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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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

The kinetics of the Au-InP interaction

An analysis of the reaction of Au and Au-In alloys with InP has permitted the identification of the mechanisms occurring during the first two stages of the Au-InP interaction. The first stage of the interaction, during which the Au is converted to a saturated Au (In) solution, is controlled by the vacancy-generation rate at the free surface of the metallization. The activation energy for this process is the activation energy for Au self-diffusion. Evidence is presented for the existence of large localized variations in this value due to surface related effects. At the completion of stage I stage II becomes active and continues until the metallization is converted to Au3In. This process, proceeding via an interstitial interchange mechanism, is many orders of magnitude slower than stage I. The rate-limiting step, with an activation energy of 2.8 eV, is shown to be the diffusion of In from the InP-metal interface. The P atoms that are released when In enters the metallization during stage I leave the system without reacting, whereas in stage II they form a compound (Au2P3) at the InP-metal interface. The presence of the Au2P3 severely retards the stage II interaction rate.

Fatemi, Navid S.↗
DOE OSTI2024

Simulating the Phonon Collection Efficiency in KIPMDs

Kinetic inductance phonon-mediated (KIPM) detectors are superconducting microcalorimeters that use microwave kinetic inductance detectors (MKIDs) to read out phonon signals in the device substrate. In order to improve the design of these detectors, we need to understand the effect of various detector design elements on the physical processes that take place within the detector through simulation efforts. One figure of merit for KIPM detectors is the phonon collection efficiency, $\eta_{ph]$, defined as the ratio of phonon energy detected by the sensitive element in the detector and the energy deposited by incident phonons in the substrate. Comparing the phonon collection efficiency obtained in simulation and in experiment for the same detector geometry provides insight to physical processes in the detector, such as phonon absorption at substrate-sensor interfaces and phonon loss to non-sensitive detector elements. This work models the phonon collection efficiency in two KIPM detectors with different geometries, one located at the Fermi National Accelerator Laboraory, the other located at the SLAC National Accelerator Laboratory.

Dang, Stella Q.↗
NASA NTRS1994

Solar system formation and the distribution of volatile species

To understand how the solar system formed we must understand the compositional distribution of the current system. Volatile species are particularly important in that their stability as condensed phases is limited in temperature-pressure space, and hence variations in their distribution at present potentially contain an imprint of processes by which temperature and pressure varied in the solar nebula. In this talk we restrict ourselves to species more volatile than water ice, and address issues related to processes in the outer solar system and the formation of bodies there; others in this conference will cover volatile species relevant to inner solar system processes. Study of the outer solar system is relevant both to understanding the interface between the solar nebula and the progenitor giant molecular cloud (since the chemical links to present-day observables in molecular clouds are species like methane, carbon monoxide, etc.), as well as the origin of terrestrial planet atmospheres and oceans (the latter to be covered by Owen). The wealth of compositional information on outer solar system bodies which has become available from spacecraft and ground-based observations challenges traditional simplistic views of the composition and hence dynamics of the solar nebula. The basic assumption of thermochemical equilibrium, promulgated in the 1950's, in which methane and ammonia dominate nitrogen- and carbon-bearing species, is demonstrably incorrect on both observational and theoretical grounds. However, the kinetic inhibition model which replaced it, in which carbon monoxide and molecular nitrogen dominate a nebula which is fully mixed and hence cycles outer solar system gases through a hot, chemically active zone near the disk center, is not supported either by observations. Instead, a picture of the outer solar system emerges in which the gas and grains are a mixture of relatively unaltered, or modestly altered, molecular cloud material, along with a fraction which has been chemically altered in the solar nebula itself (and perhaps giant planet nebulae).

Lunine, Jonathan I.↗
NASA NTRS1999

Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

NASA Discipline Environmental Health↗
NASA NTRS1992

Oxidation characteristics of Ti-25Al-10Nb-3V-1Mo

Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using X-ray diffraction techniques, electron microprobe analysis, and energy dispersive X-ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.

Wallace, T. A.↗
NASA NTRSDate not supplied

Modeling Self-Pressurization and Spray Bar Pressure Control of a Cryogenic Storage Tank in Normal Gravity

This paper presents Computational Fluid Dynamics (CFD) models for simulating self-pressurization and spray bar cooling processes in a large-scale liquid hydrogen storage tank under normal gravity. The self-pressurization model utilizes the kinetics-based Schrage equation with the Volume-Of-Fluid (VOF) model to account for the evaporative and condensing interfacial mass fluxes. It uses a laminar approach to model natural convection and compares the pressures and temperatures predicted by the CFD model with experimental data from the Multipurpose Hydrogen Test Bed (MHTB) self-pressurization experiment. Additionally, the predicted interfacial mass flux is presented. A CFD model for simulating pressure control using a spray bar is also presented. An Eulerian-Lagrangian approach models the interactions between the discrete droplets and the continuous ullage phase. The spray model is coupled with the VOF model by tracking particles in the ullage, removing particles from the ullage when they reach the interface, and then adding their contributions to the liquid. The T-sat model is used to calculate the droplet-ullage heat and mass transfer. In this model, droplets warm up to the saturation temperature corresponding to the ullage vapor pressure thereafter evaporating while remaining at the saturation temperature. The tank pressure, vapor, and liquid temperature evolutions are validated against data from the MHTB spray bar mixing experiment.

Self-Pressurization↗
DOE OSTI2026

Unveiling the High‐Voltage Reactivity and Gas Evolution With Aluminum‐Based Chloride and Oxychloride Catholytes in Solid‐State Sodium Batteries

All-solid-state sodium batteries (ASSBs) employing halide solid electrolytes (SEs) offer a cost-effective and energy-dense alternative to conventional liquid electrolyte systems. However, their high voltage (>4 V vs. Na/Na + ) performance remains limited by interfacial instability between the cathode active material (CAM) and the SE. We present here the electrochemical and interfacial behaviors of crystalline NaAlCl 4 and amorphous sodium–aluminum–oxychloride (NACO) SEs when combined with NaNi 0.5 Mn 0.5 O 2 cathode. While oxygen incorporation in NACO enhances ionic conductivity by nearly three orders of magnitude relative to NaAlCl 4 , it does not improve high-voltage cycling stability. Cells employing NACO exhibit accelerated capacity fade, increased cell impedance growth, and intrinsic oxygen evolution above 4.5 V vs. Na 3 Sn, as revealed by operando electrochemical mass spectrometry. In contrast, the NaAlCl 4 -based cells show no detectable gas release, underscoring their superior high-voltage stability and safety. Time-of-flight secondary-ion mass spectrometry confirms the formation of Al─O and Ni/Mn─Cl species, respectively, in the SE and CAM, indicating redox-driven anion exchange that contributes to kinetic hindrance of high-voltage phase transitions. The findings establish that while oxygen incorporation enhances ionic transport, it can compromise interfacial stability, suggesting pure chloride SEs may offer a more robust and intrinsically safer pathway for developing high-energy ASSBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Oxidation Temperature-Dependent Electrochemical Doping of WO 3 Deposited via Atomic Layer Deposition

Silicon-based photoelectrochemical devices show promise for the performance of light-driven CO 2 reduction but suffer from instability under photoelectrochemical conditions relevant to CO 2 reduction. Coating silicon electrodes with thin layers of metal oxides has shown promise to passivate unstable silicon surfaces, and many different metal oxides can be deposited on silicon using various techniques. In this study, we investigate the fundamental photoelectrochemical performance of WO 3 -coated silicon photoelectrodes, which were generated by oxidation of W-metal films deposited via atomic layer deposition on both degenerately doped (nSi + ) and low-doped (pSi) silicon. Two different oxidation temperatures were investigated (400 and 600 °C), and it was found that the monoclinic phase of WO 3 predominates at both temperatures but that more grain boundaries are present in the 600 °C film. From X-ray photoelectron spectroscopy, the stoichiometry of both films was found to be 1:3 W:O, and low electron energy loss experiments indicate band gaps of 3.0 and 3.1 eV for 400 and 600 °C films, respectively. Cyclic voltammetry experiments showed that the electron transfer kinetics increased after continued redox cycling, particularly for the material produced at 400 °C. X-ray photoelectron spectra suggest that the observed increase in electrode conductivity is due to the formation of oxygen vacancies in the film. Electrochemical impedance spectroscopy indicated that charge transport through the films was impacted by the grain boundaries that formed during oxidation of the film. Photoelectrochemical studies on pSi/WO 3 electrodes were highly variable, only producing a photocurrent and photovoltage with some samples. Our best sample, formed at 400 °C, produced a photovoltage of 180 mV, which is lower than what has previously been reported for WO 3 -coated silicon (500 mV). We hypothesize that the variability in photoelectrochemical experiments arose from a roughened WSiO x interface that is generated during film preparation. WO 3 shows promise as a metal oxide coating for silicon, but our results suggest that formation of a high-quality interface between Si and WO 3 is vital for best performance.

Charge transfer↗
DOE OSTI2025

Polyethylene Glycol Surface Modification and Polythiophene Side-Chain Chemistry: A Combined Strategy toward High-Capacity Lithium-Ion Battery Anodes

In the development of high-capacity lithium-ion batteries (LIBs), the combined optimization of active material interfaces and polymer binder chemistry plays a critical role in improving electrode performance and longevity. This work explores a dual design strategy incorporating polyethylene glycol (PEG) surface modification and carboxylated polythiophene side-chain tailoring to enhance the electrochemical behavior of magnetite (Fe 3 O 4 )-based anodes. PEG is employed to improve interfacial stability, while carboxylated polythiophene binders with varying alkyl side-chain lengths─poly[3-(potassium-4-butanoate)thiophene-2,5-diyl] (P3KBT), poly[3-(potassium-5-pentanoate)thiophene-2,5-diyl] (P3KPT), and poly[3-(potassium-6-hexanoate)thiophene-2,5-diyl] (P3KHT)─are used to modulate molecular interactions and ion transport. Among these three analogs, the PEG–Fe 3 O 4 –P3KHT electrode exhibits superior ion-transfer kinetics, the highest capacity retention, and the lowest charge-transfer resistance after extended cycling. Compared to their non-PEG analogs, PEG-coated electrodes demonstrate enhanced structural integrity and electrochemical behavior, emphasizing the synergistic effects of surface modification and side-chain chemistry. These findings highlight the importance of interfacial interactions and molecular design in achieving robust and high-performance composite anodes for next-generation LIBs.

Fe3O4↗
DOE OSTI2024

BioRT‐HBV 1.0: A Biogeochemical Reactive Transport Model at the Watershed Scale

Abstract Reactive Transport Models (RTMs) are essential tools for understanding and predicting intertwined ecohydrological and biogeochemical processes on land and in rivers. While traditional RTMs have focused primarily on subsurface processes, recent watershed‐scale RTMs have integrated ecohydrological and biogeochemical interactions between surface and subsurface. These emergent, watershed‐scale RTMs are often spatially explicit and require extensive data, computational power, and computational expertise. There is however a pressing need to create parsimonious models that require minimal data and are accessible to scientists with limited computational background. To that end, we have developed BioRT‐HBV 1.0, a watershed‐scale, hydro‐biogeochemical RTM that builds upon the widely used, bucket‐type HBV model known for its simplicity and minimal data requirements. BioRT‐HBV uses the conceptual structure and hydrology output of HBV to simulate processes including advective solute transport and biogeochemical reactions that depend on reaction thermodynamics and kinetics. These reactions include, for example, chemical weathering, soil respiration, and nutrient transformation. The model uses time series of weather (air temperature, precipitation, and potential evapotranspiration) and initial biogeochemical conditions of subsurface water, soils, and rocks as input, and output times series of reaction rates and solute concentrations in subsurface waters and rivers. This paper presents the model structure and governing equations and demonstrates its utility with examples simulating carbon and nitrogen processes in a headwater catchment. As shown in the examples, BioRT‐HBV can be used to illuminate the dynamics of biogeochemical reactions in the invisible, arduous‐to‐measure subsurface, and their influence on the observed stream or river chemistry and solute export. With its parsimonious structure and easy‐to‐use graphical user interface, BioRT‐HBV can be a useful research tool for users without in‐depth computational training. It can additionally serve as an educational tool that promotes pollination of ideas across disciplines and foster a diverse, equal, and inclusive user community.

Sadayappan, Kayalvizhi↗
DOE OSTI2024

Discoveries in Blast-Driven Turbulence of Astrophysical Relevance

The fluid mixing caused by variable-density instabilities is important in a wide variety of scenarios from ocean mixing and astrophysical phenomena to nuclear fusion techniques and atomic weapons. This thesis explores the mixing resulting from a specific instability known as the Blast Driven Instability (BDI). This work investigates the variable density mixing in an explosively driven environment due to the fluid instabilities at the material interfaces. Specifically, diverging Richtmyer-Meshkov (impulsive-acceleration environment) and Rayleigh-Taylor (variable-acceleration environment) instabilities (present in supernova and inertial confinement fusion) are studied using advanced high-speed diagnostics in carefully designed laboratory experiments. The BDI morphology is presented through a time development of Mie scattering images, and steps through the parameter space (varying density ratio and driver speed), highlighting the development of the structures that form during mixing. A scaling criterion is used to relate the two systems of vastly different spatiotemporal scales. Velocity fields in the BDI have been captured for the first time using the high temporal resolution PIV technique. Subsequent analysis of the dynamics of the instability from the velocity fields illustrates the distribution of kinetic energy, the transition to turbulence, and the characteristic growth of the instability are discussed. This study furthers understanding of how blast-driven instability pertains to supernova and inertial confinement fusion science. The morphology of the BDI has been characterized for the first time. This work steps through the parameter space covered in Mie scattering experiments, and how the different parameters contribute to development of structures and mixing. It also examines a scaling of the Atwood number for expanding predictive capabilities to other experimental conditions and simulations. The first collection of velocity fields acquired for the BDI are recorded, and subsequent analysis evaluating the distribution of kinetic energy throughout space and time for two density ratios from the overall parameter space, as well as the transition to turbulence, estimated from a Reynolds number calculated based on momentum mixing are all presented. This information is useful in advancing the development of models to predict physics of high energy density applications where experiments are not always readily available. This research has successfully demonstrated understanding for the time criteria defining regimes where the shock driven (Richtmyer-Meshkov instability) and the buoyancy driven (Rayleigh-Taylor instability) dominates through a parametric study of density variation (Atwood number) and driver speed (Mach number). All this furthers understanding of how the BDI pertains to SN and ICF.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Laboratory Demonstration of Collisionless Blob Formation via Laser-Produced Plasma Self-Focusing

Strongly localized, propagating plasma density structures that are capable of crossing magnetic field lines are known as “blobs.” Here we demonstrate a novel mechanism for the formation and propagation of an ion gyroradius-scale blob-cavity structure at the interface between a super-Alfvénic laser-produced plasma (LPP) and an ambient magnetized plasma. The LPP self-focuses along the edge of the diamagnetic cavity which results in a dense, jetlike structure as compared to ballistic motion. This collimated flow couples momentum to the ambient plasma through a collisionless process known as Larmor coupling. The Larmor electric fields locally displace the ambient ions forming a blob above the LPP flow. In the region between a gyrating blob and collimated LPP flow, a secondary cavity of expelled magnetic field forms. In conclusion, these findings are supported by particle-in-cell simulations that replicate the blob formation mechanism and provide insight to similar processes in space, astrophysical, and laboratory settings characterized by ion kinetic scales.

Fluorescence spectroscopy↗
NASA NTRS1986

Oxidation of commercial purity titanium

The oxidation kinetics of commercial purity Ti-A55 exposed to laboratory air in the 593-760 C temperature range were continuously monitored by thermogravimetric analysis. The oxide thickness was measured by microscopy, and the substrate contamination was estimated from microhardness measurements. The microhardness depth profiles were converted to oxygen composition profiles using calibration depth. The oxygen diffusion coefficient in alpha-Ti appears to be approximately concentration-independent in the 1-10 at. pct oxygen range. Diffusion coefficient for oxygen in TiO2 has been estimated as a function of temperature and is found to be about 50 times the value in alpha-Ti. The metallographically prepared cross sections of the oxidized specimens revealed a 'moving boundary' in the substrate, parallel to the oxide-metal interface. This boundary was associated with a specific oxygen level of 5.0 + or - 0.5 at. pct. It occurred at a distance from the oxide-metal interface which was correlatable with temperature and time of exposure. The diffusion coefficient corresponding to the composition of this moving boundary is in excellent agreement with the effective diffusion coefficient for the substrate contamination.

Unnam, J.↗
NASA NTRS1999

Thermal Conductivity and Elastic Modulus Evolution of Thermal Barrier Coatings under High Heat Flux Conditions

Laser high heat flux test approaches have been established to obtain critical properties of ceramic thermal barrier coatings (TBCs) under near-realistic temperature and thermal gradients that may he encountered in advanced engine systems. Thermal conductivity change kinetics of a thin ceramic coating were continuously monitored in real time at various test temperatures. A significant thermal conductivity increase was observed during the laser simulated engine heat flux tests. For a 0.25 mm thick ZrO2-8%Y2O3 coating system, the overall thermal conductivity increased from the initial value of 1.0 W/m-K to 1. 15 W/m-K, 1. 19 W/m-K and 1.5 W/m-K after 30 hour testing at surface temperatures of 990C, 1100C, and 1320C. respectively. Hardness and modulus gradients across a 1.5 mm thick TBC system were also determined as a function of laser testing time using the laser sintering/creep and micro-indentation techniques. The coating Knoop hardness values increased from the initial hardness value of 4 GPa to 5 GPa near the ceramic/bond coat interface, and to 7.5 GPa at the ceramic coating surface after 120 hour testing. The ceramic surface modulus increased from an initial value of about 70 GPa to a final value of 125 GPa. The increase in thermal conductivity and the evolution of significant hardness and modulus gradients in the TBC systems are attributed to sintering-induced micro-porosity gradients under the laser-imposed high thermal gradient conditions. The test techniques provide a viable means for obtaining coating data for use in design, development, stress modeling, and life prediction for various thermal barrier coating applications.

Zhu, Dongming↗
NASA NTRS1997

Interfacing Relativistic and Nonrelativistic Methods: A Systematic Sequence of Approximations

A systematic sequence of approximations for the introduction of relativistic effects into nonrelativistic molecular finite-basis set calculations is described. The theoretical basis for the approximations is the normalized elimination of the small component (ESC) within the matrix representation of the modified Dirac equation. The key features of the normalized method are the retention of the relativistic metric and the ability to define a single matrix U relating the pseudo-large and large component coefficient matrices. This matrix is used to define a modified set of one- and two-electron integrals which have the same appearance as the integrals of the Breit-Pauli Hamiltonian. The first approximation fixes the ratios of the large and pseudo-large components to their atomic values, producing an expansion in atomic 4-spinors. The second approximation defines a local fine-structure constant on each atomic centre, which has the physical value for centres considered to be relativistic and zero for nonrelativistic centres. In the latter case, the 4-spinors are the positive-energy kinetic al ly-balanced solutions of the Levy-Leblond equation, and the integrals involving pseudo-large component basis functions on these centres, are set to zero. Some results are presented for test systems to illustrate the various approximations.

Dyall, Ken↗
DOE OSTI2024

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

In this article, lithium metal (Li 0 ) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode–electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h -1 . A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li 0 stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li 0 deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li + diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li 0 –Li 0 cells, reaching 12 000 h at 0.2 mA cm -2 and 5000 h at 0.5 mA cm -2 . Furthermore, owing to its high critical current density of 9 mA cm -2 , the Li 0 –LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cell demonstrates stable cycling at 5 mA cm -2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

25 ENERGY STORAGE↗
NASA NTRS2000

Phase Shift Interferometer and Growth Set Up to Step Pattern Formation During Growth From Solutions. Influence of the Oscillatory solution Flow on Stability

We have assembled an experimental setup based on Michelson interferometry with the growing crystal surface as one of the reflective surfaces. The crystallization part of the device allows optical monitoring of a face of a crystal growing at temperature stable within 0.05 C in a flow of solution of controlled direction and speed. The reference arm of the interferometer contains a liquid crystal element that allows controlled shifts of the phase of the interferograms. We employ an image-processing algorithm, which combines five images with a pi/2 phase difference between each pair of images. The images are transferred to a computer by a camera capable of capturing 60 frames per second. The device allows data collection on surface morphology and kinetics during the face layers growth over a relatively large area (approximately 4 sq. mm) in situ and in real time during growth. The estimated depth resolution of the phase shifting interferometry is approximately 50 Angstroms. The data will be analyzed in order to reveal and monitor step bunching during the growth process. The crystal chosen as a model for study in this work is KH2PO4 (KDP). This optically non-linear material is widely used in frequency doubling applications. There have been a number of studies of the kinetics of KDP crystallization that can serve as a benchmark for our investigations. However, so far, systematic quantitative characteristics of step interaction and bunching are missing. We intend to present our first quantitative results on the onset, initial stages and development of instabilities in moving step trains on vicinal crystal surfaces at varying supersaturation, flow rate, and flow direction. Behavior of a vicinal face growing from solution flowing normal to the steps and periodically changing its direction in time was considered theoretically. It was found that this oscillating flow reduces both stabilization and destabilization effects resulted from the unidirectional solution flow directed up the step stream and down the step stream. This reduction of stabilization and destabilization comes from effective mixing which entangles the phase shifts between the spatially periodic interface perturbation and the concentration wave induced by this perturbation. Numerical results and simplified mixing criterion will be discussed.

Chernov, Alex A.↗
DOE OSTI2026

Modulating Operational Conditions to Mitigate Deactivation in Formate Dehydrogenation on Pd Phases

In heterogeneous catalysis, poisoning by surface-bound intermediates poses a major barrier to sustained catalyst performance in (de)hydrogenation reactions. Formate/bicarbonate systems, as liquid organic hydrogen carriers (LOHCs), offer a CO 2 -integrated, low-temperature pathway for hydrogen storage and release, making them attractive for circular energy applications. However, their lower hydrogen density and susceptibility to catalyst deactivation limit their competitiveness compared to conventional LOHCs like methylcyclohexane. Here, this study investigates the mechanistic origins of formate (HCOO – ) dehydrogenation and associated deactivation on Pd interfaces. Using density functional theory (DFT) simulations, we show that under thermocatalytic conditions, strongly bound formate accumulates on the catalyst surface (Pd(111)), blocking active sites, raising activation barriers, and leading to progressive performance loss. Because formate adsorption involves charge transfer, we exploit its sensitivity to electronic structure by modulating the electrochemical potential of the catalyst. Our results reveal that hydrogen transfer from water and formate exhibits opposing potential dependencies, providing insights into the opposing driving forces behind both catalytic activity and poisoning. To further probe this phenomenon, we examine electrochemically induced phase transitions in Pd, focusing on PdO(100) and PdH(110), which are stable under oxidizing and reducing potentials, respectively, and demonstrate enhanced dehydrogenation activity between −0.4 and 0.2 V vs standard hydrogen electrode (SHE). Complementary thermal treatments help decouple kinetic and thermodynamic contributions to intermediate binding. These findings underscore the critical role of the catalyst phase and external stimuli in dictating poison-active site interactions and highlight phase engineering as a promising strategy to mitigate deactivation. This work offers mechanistic insights and design principles for developing more resilient and efficient catalysts for LOHC applications under realistic operating conditions.

Pd phase↗