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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Effect of lattice excitations on transient near-edge x-ray absorption spectroscopy

Here, time-dependent and constituent-specific spectral changes in soft near-edge x-ray absorption spectroscopy (XAS) of an [Fe/MgO] 8 metal/insulator heterostructure after laser excitation are analyzed at the O K-edge with picosecond time resolution. The oxygen absorption edge of the insulator features a uniform intensity decrease of the fine structure at elevated phononic temperatures, which can be quantified by a simple simulation and fitting procedure presented here. Combining XAS with ultrafast electron diffraction measurements and ab initio calculations demonstrates that the transient intensity changes in XAS can be assigned to a transient lattice temperature. Thus, the sensitivity of transient near-edge XAS to phonons is demonstrated.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Oxygen Evolution on Mechanically Strained TiO2/NiTi: Implications of Compositional Heterogeneity at (Photo)Electrocatalytic Interfaces

The adsorption and activation energetics underpinning small molecule conversion on heterogeneous (photo)electrocatalysts are intrinsically tied to catalyst surface properties. Absent compositional characterization techniques with sufficient interface sensitivity, however, (photo)electrochemical performance can be misinterpreted in the context of bulk or near-surface material properties. Here we provide a fundamental investigation of the convoluting role of near-surface compositional heterogeneity in the interpretation of (photo)electrochemical alkaline oxygen evolution reaction (OER) activity, highlighting challenges in correlating composition measured by surface- and near-surface-sensitive probes. TiO2 thin films grown by air-annealing the superelastic alloy Nitinol (TiO2/NiTi) crack under tensile mechanical strain, increasing the number of electrochemically active Ni sites (Ni site density) that are probed via voltammetric features corresponding to Ni3+/Ni2+ redox events. (Photo)electrochemical OER kinetics trend with Ni site density, with overpotentials and Tafel slopes decreasing for Ni site densities < 1013 Ni/cm2geo and asymptotically approaching the performance of the base NiTi substrate for Ni site densities > 1013 Ni/cm2geo. Photoelectrochemical fill factors follow similar Ni site density dependent trends. When probing unstrained TiO2/NiTi, Ni site densities are two orders of magnitude higher when comparing near-surface-sensitive techniques (e.g., X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectrometry (TOF-SIMS), and scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDS)) to surface-sensitive electrochemical measurements. This result highlights the challenge of correlating kinetic performance with intrinsic surface properties of electrochemical interfaces in the presence of near-surface compositional heterogeneity. Further, it reinforces the importance of fundamental investigations of surfaces with well-controlled composition and structure and the need for physically grounded and self-consistent interpretation of multiple near-surface characterization techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Quantum-amplified global-phase spectroscopy on an optical clock transition

Optical lattice clocks are at the forefront of precision metrology, operating near a standard quantum limit set by quantum noise. Harnessing quantum entanglement offers a promising route to surpass this limit; however, there are practical difficulties in terms of scalability and measurement resolution requirements. Here we adapt the holonomic quantum gate concept to develop a new Rabi-type ‘global-phase spectroscopy’ that uses the detuning-sensitive global Aharonov–Anandan phase19. With this approach, we can demonstrate quantum-amplified time-reversal spectroscopy on an optical clock transition that achieves directly measured 2.4(7) dB metrological gain and 4.0(8) dB improvement in laser noise sensitivity beyond the standard quantum limit. To this end, we introduce rotary echo to protect the dynamics from inhomogeneities in light–atom coupling and implement a laser-noise-cancelling differential measurement through symmetric phase encoding in two nuclear spin states. Our technique is not limited by measurement resolution, scales easily because of the global nature of entangling interaction and exhibits high resilience to typical experimental imperfections. As a result, we expect it to be broadly applicable to next-generation atomic clocks and other quantum sensors approaching the fundamental quantum precision limits.

Zaporski, Leon [Massachusetts Institute of Technol↗
DOE OSTI2025

Current interrupt method for calculating the electrochemical impedance in a solid oxide electrolysis stack

Here, in this work the time domain response of Solid Oxide Electrolysis Cells (SOEC) to a current interruption was transformed into the frequency domain using a carrier function Laplace transform, which is fit to the experimental data using a MATLAB Complex Nonlinear Least Squares (CNLS) solver. The hardware implementation, consisting principally of a high-speed switch and a fast-logging Analog to Digital Converter (ADC), was assembled and tested using a calibration module to assess the accuracy, repeatability, and speed of acquisition of the prototype device as compared against a calibrated commercial impedance spectrometer. Additionally, the current interrupt device and commercial FRA were used to acquire the impedance spectra of a four cell SOEC stack with a large, 300 cm 2 , active cell area.

SOEC↗
NASA NTRS1995

Time-Resolved IR-Absorption Spectroscopy of Hot-Electron Dynamics in Satellite and Upper Conduction Bands in GaP

The relaxation dynamics of hot electrons in the X6 and X7 satellite and upper conduction bands in GaP was directly measured by femtosecond UV-pump-IR-probe absorption spectroscopy. From a fit to the induced IR-absorption spectra the dominant scattering mechanism giving rise to the absorption at early delay times was determined to be intervalley scattering of electrons out of the X7 upper conduction-band valley. For long delay times the dominant scattering mechanism is electron-hole scattering. Electron transport dynamics of the upper conduction band of GaP has been time resolved.

Cavicchia, M. A.↗
DOE OSTI2025

Zinc(II) Monomeric, Dimeric, and Trimeric Photosensitizers with Microsecond‐Lived Intra‐ligand Charge Transfer Excited States Investigated through Time‐Resolved Optical and X‐Ray Spectroscopy

Zn II photosensitizers relative to Cu I complexes have received less attention due to their energetically higher metal‐to‐ligand charge transfer states. Three Zn II complexes, namely a Monomer, a bimetallic helicate, and a trimetallic helicate, bearing phenanthroline ligands are hereby studied through time‐resolved X‐ray absorption (tr‐XAS) and femto‐microsecond optical transient absorption spectroscopy (OTA). The formation of intraligand singlet charge transfer ( I ILCT) excited states is achieved within femtoseconds, followed by intersystem crossing (ISC) in nanoseconds to generate microsecond‐lived triplet ( 3 ILCT) states. Femtosecond OTA shows that the 1 ILCT states in the Monomer, Dimer, and Trimer occur within 235 fs, 683 fs, and 730 fs, respectively, while nano‐microsecond OTA and tr‐XAS show their 3 ILCT states to decay within 1.00 µs, 1.48 µs, and 1.51 µs. The ISC from the 1 ILCT to the 3 ILCT state for the Trimer is 42.8 ns compared to the Monomer and Dimer with ISC rates of less than 13 ns. These differences arise due to the stabilization by π‐π and CH‐π noncovalent interactions of the phenanthroline ligands. The dihedral and torsional angles indicate stronger ligand strains in the excited states of the Dimer and Trimer versus the Monomer. DFT calculations for the electrochemical oxidation potentials further highlight their capability in inducing photoredox processes.

earth-abundant Zn-based photosensitizers↗
DOE OSTI2021

A NICER View of the Massive Pulsar PSR J0740+6620 Informed by Radio Timing and XMM-Newton Spectroscopy

We report on Bayesian estimation of the radius, mass, and hot surface regions of the massive millisecond pulsar PSR J0740+6620, conditional on pulse-profile modeling of Neutron Star Interior Composition Explorer X-ray Timing Instrument event data. We condition on informative pulsar mass, distance, and orbital inclination priors derived from the joint North American Nanohertz Observatory for Gravitational Waves and Canadian Hydrogen Intensity Mapping Experiment/Pulsar wideband radio timing measurements of Fonseca et al. We use XMM-Newton European Photon Imaging Camera spectroscopic event data to inform our X-ray likelihood function. The prior support of the pulsar radius is truncated at 16 km to ensure coverage of current dense matter models. We assume conservative priors on instrument calibration uncertainty. We constrain the equatorial radius and mass of PSR J0740+6620 to be ${12.39}_{-0.98}^{+1.30}$ km and ${2.072}_{-0.066}^{+0.067}$ M ⊙ respectively, each reported as the posterior credible interval bounded by the 16% and 84% quantiles, conditional on surface hot regions that are non-overlapping spherical caps of fully ionized hydrogen atmosphere with uniform effective temperature; a posteriori, the temperature is ${\mathrm{log}}_{10}(T\,[{\rm{K}}])={5.99}_{-0.06}^{+0.05}$ for each hot region. All software for the X-ray modeling framework is open-source and all data, model, and sample information is publicly available, including analysis notebooks and model modules in the Python language. Furthermore, our marginal likelihood function of mass and equatorial radius is proportional to the marginal joint posterior density of those parameters (within the prior support) and can thus be computed from the posterior samples.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2021

A NICER View of the Massive Pulsar PSR J0740+6620 Informed by Radio Timing and XMM-Newton Spectroscopy

We report on Bayesian estimation of the radius, mass, and hot surface regions of the massive millisecond pulsar PSR J0740+6620, conditional on pulse-profile modeling of Neutron Star Interior Composition Explorer X-ray Timing Instrument event data. We condition on informative pulsar mass, distance, and orbital inclination priors derived from the joint North American Nanohertz Observatory for Gravitational Waves and Canadian Hydrogen Intensity Mapping Experiment/Pulsar wideband radio timing measurements of Fonseca et al. We use XMM-Newton European Photon Imaging Camera spectroscopic event data to inform our X-ray likelihood function. The prior support of the pulsar radius is truncated at 16 km to ensure coverage of current dense matter models. We assume conservative priors on instrument calibration uncertainty. We constrain the equatorial radius and mass of PSR J0740+6620 to be-+12.390.981.30km and-+2.0720.0660.067Me respectively, each reported as the posterior credible interval bounded by the 16% and 84% quantiles, conditional on surface hot regions that are non-overlapping spherical caps of fully ionized hydrogen atmosphere with uniform effective temperature; a posteriori, the temperature is=-+TlogK5.99100.060.05([])for each hot region. All software for the X-ray modeling framework is open-source and all data, model, and sample information is publicly available, including analysis notebooks and model modules in the Python language. Our marginal likelihood function of mass and equatorial radius is proportional to the marginal joint posterior density of those parameters(within the prior support)and can thus be computed from the posterior samples.

Millisecond pulsars↗
NASA NTRS1972

Laser-induced gas breakdown - Spectroscopic and chemical studies.

Discussion of the results of several experimental investigations on laser-induced gas breakdown. The experiments included time-resolved spectroscopy, direct detection of H atoms with a TiO2 probe, and chemical reactions; each of them provided insight into the behavior of the medium at different times. Chemical reactions and explosions have been initiated by the laser beam when a plasma was created. No primary multiphotonic absorption and no macroscopic chemical reactions were observed below the breakdown threshold.

De Montgolfier, PH.↗
DOE OSTI2021

Raman Spectroscopy Coupled with Chemometric Analysis for Speciation and Quantitative Analysis of Aqueous Phosphoric Acid Systems

Complex chemical systems that exhibit varied and matrix-dependent speciation are notoriously difficult to monitor and characterize on-line and in real-time. Optical spectroscopy is an ideal tool for in situ characterization of chemical species that can enable quantification as well as species identification. Chemometric modeling, a multivariate method, has been successfully paired with optical spectroscopy to enable measurement of analyte concentrations even in complex solutions where univariate methods such as Beer’s law analysis fail. Here, Raman spectroscopy is used to quantify the concentration of phosphoric acid and its three deprotonated forms during a titration. In this system, univariate approaches would be difficult to apply due to multiple species being present simultaneously within the solution as pH is varied. Locally Weighted Regression (LWR) modeling was used to determine phosphate concentration from spectral signature. LWR results, in tandem with Multivariate Curve Resolution modeling, provide direct measurement of the concentration of each phosphate species using only the Raman signal. Furthermore, results are presented within the context of fundamental solution chemistry, including Pitzer equations to compensate for activity coefficients and non-idealities associated with high ionic strength systems.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

In situ potassium and hydrogen ion exchange into a cubic zirconium silicate microporous material

The selective separation of ions from aqueous systems, and even in the human body, is a crucial to overall environmental management and health. Nanoporous materials are widely known for their selective removal of cations from aqueous media, and therefore have been targeted for use as a pharmaceutical to treat hyperkalemia. This study investigated the detailed crystallographic molecular mechanisms that control the potassium ion selectivity in the nanoporous cubic zirconium silicate (CZS) related materials. Using time-resolved in situ Raman spectroscopy and time-resolved in situ X-ray diffraction, the selectivity mechanisms were determined to involve a synchronous cation-cation repulsion process that serves to open a favorable coordination bonding environment for potassium, not unlike the ion selectivity filter process found in potassium ion channels in proteins. Enhancement of ion exchange was observed when the CZS material was in a partial protonated state (≈3:1 Na:H), causing an expansion of the unit-cell volume, enlargement of the 7 member-ring window, and distortion of framework polyhedra, which allowed increased accessibility to the cage structures and resulted in rapid irreversible potassium ion exchange.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Experimental and theoretical evidence for hydrogen doping in polymer solution-processed indium gallium oxide

The field-effect electron mobility of aqueous solution-processed indium gallium oxide (IGO) thin-film transistors (TFTs) is significantly enhanced by polyvinyl alcohol (PVA) addition to the precursor solution, a >70-fold increase to 7.9 cm 2 /Vs. To understand the origin of this remarkable phenomenon, microstructure, electronic structure, and charge transport of IGO:PVA film are investigated by a battery of experimental and theoretical techniques, including In K-edge and Ga K-edge extended X-ray absorption fine structure (EXAFS); resonant soft X-ray scattering (R-SoXS); ultraviolet photoelectron spectroscopy (UPS); Fourier transform-infrared (FT-IR) spectroscopy; time-of-flight secondary-ion mass spectrometry (ToF-SIMS); composition-/processing-dependent TFT properties; high-resolution solid-state 1 H, 71 Ga, and 115 In NMR spectroscopy; and discrete Fourier transform (DFT) analysis with ab initio molecular dynamics (MD) liquid-quench simulations. The 71 Ga{ 1 H} rotational-echo double-resonance (REDOR) NMR and other data indicate that PVA achieves optimal H doping with a Ga···H distance of ~3.4 Å and conversion from six- to four-coordinate Ga, which together suppress deep trap defect localization. This reduces metal-oxide polyhedral distortion, thereby increasing the electron mobility. Finally, hydroxyl polymer doping thus offers a pathway for efficient H doping in green solvent-processed metal oxide films and the promise of high-performance, ultra-stable metal oxide semiconductor electronics with simple binary compositions.

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

Time–connectivity superposition and the gel/glass duality of weak colloidal gels

Colloidal gels result from the aggregation of Brownian particles suspended in a solvent. Gelation is induced by attractive interactions between individual particles that drive the formation of clusters, which in turn aggregate to form a space-spanning structure. We study this process in aluminosilicate colloidal gels through time-resolved structural and mechanical spectroscopy. Using the time–connectivity superposition principle a series of rapidly acquired linear viscoelastic spectra, measured throughout the gelation process by applying an exponential chirp protocol, are rescaled onto a universal master curve that spans over eight orders of magnitude in reduced frequency. This analysis reveals that the underlying relaxation time spectrum of the colloidal gel is symmetric in time with power-law tails characterized by a single exponent that is set at the gel point. The microstructural mechanical network has a dual character; at short length scales and fast times it appears glassy, whereas at longer times and larger scales it is gel-like. These results can be captured by a simple three-parameter constitutive model and demonstrate that the microstructure of a mature colloidal gel bears the residual skeleton of the original sample-spanning network that is created at the gel point. Our conclusions are confirmed by applying the same technique to another well-known colloidal gel system composed of attractive silica nanoparticles. The results illustrate the power of the time–connectivity superposition principle for this class of soft glassy materials and provide a compact description for the dichotomous viscoelastic nature of weak colloidal gels.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Real-Time Alignment and Reorientation of Polymer Chains in Liquid Crystal Elastomers

Liquid crystal elastomers (LCEs) exhibit soft elasticity due to the alignment and reorientation of mesogens upon mechanical loading, which provides additional mechanisms to absorb and dissipate energy. This enhanced response makes LCEs potentially transformative materials for biomedical devices, tissue replacements, and protective equipment. However, there is a critical knowledge gap in understanding the highly rate-dependent dissipative behaviors of LCEs due to the lack of real-time characterization techniques that probe the microscale network structure and link it to the mechanical deformation of LCEs. In this work, we employ in situ optical measurements to evaluate the alignment and reorientation degree of mesogens in LCEs. The data are correlated to the quantitative physical analysis using polarized Fourier-transform infrared spectroscopy. The time scale of mesogen alignment is determined at different strain levels and loading rates. The mesogen reorientation kinetics is characterized to establish its relationship with the macroscale tensile strain, and compared to theoretical predictions. Overall, this work provides the first detailed study on the time-dependent evolution of mesogen alignment and reorientation in deformed LCEs. It also provides an effective and more accessible approach for other researchers to investigate the structural-property relationships of different types of polymers.

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

Surfactant inhibition mechanisms of carbonate mineral dissolution in shale

Surfactants are common additives to hydraulic fracturing and enhanced oil recovery (EOR) fluids, and are under consideration for amendment to supercritical carbon dioxide for geological carbon sequestration (GCS). The effect of a common anionic surfactant, internal olefin sulfonate (IOS), on mineral dissolution from shale into brine was evaluated. When added to brine at concentrations exceeding the critical micelle concentration (94 mg/L), IOS inhibited carbonate mineral dissolution in an Eagle Ford shale, as well as dissolution of optical quality calcite (the dominant carbonate in the shale). Laser profilometry images provide spatial resolution across > 3 orders of magnitude, and indicate that IOS addition to brine both enhances the formation of new etch pits in calcite, and impedes their further growth. Time-of-flight secondary ion mass spectrometry surface profiles show for the first time that IOS preferentially adsorbs at calcite pit edges versus flat calcite surfaces (i.e., terraces). Surface pressure calculations, sulfur K-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy results, and density functional theory (DFT) calculations support this observation; the DFT results indicate that the sulfonate head group of the IOS molecule binds strongly to the calcite step site as compared to the terrace site. The S K-edge NEXAFS results indicate that IOS adsorbed more to etched calcite surfaces compared to smooth calcite surfaces. Overall, the results indicate that weak adsorption on flat calcite surfaces (i.e., terraces) disrupts water structure and enhances mass transfer of dissolution, while strong adsorption on calcite pit edges displaces adsorbed water and inhibits further etch pit growth. This work provides the first direct evidence of preferential adsorption of IOS to etched calcite surfaces and links it to macroscopic dissolution kinetics. Finally, this work has implications for surfactant-containing fluids used in hydraulic fracturing, EOR and potentially GCS for subsurface injection into carbonate rich reservoirs.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Time-Resolved Structural Kinetics of an Organic Mixed Ionic–Electronic Conductor

The structure and packing of organic mixed ionic–electronic conductors have an especially significant effect on transport properties. In operating devices, this structure is not fixed but is responsive to changes in electrochemical potential, ion intercalation, and solvent swelling. Toward this end, the steady-state and transient structure of the model organic mixed conductor, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), is characterized using multimodal time-resolved operando techniques. Steady-state operando X-ray scattering reveals a doping-induced lamellar expansion of 1.6 Å followed by 0.4 Å relaxation at high doping levels. Time-resolved operando X-ray scattering reveals asymmetric rates of lamellar structural change during doping and dedoping that do not directly depend on potential or charging transients. Further, time-resolved spectroscopy establishes a link between structural transients and the complex kinetics of electronic charge carrier subpopulations, in particular the polaron–bipolaron equilibrium. These findings provide insight into the factors limiting the response time of organic mixed-conductor-based devices, and present the first real-time observation of the structural changes during doping and dedoping of a conjugated polymer system via X-ray scattering.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Real-Time Diagnostics of 2D Crystal Transformations by Pulsed Laser Deposition: Controlled Synthesis of Janus WSSe Monolayers and Alloys

Energetic processing methods such as hyperthermal implantation hold special promise to achieve the precision synthesis of metastable two-dimensional (2D) materials such as Janus monolayers; however, they require precise control. Here, we report a feedback approach to reveal and control the transformation pathways in materials synthesis by pulsed laser deposition (PLD) and apply it to investigate the transformation kinetics of monolayer WS 2 crystals into Janus WSSe and WSe 2 by implantation of Se clusters with different maximum kinetic energies (<42 eV/Se-atom) generated by laser ablation of a Se target. Real-time Raman spectroscopy and photoluminescence are used to assess the structure, composition, and optoelectronic quality of the monolayer crystal as it is implanted with well-controlled fluxes of selenium for different kinetic energies that are regulated with in situ ICCD imaging, ion probe, and spectroscopy diagnostics. First-principles calculations, XPS, and atomic-resolution HAADF STEM imaging are used to understand the intermediate alloy compositions and their vibrational modes to identify transformation pathways. The real-time kinetics measurements reveal highly selective top-layer conversion as WS 2 transforms through WS 2(1–x) Se 2x alloys to WSe 2 and provide the means to adjust processing conditions to achieve fractional and complete Janus WSSe monolayers as metastable transition states. The general approach demonstrates a real-time feedback method to achieve Janus layers or other metastable alloys of the desired composition, and a general means to adjust the structure and quality of materials grown by PLD, addressing priority research directions for precision synthesis with real-time adaptive control.

2D materials↗