, we introduce transition metal oleates as a new class of ligands to engineer the catalytically active and very selective surface in organic solvents. Using citral hydrogenation and 5 nm Pt NPs as a model reaction and model catalytic system, respectively, we show that surface engineering of Pt nanocatalysts with metal oleates allows synthesis of desired partially hydrogenated product (geraniol) with ∼90% conversion with selectivity over 93%. We demonstrate that the selective synthesis of the unsaturated alcohols catalyzed by Pt NPs modified by adsorption of the transition metal salts cannot be explained by the widely accepted mechanism of preferred coordination of C$=$O groups by Lewis acids (e.g. partially oxidized transition surface metals). Our results indicate that C$=$O groups prefer to bind to negatively charged surfaces. We propose the explanation on how the adsorption of transition metal oleates can result in the increased electron density at the surface of Pt nanoparticles. Our study not only provides reliable solutions to selective hydrogenation but opens a new possibility of using metal oleates for the electronic ligand effect.

Kwon, Soon Gu [Argonne National Laboratory (ANL), ↗
DOE OSTI2024

On-line installation of the Superallowed Transition Beta-Neutrino Decay Ion Coincidence Trap

The Cabibbo-Kobayashi-Maskawa quark mixing matrix currently does not satisfy unitarity at the 2σ-level. This could be the result of an inaccurate value of one or both of its largest matrix elements V us and V ud . In the case of V ud , the most precise measurement is obtained from the f t -value measurements of superallowed beta-transitions between 0 + states. The accuracy of this determination can, in turn, be tested by extracting V ud in other transitions including superallowed transitions between mirror nuclei. The Superallowed Transition Beta-Neutrino Decay Ion Coincidence Trap (St. Benedict) is currently under construction at the Nuclear Science Laboratory of the University of Notre Dame to perform such a determination, with the goal of shedding more light on this tension with unitarity. St. Benedict will take a radioactive ion beam produced by TwinSol , thermalize it in a large volume gas catcher, then transport it in two separate differentially-pumped volumes using a radio-frequency (RF) carpet and a radio-frequency quadrupole (RFQ) ion guide before injecting it in an RFQ trap to create cool ion bunches for injection in the measurement Paul trap. In this paper, we detail the installation of the beam preparation components of St. Benedict, and present the results of the first RIBs successfully stopped and extracted from its gas catcher.

Brodeur, M.↗
DOE OSTI2020

Pinning of energy transitions of defects, complexes, and surface states in AlGaN alloys

In this work, we determine the dependence of the defect transition energies, electronic bands, and surface charge neutrality levels in AlGaN. With Vacuum level as reference, we show that energy transitions of localized defects and the surface Fermi level are independent of the alloy composition as electronic bands diverge with the increase in the bandgap as a function of alloy composition. The invariance of localized states on the alloy composition creates a convenient internal reference energy with respect to which other energy states may be measured. We demonstrate a higher generality to the universality rule with the independence of deep transition states of otherwise shallow donor type defects [(+1/+3) transition for VN] and defect complexes (C N +Si III ) in addition to the earlier predicted independent nature of mid-gap states when they are either the antibonding state between cationic impurities and host anion or acceptors at anion sites.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Impact of Numerical Hydrodynamics in Turbulent Mixing Transition Simulations

Underresolved simulations are unavoidable in high Reynolds (Re) and Mach (Ma) number turbulent flow applications at scale. Implicit large-Eddy simulation (ILES) often becomes the effective strategy to capture the dominating effects of convectively driven flow instabilities. We evaluate the impact of three distinct numerical strategies in simulations of transition and turbulence decay with ILES: the Harten–Lax–van Leer (HLL) Riemann solver applying Strang splitting and a Lagrange-plus-Remap formalism to solve the directional sweep—denoted split; the Harten–Lax–Van Leer-Contact (HLLC) Riemann solver using a directionally unsplit strategy and parabolic reconstruction—denoted unsplit; and the HLLC Riemann solver using unsplit and a low-Ma correction (LMC)—denoted unsplit*. Three case studies are considered: (1) a shock tube problem prototyping shock-driven turbulent mixing, (2) the Taylor–Green Vortex (TGV) prototyping transition to turbulence, and, (3) an homogeneous isotropic turbulence (HIT) case, focusing on the impact of discretization on transition and decay from fixed well-characterized initial conditions. Significantly more accurate predictions are provided by the unsplit schemes, in particular, when augmented with the LMC. For given resolution, only the unsplit schemes predict the turbulent mixing transition after reshock observed in the shock tube experiments. Relevant comparisons of ILES based on Euler and Navier–Stokes equations addressing potential occurrence of low-Re regimes in the applications are presented. Unsplit schemes are instrumental in allowing to capture the spatial development of the TGV flow and its validation at prescribed Re with significantly less resolution. HIT analysis confirms higher simulated turbulence Re and increased small-scale content associated with the unsplit discretizations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

The plasma–sheath transition and Bohm criterion in a high recycling divertor

The high recycling regime of a divertor is characterized by high plasma particle fluxes and low temperature at the target, where a strong hydrogen recirculation loop exists. Atomic processes in the high recycling regime, such as ion–neutral friction and radiation, can affect the plasma momentum and energy transport in the sheath transition region. Here, in this work, the plasma–sheath transition near a high recycling wall is investigated. The Bohm speed, which constraints the ion exit flow speed, is evaluated from a transport model that accounts for the effect of the anisotropic transport and atomic collisions in the transition layer. A first principles kinetic code vector particle-in-cell with the atomic collision package is used to investigate a 1D self-consistent slab plasma with a high recycling boundary for the tungsten and carbon divertors. The results demonstrate the accuracy of the Bohm speed model in predicting the ion exit flow speed in the transition region, as well as the reduction of the Bohm speed due to the ion–neutral friction. The effect of different wall materials, tungsten, and carbon, on the Bohm speed and near-wall plasma profile is shown.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Mott vs Kondo: Influence of various density functional based methods on the Ce isostructural phase transition mechanism

The cerium iso-structural phase transition (γ–α) is dominated by f-electron localization changes that results in a magnetic ordering change and a volume collapse. Generally, these physics are difficult to capture with ab initio and first principles methods. However, previous works have shown various methods to be successful in predicting at least some of the physics of the γ to α phase transition. Therefore, here, we perform a broad survey of density functional based methods across three levels of theory and types of functions [GGA (generalized gradient approximation), MetaGGA, and hybrid functionals] and compare the results, focusing on hydrostatic compression across the phase boundary at zero kelvin. For the methods that best reproduce experimental results, we directly probe the predicted mechanisms and frame the results in the Mott/Kondo debate, assessing how the underlying methods and assumptions of different functionals can assess the physical drivers in the phase transition, providing insight into the governing processes of this unique phase transition.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Validation of 266 nm UV Raman thermometry using the alpha-to-beta quartz transition

Ultraviolet Raman scattering is a promising diagnostic for temperature measurements relevant to dynamic compression experiments, where improved signal strength and reduced background are critical. In this work, we experimentally validate Raman thermometry at 266 nm using crystalline quartz heated through the α to β phase transition in a tube furnace. Quartz provides a useful benchmark because of its well-characterized transition temperature near 846 K at ambient pressure. Temperatures inferred from the Stokes to anti-Stokes intensity ratio are compared with thermocouple measurements and with the observed phase transition. Single-shot Raman temperatures track the thermocouple closely, with an empirical single-shot scatter of approximately ±15 K under the present conditions. Temporal averaging reduces shot-to-shot scatter and improves agreement between the Raman temperatures and thermocouple readings to within approximately 8 K, while the transition is identified within 5 K of the accepted value. Measurements are performed using the fourth harmonic of a nanosecond pulsed Nd:YAG laser at 266 nm. The shorter excitation wavelength provides enhanced Raman scattering efficiency and reduced visible background relative to conventional visible excitation. Comparison with 532 nm Raman measurements acquired in the same experimental geometry demonstrates substantially improved signal-to-noise ratio for the UV configuration. These results establish 266 nm Raman thermometry as a reliable and accurate temperature diagnostic under controlled heating conditions and provide a quantitative benchmark for future application in dynamic compression and shock physics experiments.

Chemistry - Chemical explosives↗
DOE OSTI2020

Rabi spectroscopy of the clock transition in thulium atoms in a one-dimensional optical lattice

The clock transition at a wavelength of 1.14 μm in thulium atoms in an optical lattice in the Lamb – Dick regime is studied. The capture of thulium atoms makes it possible to suppress completely both the transition broadening due to the first-order Doppler effect and the shift of the transition frequency caused by the recoil effect. The excitation spectra of sideband oscillation frequencies and Rabi oscillations of population between the clock transition levels upon resonance excitation are investigated. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Elucidating the G″ overshoot in soft materials with a yield transition via a time-resolved experimental strain decomposition

Significance The yielding transition in soft materials manifests macroscopically as a reversible transition from solid-like deformation to liquid-like flow under sufficiently large loading or deformation. Despite the ubiquity of materials that exhibit yielding, an understanding of the transition has remained elusive due to experimental limitations of the simple rheological tests typically used to study it. We present here a more thorough understanding of yielding, obtained via an iterative test protocol and analysis that allow for the separation of solid-like and liquid-like behaviors in the response of these materials. We show that yielding is a gradual transition, occurring to an increased extent as the deformation increases.

Donley, Gavin J.↗
DOE OSTI2022

Differentiated roles of Lifshitz transition on thermodynamics and superconductivity in La 2- x Sr x CuO 4

The effect of Lifshitz transition on thermodynamics and superconductivity in hole-doped cuprates has been heavily debated but remains an open question. In particular, an observed peak of electronic specific heat is proposed to originate from fluctuations of a putative quantum critical point p* (e.g., the termination of pseudogap at zero temperature), which is close to but distinguishable from the Lifshitz transition in overdoped La-based cuprates where the Fermi surface transforms from hole-like to electron-like. Here we report an in situ angle-resolved photoemission spectroscopy study of three-dimensional Fermi surfaces in La 2- x Sr x CuO 4 thin films ( x = 0.06 to 0.35). With accurate k z dispersion quantification, the said Lifshitz transition is determined to happen within a finite range around x = 0.21. Normal state electronic specific heat, calculated from spectroscopy-derived band parameters, reveals a doping-dependent profile with a maximum at x = 0.21 that agrees with previous thermodynamic microcalorimetry measurements. The account of the specific heat maximum by underlying band structures excludes the need for additionally dominant contribution from the quantum fluctuations at p* . A d -wave superconducting gap smoothly across the Lifshitz transition demonstrates the insensitivity of superconductivity to the dramatic density of states enhancement.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

CI-MBPT line strengths and atomic probabilities for some transitions of neutral iodine

Iodine is a promising alternative to expensive xenon as a propellant for electric propulsion devices. Iodine optical spectroscopy is a valuable diagnostic tool for optimization of the iodine propellant. Recently, some measurements have been conducted with cells containing iodine plasma, and iodine atomic absorption at several wavelengths (911, 906, 206 and 1315 nm) was measured with a Ti:sapphire laser. Motivated by these experiments and future applications, here we have calculated line strengths and atomic probabilities for the transitions between different types of 5s 2 5p 5 , 5s 2 5p 4 6s, 5s 2 5p 4 6p and 5s 2 5p 4 5d states of atomic iodine, using configuration-interaction many-body perturbation theory. Since experimental transition data for atomic iodine are only available for a relatively small number of transitions, we also performed calculations for the bromine atom, to further validate our approach. We found good agreement between our theory and available experimental data for both elements in most cases. Therefore, we believe that our predicted line strengths and transition probabilities are quite reliable and will be useful for iodine spectroscopy.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Strong ultrafast demagnetization due to the intraband transitions

Abstract Demagnetization in ferromagnetic transition metals driven by a femtosecond laser pulse is a fundamental problem in solid state physics, and its understanding is essential to the development of spintronic devices.Ab initiocalculation of time-dependent magnetic moment in the velocity gauge so far has not been successful in reproducing the large amount of demagnetization observed in experiments. In this work, we propose a method to incorporate intraband transitions within the velocity gauge through a convective derivative in the crystal momentum space. Our results for transition-element bulk crystals (bcc Fe, hcp Co and fcc Ni) based on the time-dependent quantum Liouville equation show a dramatic enhancement in the amount of demagnetization after the inclusion of an intraband term, in agreement with experiments. We also find that the effect of intraband transitions on each ferromagnetic material is distinctly different because of their band structure and spin property differences. Our finding has a far-reaching impact on understanding of ultrafast demagnetization.

Physics↗