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Results for “Surface functionalization”

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 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Electrochemical flow cell enabling operando probing of electrocatalyst surfaces by X-ray spectroscopy and diffraction

The rational improvement of current and developing electrochemical technologies requires atomistic understanding of electrode–electrolyte interfaces. However, examining these interfaces under operando conditions, where performance is typically evaluated and benchmarked, remains challenging, as it necessitates incorporating an operando probe during full electrochemical operation. In this study, we describe a custom electrochemical flow cell that enables near-surface-sensitive operando investigation of planar thin-film catalysts at significant hydrogen evolution reaction (HER) rates (in excess of -100 mA cm-2) using grazing incidence X-ray methods. Grazing-incidence X-ray spectroscopy and diffraction were implemented on the same sample under identical HER conditions, demonstrating how the combined measurements track changing redox chemistry and structure of Cu thin-film catalyst surfaces as a function of electrochemical conditions. The coupling of these methods with improved mass transport and hydrodynamic control establishes a new paradigm for operando measurement design, enabling unique insights into the key fundamental processes occurring at the catalyst–electrolyte interface.

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

Small energy gap revealed in CrBr 3 by scanning tunneling spectroscopy

CrBr 3 is a layered van der Waals material with magnetic ordering down to the 2D limit. For decades, based on optical measurements, it is believed that the energy gap of CrBr 3 is in the range of 1.68–2.1 eV. However, controversial results have indicated that the band gap of CrBr 3 is possibly smaller than that. An unambiguous determination of the energy gap is critical to the correct interpretations of the experimental results of CrBr 3 . Here, we present the scanning tunneling microscopy and spectroscopy (STM/S) results of CrBr 3 thin and thick flakes exfoliated onto highly ordered pyrolytic graphite (HOPG) surfaces and density functional theory (DFT) calculations to reveal the small energy gap (peak-to-peak energy gap to be 0.57 ± 0.04 eV; or the onset signal energy gap to be 0.29 ± 0.05 eV from dI/dV spectra). Atomic resolution topography images show the defect-free crystal structure and the dI/dV spectra exhibit multiple peak features measured at 77 K. The conduction band – valence band peak pairs in the multi-peak dI/dV spectrum agree very well with all reported optical transitions. STM topography images of mono- and bi-layer CrBr 3 flakes exhibit edge degradation due to short air exposure (~15 min) during sample transfer. The unambiguously determined small energy gap settles the controversy and is the key in better understanding CrBr 3 and similar materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Modelling drug adsorption in metal–organic frameworks: the role of solvent

Solvent plays a key role in biological functions, catalysis, and drug delivery. Metal–organic frameworks (MOFs) due to their tunable functionalities, porosities and surface areas have been recently used as drug delivery vehicles. To investigate the effect of solvent on drug adsorption in MOFs, we have performed integrated computational and experimental studies in selected biocompatible MOFs, specifically, UiO-AZB, HKUST-1 (or CuBTC) and NH 2 -MIL-53(Al). The adsorption of three drugs, namely, 5-fluorouracil (5-FU), ibuprofen (IBU), and hydroxyurea (HU) were performed in the presence and absence of the ethanol. Our computational predictions, at 1 atmospheric pressure, showed a reasonable agreement with experimental studies performed in the presence of ethanol. We find that in the presence of ethanol the drug molecules were adsorbed at the interface of solvent and MOFs. Moreover, the computationally calculated adsorption isotherms suggested that the drug adsorption was driven by electrostatic interactions at lower pressures (<10 –4 Pa). Our computational predictions in the absence of ethanol were higher compared to those in the presence of ethanol. The MOF–adsorbate interaction (U HA ) energy decreased with decrease in the size of a drug molecule in all three MOFs at all simulated pressures. At high pressure the interaction energy increases with increase in the MOFs pore size as the number of molecules adsorbed increases. Thus, our research shows the important role played by solvent in drug adsorption and suggests that it is critical to consider solvent while performing computational studies.

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

Spectroscopic observation and structure-insensitivity of hydroxyls on gold

Here, the O–H stretching vibration of surface hydroxyls remained at 3691 cm –1 for gold structures ranging in size from clusters to nanoparticles, to non-flat bulk surfaces. In contrast, this vibration was not observed on flat gold surfaces. Therefore, this vibration can serve as an indicator of the roughness of the gold surface and associated functional properties, such as catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Precision control of thermal transport in cryogenic single-crystal silicon devices

We report on the diffusive-ballistic thermal conductance of multi-moded single-crystal silicon beams measured below 1 K. It is shown that the phonon mean-free-path ℓ is a strong function of the surface roughness characteristics of the beams. This effect is enhanced in diffuse beams with lengths much larger than ℓ, even when the surface is fairly smooth, 5–10 nm rms, and the peak thermal wavelength is 0.6 μm. Resonant phonon scattering has been observed in beams with a pitted surface morphology and characteristic pit depth of 30 nm. Hence, if the surface roughness is not adequately controlled, the thermal conductance can vary significantly for diffuse beams fabricated across a wafer. In contrast, when the beam length is of order ℓ, the conductance is dominated by ballistic transport and is effectively set by the beam cross-sectional area. We have demonstrated a uniformity of ±8% in fractional deviation for ballistic beams, and this deviation is largely set by the thermal conductance of diffuse beams that support the micro-electro-mechanical device and electrical leads. In addition, we have found no evidence for excess specific heat in single-crystal silicon membranes. This allows for the precise control of the device heat capacity with normal metal films. We discuss the results in the context of the design and fabrication of large-format arrays of far-infrared and millimeter wavelength cryogenic detectors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

An in-flight radiography platform to measure hydrodynamic instability growth in inertial confinement fusion capsules at the National Ignition Facility

A new in-flight radiography platform has been established at the National Ignition Facility (NIF) to measure Rayleigh–Taylor and Richtmyer–Meshkov instability growth in inertial confinement fusion capsules. The platform has been tested up to a convergence ratio of 4. An experimental campaign is underway to measure the growth of pre-imposed sinusoidal modulations of the capsule surface, as a function of wavelength, for a pair of ignition-relevant laser drives: a “low-foot” drive representative of what was fielded during the National Ignition Campaign (NIC) [Edwards et al., Phys. Plasmas 20, 070501 (2013)] and the new high-foot [Dittrich et al., Phys. Rev. Lett. 112, 055002 (2014); Park et al., Phys. Rev. Lett. 112, 055001 (2014)] pulse shape, for which the predicted instability growth is much lower. We present measurements of Legendre modes 30, 60, and 90 for the NIC-type, low-foot, drive, and modes 60 and 90 for the high-foot drive. The measured growth is consistent with model predictions, including much less growth for the high-foot drive, demonstrating the instability mitigation aspect of this new pulse shape. We present the design of the platform in detail and discuss the implications of the data it generates for the on-going ignition effort at NIF.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Competing adsorption mechanisms of pyridine on Cu, Ag, Au, and Pt(110) surfaces

We explore the adsorption of pyridine on Cu, Ag, Au, and Pt(110) surfaces using density functional theory. To account for the van der Waals interaction, we use the optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, and rPW86-vdW2 functionals. For comparison, we also run calculations using the generalized gradient approximation-PBE (Perdew–Burke–Ernzerhof) functional. We find the most stable adsorption site to depend on both metal and functional, with two energetically favorable adsorption sites, namely, a vertically oriented site and a flat pyridine site. We calculate that every functional predicts pyridine to lie in the vertical configuration on the coinage metals at a low coverage. On Pt(110), by contrast, we calculate all the functionals—except rPW86-vdW2—to predict pyridine to lie flat at a low coverage. By analyzing these differences for these adsorption configurations, along with various geometric and electronic properties of the adsorbate/substrate system, we access in detail the performance of the 6 functionals we use. We also characterize the nature of the bonding of pyridine on the coinage metals from weak to strong physisorption, depending on the functional used. On Pt(110), we characterize the nature of the bonding of pyridine as ranging from strong physisorption to strong chemisorption depending again on the functional used, illustrating both the importance of the van der Waals interaction to this system and that this system can make a stringent test for computational methods.

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

Exploring spin symmetry-breaking effects for static field ionization of atoms: Is there an analog to the Coulson–Fischer point in bond dissociation?

Löwdin's symmetry dilemma is an ubiquitous issue in approximate quantum chemistry. In the context of Hartree-Fock (HF) theory, the use of Slater determinants with some imposed constraints to preserve symmetries of the exact problem may lead to physically unreasonable potential energy surfaces. On the other hand, lifting these constraints leads to the so-called broken symmetry solutions that usually provide better energetics, at the cost of losing information about good quantum numbers that describe the state of the system. This behavior has previously been extensively studied in the context of bond dissociation. Here, this paper studies the behavior of different classes of HF spin polarized solutions (restricted, unrestricted, and generalized) in the context of ionization by strong static electric fields. We find that, for simple two electron systems, unrestricted Hartree-Fock (UHF) is able to provide a qualitatively good description of states involved during the ionization process (neutral, singly ionized, and doubly ionized states), whereas RHF fails to describe the singly ionized state. For more complex systems, even though UHF is able to capture some of the expected characteristics of the ionized states, it is constrained to a single M s (diabatic) manifold in the energy surface as a function of field intensity. In this case, a better qualitative picture can be painted by using generalized Hartree-Fock as it is able to explore different spin manifolds and follow the lowest solution due to lack of collinearity constraints on the spin quantization axis.

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

The N3/TiO 2 interfacial structure is dependent on the pH conditions during sensitization

The electronic structure of the N3/TiO 2 interface can directly influence the performance of a dye sensitized solar cell (DSSC). Therefore, it is crucial to understand the parameters that control the dye’s orientation on the semiconductor’s surface. A typical step in DSSC fabrication is to submerge the nanoparticulate semiconductor film in a solution containing the dye, the sensitizing solution. The pH of the N3 sensitizing solution determines the distribution of the N3 protonation states that exist in solution. Altering the pH of the sensitizing solution changes the N3 protonation states that exist in solution and, subsequently, the N3 protonation states that anchor to the TiO 2 substrate. We utilize the surface specific technique of heterodyne detected vibrational sum frequency generation spectroscopy to determine the binding geometry of N3 on a TiO 2 surface as a function of the sensitizing solution pH conditions. It is determined that significant reorientation of the dye occurs in pH ≤ 2.0 conditions due to the lack of N3-dye carboxylate anchoring groups participating in adsorption to the TiO 2 substrate. Consequently, the change in molecular geometry is met with a change in the interfacial electronic structure that can hinder electron transfer in DSSC architectures.

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

Cinematic reflectometry using QIKR, the quite intense kinetics reflectometer

The Quite Intense Kinetics Reflectometer (QIKR) will be a general-purpose, horizontal-sample-surface neutron reflectometer. Reflectometers measure the proportion of an incident probe beam reflected from a surface as a function of wavevector (momentum) transfer to infer the distribution and composition of matter near an interface. The unique scattering properties of neutrons make this technique especially useful in the study of soft matter, biomaterials, and materials used in energy storage. Exploiting the increased brilliance of the Spallation Neutron Source Second Target Station, QIKR will collect specular and off-specular reflectivity data faster than the best existing such machines. It will often be possible to collect complete specular reflectivity curves using a single instrument setting, enabling “cinematic” operation, wherein the user turns on the instrument and “films” the sample. Samples in time-dependent environments (e.g., temperature, electrochemical, or undergoing chemical alteration) will be observed in real time, in favorable cases with frame rates as fast as 1 Hz. Cinematic data acquisition promises to make time-dependent measurements routine, with time resolution specified during post-experiment data analysis. This capability will be deployed to observe such processes as in situ polymer diffusion, battery electrode charge–discharge cycles, hysteresis loops, and membrane protein insertion into lipid layers.

47 OTHER INSTRUMENTATION↗
DOE OSTI2012

Insights into the Molecular Activation Mechanism of the RhoA-specific Guanine Nucleotide Exchange Factor, PDZRhoGEF

PDZRhoGEF (PRG) belongs to a small family of RhoA-specific nucleotide exchange factors that mediates signaling through select G-protein-coupled receptors via G{alpha}{sub 12/13} and activates RhoA by catalyzing the exchange of GDP to GTP. PRG is a multidomain protein composed of PDZ, regulators of G-protein signaling-like (RGSL), Dbl-homology (DH), and pleckstrin-homology (PH) domains. It is autoinhibited in cytosol and is believed to undergo a conformational rearrangement and translocation to the membrane for full activation, although the molecular details of the regulation mechanism are not clear. It has been shown recently that the main autoregulatory elements of PDZRhoGEF, the autoinhibitory 'activation box' and the 'GEF switch,' which is required for full activation, are located directly upstream of the catalytic DH domain and its RhoA binding surface, emphasizing the functional role of the RGSL-DH linker. Here, using a combination of biophysical and biochemical methods, we show that the mechanism of PRG regulation is yet more complex and may involve an additional autoinhibitory element in the form of a molten globule region within the linker between RGSL and DH domains. We propose a novel, two-tier model of autoinhibition where the activation box and the molten globule region act synergistically to impair the ability of RhoA to bind to the catalytic DH-PH tandem. The molten globule region and the activation box become less ordered in the PRG-RhoA complex and dissociate from the RhoA-binding site, which may constitute a critical step leading to PRG activation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Cross slip of extended dislocations in face-centered cubic metals through phase-field modeling

Cross slip is a dislocation mechanism that significantly impacts the mechanical behavior of engineering alloys. Here, in this work, we advance a 3D phase-field dislocation dynamics (PFDD) mesoscale technique to simulate cross slip across a broad range of face-centered cubic (FCC) metals. The formulation incorporates elastic anisotropy, an FCC numerical grid, and a high-fidelity representation of the entire γ -surface from density functional theory for eight FCC metals and no adjustable parameters or rules. The relaxed core structures under zero stress for all metals are predicted to extend in plane. The analytical model for stacking fault width agrees well with the PFDD result under the assumption of elastic isotropy but overestimates it under elastic anisotropy, when the degree of anisotropy is large. The dynamic simulations are designed to elucidate the material parameters that influence the propensity for cross slip. Whether cross slip occurs under a non-Schmid stress or to bypass a hard obstacle, the critical stress to cross slip scales strongly with the anisotropic energy coefficient for a screw dislocation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A transient site balance model for atomic layer etching

We present a transient site balance model of plasma-assisted atomic layer etching of silicon (Si) with alternating exposure to chlorine gas (Cl 2 ) and argon ions (Ar + ). Molecular dynamics (MD) simulation results are used to provide parameters for the model. The model couples the dynamics of a top monolayer surface region ('top layer') and a perfectly mixed subsurface region ('mixed layer'). The differential equations describing the rates of change of the Cl coverage in the two layers are transient mass balances. Model predictions include Cl coverages and rates of etching of various species from the surface as a function of Cl 2 or Ar + fluence. The simplified phenomenological model reproduces the MD simulation results well over a range of conditions. Comparing model predictions directly to experimental optical emission spectroscopy data, as reported in a previous paper, provides further evidence of the accuracy of the model.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

A methodology to compute the critical current limit in Nb3Sn magnets

Numerous experiments have shown that the loads applied to Nb3Sn strands and cables can reduce their critical current. Experiments, performed on uniaxially loaded strands, allowed to define clear laws to describe the evolution of the critical surface as a function of the applied current, field, temperature and strain. It is, however, still unclear how these laws can be applied to superconducting magnets. The present paper proposes a methodology to estimate the critical current and temperature margin reduction on superconducting magnets due to stress on the superconducting material. The methodology is tested on the MQXF magnets, a quadrupole developed for the High Luminosity LHC project, and successfully validated by comparing computed strain with data from strain gauge measurements. Overall, results suggested that, because of the stresses arising in winding during assembly, cool-down and powering, the current limit of the magnet is lower than the expected short sample limit, and that the most critical region does not coincide with the peak field location.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Never judge a black hole by its area

Christodoulou and Rovelli have shown that black holes have large interiors that grow asymptotically linearly in advanced time, and speculated that this may be relevant to the information loss paradox. We show that there is no simple relation between the interior volume of an arbitrary black hole and its horizon area. That is, the volume enclosed is not necessarily a monotonically increasing function of the surface area.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Neutron knockout from 68,70 Ni ground and isomeric states

Neutron-rich isotopes are an important source of new information on nuclear physics. Specifically, the spin-isospin components in the nucleon-nucleon (NN) interaction, e.g., the proton-neutron tensor force, are expected to modify shell structure in exotic nuclei. These potential changes in the intrinsic shell structure are of fundamental interest. The study of the excitation energy of states corresponding to specific configurations in even-even isotopes, together with the single-particle character of the first excited states of odd-A, neutron-rich Ni isotopes, probes the evolution of the neutron orbitals around the Fermi surface as a function of the neutron number a step forward in the understanding of the region and the nature of the NN interaction at large N/Z ratios. In an experiment carried out at the National Superconducting Cyclotron Laboratory, new spectroscopic information was obtained for 68 Ni and the distribution of single-particle strengths in 67,69 Ni was characterized by means of single-neutron knockout from 68,70 Ni secondary beams. The spectroscopic strengths, deduced from the measured partial cross sections to the individual states tagged by their de-exciting gamma rays, is used to identify and quantify configurations that involve neutron excitations across the N = 40 harmonic oscillator shell closure. Finally, the de-excitation rays were measured with the GRETINA tracking array.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2014

FINDING ROCKY ASTEROIDS AROUND WHITE DWARFS BY THEIR PERIODIC THERMAL EMISSION

Since white dwarfs (WDs) are small, the contrast between the thermal emission of an orbiting object and a WD is dramatically enhanced compared to a main-sequence host. Furthermore, rocky objects much smaller than the moon have no atmospheres and are tidally locked to the WD. We show that this leads to temperature contrasts between their day and night side of the order of unity that should lead to temporal variations in infrared flux over an orbital period of ∼0.2 to ∼2 days. Ground-based telescopes could detect objects with a mass as small as 1% of the lunar mass M{sub L} around Sirius B with a few hours of exposure. The James Webb Space Telescope may be able to detect objects as small as 10{sup –3} M{sub L} around most nearby WDs. The tightest constraints will typically be placed on 12,000 K WDs, whose Roche zone coincides with the dust sublimation zone. Constraining the abundance of minor planets around WDs as a function of their surface temperatures (and therefore age) provides a novel probe for the physics of planetary formation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Evaluation of the Radioactive Material Released in the Harborview Research and Training Building and Some Implications for Emergency Response

On 2 May 2019, during the 137 Cs source recovery operation, a source capsule in a research irradiator containing approximately 77.1 TBq was breached. Based on a geometric reconstruction analysis of the damage to the capsule, approximately 46.3 GBq (0.04%) was impacted by the chop saw (grinder) inside a mobile hot cell on the loading dock at the University of Washington Harborview Research and Training (HRT) Building. A very small fraction of the material impacted, less than 1%, was released from the mobile hot cell and then to the rest of the HRT Building. The objectives of this project were to assess the accidental release of 137 CsCl and its implications related to emergency response methods and the ramifications of 137 CsCl transport. The phenomenology of this event was also compared with past alkali halide dispersal events. The vast number of measurements and samples collected by the remediation contractors, the Department of Energy’s Nuclear Emergency Support Team, and the small number of retrospective samples collected by the authors informed the analysis. The techniques included (1) autoradiography and electron microscopy of samples collected from the HRT Building and the irradiator, (2) 3D visualization of deposition on surfaces and within the ventilation system, and (3) a study of the damage to the source capsule to evaluate the Cs particle size and particle composition due to the grinding accident. Subsequently, the cesium contaminant transport through the numerous pathways in the building was reconstructed to assess the deposition on surfaces as a function of particle size. Furthermore, the implications for emergency response are relevant to data quality and management. A Data Quality Objective guides data collection methods so that they have appropriate accuracy and precision for the intended application. Recommendations were made with respect to the sample collection protocols and archiving of samples.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗