Search NASA⌕ Search

SEARCH · Search NASA

Results for “surface structure”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

The role of defects in Fe(II) – goethite electron transfer

Despite accumulating experimental evidence for Fe(II)-Fe(III) oxide electron transfer, computational chemical calculations suggest that oxidation of sorbed Fe(II) is not energetically feasible unless defects are present. Here we used isotope specific 57Fe Mössbauer spectroscopy to investigate whether Fe(II)-goethite electron transfer is influenced by defects. Specifically, we heated the mineral to try to anneal the goethite surface and ground goethite to try to create defects. We found that heating goethite results in less oxidation of sorbed Fe(II) by goethite. When goethite was re-ground after heating, electron transfer was partially restored. X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) of heated and ground goethite confirm that heating and grinding alter the surface structure of the goethite. We propose that the heating process annealed the surface and decreased the number of sites where electron transfer could occur. Our experimental findings suggest that surface defects play an important role in Fe(II)-goethite electron transfer as suggested by computational calculations. Our finding that defects influence heterogeneous Fe(II)-goethite electron transfer has important implications for Fe(II) driven recrystallization of Fe oxides, as well as X and Y.

Notini, Luiza↗
DOE OSTI2017

Pore-scale water dynamics during drying and the impacts of structure and surface wettability

Plants and microbes secrete mucilage into soil during dry conditions, which can alter soil structure and increase contact angle. Structured soils exhibit a broad pore size distribution with many small and many large pores, and strong capillary forces in narrow pores can retain moisture in soil aggregates. Meanwhile, contact angle determines the water repellency of soils, which can result in suppressed evaporation rates. Although they are often studied independently, both structure and contact angle influence water movement, distribution, and retention in soils. Here drying experiments were conducted using soil micromodels patterned to emulate different aggregation states of a sandy loam soil. Micromodels were treated to exhibit contact angles representative of those in bulk soil (8.4° ± 1.9°) and the rhizosphere (65° ± 9.2°). Drying was simulated using a lattice Boltzmann single-component, multiphase model. In our experiments, micromodels with higher contact angle surfaces took 4 times longer to completely dry versus micromodels with lower contact angle surfaces. Microstructure influenced drying rate as a function of saturation and controlled the spatial distribution of moisture within micromodels. In conclusion, lattice Boltzmann simulations accurately predicted pore-scale moisture retention patterns within micromodels with different structures and contact angles.

4↗
DOE OSTI2026

Task Sharing of Proton Incorporation in Vertically Aligned Nanocomposite Triple Conductors: Growth, Structure, and Surface Exchange Kinetics

As protonic ceramic electrolysis cells emerge for efficient H 2 production, there is a need to develop air electrode materials enabling fast, durable steam splitting and proton incorporation. Single-phase triple conductors may fail to satisfy the myriad performance/stability requirements, and their critical charge-carriers (holes, oxygen vacancies, and protons) are in competition, limiting their concentrations. Instead, we propose task-sharing, vertically aligned nanocomposites (VANs), comprising a proton conductor (BaZr 0.9 Y 0.1 O 3-δ ) and a redox-active mixed ionic electronic conductor (Ce 0.9 Pr 0.1 O 2-δ ), that may enable rapid proton surface exchange at the solid–gas interface and transport along the solid–solid heterointerfaces. We grew VANs by pulsed laser deposition and investigated the interplay between their processing conditions, structure, and proton and oxygen surface exchange kinetics. We varied the substrate temperature, laser repetition rate, laser fluence, and processing oxygen pressure. The crystallinity and phases were characterized by grazing-incidence X-ray diffraction, and the strain and structural order as a function of depth were evaluated by angle-dependent synchrotron X-ray pair distribution function analysis. To evaluate the potential for interdiffusion, the formation energies of substitutional defects were simulated with density functional theory. Corresponding structural analysis and elemental mapping were performed by scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy-loss spectroscopy, indicating distinct nanoscale compositional regions with a hierarchical structure embedded in individual VANs columns and minimal interdiffusion across a bilayer film. Proton and oxygen surface exchange coefficients (k H , k O ) and polarization resistances were evaluated by electrical and optical relaxations and impedance spectroscopy of VAN-incorporated protonic ceramic electrochemical cells, respectively, at 400–500 °C, demonstrating values comparable to some of the best-known triple and mixed conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Effects of Co contents on the microstructures and properties of the electrodeposited NiCo–Zr composite coatings

Highlights: • The novel NiCo–Zr coatings were prepared by electro-deposition. • Surface morphology, crystal structure, grain size and microstrain were examined. • Texture, residual stress and corrosion resistance were investigated. • Addition of Co increased the hardness and corrosion resistance of the coatings. - Abstract: In this study, the NiCo–Zr composite coatings were prepared from the electrolytes with different Co{sup 2+} concentrations by electrodeposition method. The effects of Co contents on the crystal structure, surface morphology, grain size, microstrain and residual stress were examined by X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), Energy dispersive X-ray spectroscopy (EDX) and atomic force microscope (AFM). The corrosion resistance of the composite coatings was also examined by the potentiodynamic polarization and electrochemical impedance (EIS) measurements. The results revealed that the crystal structures of the coatings were dependent on the Co contents and addition of Co content of 58 wt% resulted in the formation of hexagonal (hcp) Co. The increasing Co contents in the NiCo–Zr composite coatings resulted in the smoother and more compact surface, decreased the grain size and increased the microstrain. The micro-hardness and residual stress also increased with increasing Co contents. The addition of Co increased the corrosion resistance of the NiCo–Zr composite coatings compared with the Ni–Zr coating while the corrosion resistance of the NiCo–Zr composite coatings decreased as the Co contents increased.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Atomic structure and grain shape evolution of nanodiamond during annealing in oxidizing atmosphere from neutron diffraction and MD simulations

In this work, real space pair-distribution function (PDF) analysis in conjunction with molecular dynamics (MD) simulations was applied to characterize crystal structure, shape and surface structure of diamond nanoparticles annealed in air up to 880 °C. MD simulated models of individual nanodiamond particles of various shapes and sizes were used to calculate theoretical radial distribution functions G(r) for powders with different grain size distributions. The calculated curves, showing distinct differences for the explored parameter space, were compared to the experimental G(r) functions obtained from neutron scattering for annealed detonated nanodiamond samples in a search for a model best describing the actual powders. It was found that as-synthesized nanodiamond grains are terminated by equally abundant (100), (110) and (111) crystallographic faces and their structure does not change upon annealing in air up to 280 °C. The shape and size of grains annealed above 480 °C changes due to surface etching. The etching rate differs between crystals faces and depends on temperature, resulting in the observed differences in grain shape. Below 680 °C the share of the (110) facets gradually increases and at 680 °C the grains become rhombic dodecahedra terminated solely by (110) surfaces. Further increase of the annealing temperature promotes formation of (111) surfaces and at 880 °C the preferred grain shape becomes an octahedron terminated by a variant of (111) surfaces possessing three dangling sp3 bonds per atom. At lower temperatures all grains become smaller and the size distribution moves towards the lower values. Furthermore, as the annealing temperature increases, the smallest grains disappear entirely and the average grain size grows back.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ions Tune Interfacial Water Structure and Modulate Hydrophobic Interactions at Silica Surfaces

The structure and ultrafast dynamics of the electric double layer (EDL) are central to chemical reactivity and physical properties at solid/aqueous interfaces. While the Gouy–Chapman–Stern model is widely used to describe EDLs, it is solely based on the macroscopic electrostatic attraction of electrolytes for the charged surfaces. Structure and dynamics in the Stern layer are, however, more complex because of competing effects due to the localized surface charge distribution, surface–solvent–ion correlations, and the interfacial hydrogen bonding environment. Here, we report combined time-resolved vibrational sum frequency generation (TR-vSFG) spectroscopy with ab initio DFT-based molecular dynamics simulations (AIMD/DFT-MD) to get direct access to the molecular-level understanding of how ions change the structure and dynamics of the EDL. We show that innersphere adsorbed ions tune the hydrophobicity of the silica–aqueous interface by shifting the structural makeup in the Stern layer from dominant water–surface interactions to water–water interactions. This drives an initially inhomogeneous interfacial water coordination landscape observed at the neat interface toward a homogeneous, highly interconnected in-plane 2D hydrogen bonding (2D-HB) network at the ionic interface, reminiscent of the canonical, hydrophobic air–water interface. This ion-induced transformation results in a characteristic decrease of the vibrational lifetime (T 1 ) of excited interfacial O–H stretching modes from T 1 ~ 600 fs to T 1 ~ 250 fs. Hence, we propose that the T 1 determined by TR-vSFG in combination with DFT-MD simulations can be widely used for a quantitative spectroscopic probe of the ion kosmotropic/chaotropic effect at aqueous interfaces as well as of the ion-induced surface hydrophobicity.

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

New Insights into the Bulk and Surface Defect Structures of Ceria Nanocrystals from Neutron Scattering Study

Neutron diffraction and pair distribution function studies coupled with Raman spectroscopy have successfully unraveled the detailed oxygen defect structures of ceria nanocubes and nanorods. Two types of defect sites are revealed for the ceria nanocrystals: surface and bulk defects. It is proposed that the surface oxygen defects in both types of CeO 2 nanocrystals are predominantly the partially reduced Ce 3 O 5+x , with the bulk defect structures dominated by interstitial Frenkel-type oxygen vacancies. Ceria nanorods possess much higher concentration of surface oxygen defects relative to the nanocubes, albeit with only slightly higher concentration of bulk Frenkel-type oxygen vacancies. Upon annealing the nanorod sample at 600 °C under vacuum (~10 –4 to 10 –5 mbar), a partially reduced ceria phase with long-range oxygen vacancy ordering (Ce 3 O 5+x ) has been observed experimentally for the first time. This intriguing observation that surface defect phases can take on ordered defect sublattices under certain conditions is of great value in understanding the temperature-dependent catalytic performance of ceria nanocrystals. Furthermore, a drastic decrease of the surface vacancies in the ceria nanocrystals is observed upon exposure to SO 2 , especially for the nanorods, a likely origin for the sulfur poisoning effect on ceria-based materials. This study suggests that tailoring surface morphology is a promising strategy to control defect properties of ceria nanomaterials. It also provides fundamental insights to stabilize surface oxygen defects in CeO 2 nanocrystals to achieve high redox performance under corrosive environments such as under SO 2 /SO x exposure.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Preliminary Modeling of Triply Periodic Minimal Surface (TPMS) Structures with RELAP5-3D

This poster goes over preliminary work performed on modeling triply periodic minimal surfaces (TPMS) with RELAP5-3D. The poster starts off with the need for advanced nuclear fuel designs for future reactors, and how TPMS are being researched for this purpose. There is then a focus on what a TPMS is and then moves onto the motivation for why this geometry is being modeled and looked into. The methodology is then shown for how data from different experiments will be used for pre-test predictions and eventual creation of empirical coefficients and multipliers to be used in models. Then there is a show of how data would be compared between the experimental tests, CFD, and RELAP5-3D values. The results from the simulations and comparisons are then presented to show how the CFD and RELAP5-3D compare to each other currently, with no experimental data to compare to for one test model. Results from the second test model are also presented to show that there is stability in the solving of that model.

42 - ENGINEERING↗
DOE OSTI2026

Combustion-assisted ink-jet printing of nuclear targets

Advances in target fabrication are critical to high-precision measurements in nuclear physics. This work details the preparation of patterned CeO 2 and ThO 2 architectures and thin-film targets via ink-jet deposition of combustible solutions. The produced targets were characterized by scanning electron microscopy (SEM), and by alpha-particle spectroscopy for radioactive targets to determine densities. Ink jet printing of the targets, used both ethanol and 2-methoxyethanol as solvents, with cerium or thorium nitrate as the oxidizer and acetylacetone as the fuel. Additionally, we found that the distance between each droplet dispersion (step size) played the most significant role in determining the final pattern uniformity and thickness. A 50 μm step size leads to relatively thick targets with a density of 350 μg/cm 2 . Significant overlap in droplet sizes leads to a heterogeneous target with an undesirable cracked surface structure. In contrast, 150 μm spacing yields thinner (20 μg/cm 2 ) patterned structures with excellent surface coverage. This method of Ink-jet printing provides a straightforward, scalable, and high-efficiency pathway to prepare custom made, high-quality targets for nuclear physics experiments.

CeO2↗
DOE OSTI2016

Protein–Mineral Interactions: Molecular Dynamics Simulations Capture Importance of Variations in Mineral Surface Composition and Structure

Molecular dynamics simulations, conventional and metadynamics, were performed to determine the interaction of model protein Gb1 over kaolinite (001), Na+-montmorillonite (001), Ca2+-montmorillonite (001), goethite (100), and Na+-birnessite (001) mineral surfaces. Gb1, a small (56 residue) protein with a well-characterized solution-state nuclear magnetic resonance (NMR) structure and having α-helix, four-fold β-sheet, and hydrophobic core features, is used as a model protein to study protein soil mineral interactions and gain insights on structural changes and potential degradation of protein. From our simulations, we observe little change to the hydrated Gb1 structure over the kaolinite, montmorillonite, and goethite surfaces relative to its solvated structure without these mineral surfaces present. Over the Na+-birnessite basal surface, however, the Gb1 structure is highly disturbed as a result of interaction with this birnessite surface. Unraveling of the Gb1 β-sheet at specific turns and a partial unraveling of the α-helix is observed over birnessite, which suggests specific vulnerable residue sites for oxidation or hydrolysis possibly leading to fragmentation.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2023

Effect of the Molecular Structure of Surface Vanadia on Activity and Regenerability of VO $x$ /In 2 O 3 Catalysts for CO 2 -Assisted Oxidative Dehydrogenation of Propane

Our recent work has reported that higher propylene selectivity and improved stability can be achieved by combining redox-active VO $x$ and basic In 2 O 3 for CO 2 -assisted oxidative dehydrogenation of propane (CO 2 -ODHP). In the present work, we continued to explore the stability and regenerability of V/In catalysts. In particular, our interest lies in identifying the effect of mono- and polyvanadate on catalytic performance and regenerability. A V/In catalyst with an increased proportion of monovanadate was prepared using the Schlenk line under moisture-free conditions (V/In–S), while the fully polymerized vanadate catalyst was prepared through a regular impregnation (V/In) for comparison. The Schlenk-line-prepared catalyst, namely, V/In–S, not only exhibits a 17–30% enhanced propylene yield at high temperatures (500–540 °C) over V/In but also presents improved stability and regenerability with nearly 88% activity recovered after regeneration in O 2 . Detailed characterizations have been performed to reveal the catalyst structure–performance relationship, including chemisorption (NH 3 /CO 2 -temperature-programmed desorption, NH 3 /CO 2 -TPD), H 2 -temperature-programmed reduction (H 2 -TPR), and spectroscopic studies [Raman spectroscopy, UV–vis diffuse reflectance spectroscopy (UV–vis DRS), near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS), and high-sensitivity low-energy ion scattering (HS-LEIS)]. Characterization results demonstrate that compared with polyvanadates, monovanadates lead to strengthened interaction with In 2 O 3 and a more stabilized V/In surface and subsurface, as well as improved redox properties of VO $x$ . These advantages give rise to the observed enhancement in activity, stability, and regenerability. In conclusion, these findings advance the understanding of the relationship between the activity/stability and the molecular structure of surface oxide species (vanadia) and the interplay between acid–base interactions and redox properties of mixed metal-oxide catalysts for efficient CO 2 -ODHP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

The Structure Evolution Mechanism of Ni Films Depending on Hydrogen Evolution Property During Electrodeposition Process

Hydrogen evolution property is an important factor to regulate the surface structure of the electrodeposited Ni film. In this work, the dependence of current density on hydrogen evolution property is researched. The structure evolution mechanism of the Ni film depending on current density is analyzed in terms of the hydrogen evolution characteristic. It is found that the surface structure of the Ni film from compact to porous structure could be achieved by adjusting the electrodeposition current density. At low current density (less than 0.07 A cm{sup −2}), the current efficient of hydrogen evolution is very weak. Ni electrodeposition is the main reaction, so compact Ni film is formed. At high current density (higher than 0.3 A cm{sup −2}), hydrogen evolution reaction is enhanced with the increase of current density. At this time, there are plenty of bubbles which can act as templates. As a result, porous Ni film is electrodeposited. However, when the current density is lower than 0.7 A cm{sup −2}, dish-like pore with large diameter is formed due to the large break-off diameter and the long resident time of the hydrogen bubble. And honeycomb-like pore with small diameter is formed at current density larger than 1 A cm{sup −2}, because of reduced break-off diameter and resident time of the hydrogen bubble. Porous film with uniform structure is electrodeposited at 1 A cm{sup −2}, which possesses the higher catalytic activity for hydrogen evolution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

The Role of Secondary Particle Structures in Surface Phase Transitions of Ni-Rich Cathodes

Nanometer-thick reconstruction layers on layered cathode surfaces have been widely observed on both pristine and cycled materials. However, the mechanisms of reconstruction and the role that these structures play in electrochemical performance are not fully understood. From a crystallographic perspective, such surface reconstruction layers result from cation site-mixing between Li and transition-metal ions, but it remains far from clear as to what the critical factors are that control such cation mixing for various cathode chemistries. In this paper, we report observations on surface transformations during cycling of a Ni-rich cathode-oxide that are governed by direct contact with the liquid electrolyte. Specifically, within a secondary particle, the three-dimensional hierarchical aggregate of primary particles leads to the formation of grain boundaries of different characteristics, including open grain boundaries that allow the permeation of liquid electrolyte, and closed grain boundaries that exclude liquid electrolyte penetration. Upon battery cycling, surfaces in direct contact with the liquid electrolyte showed a surface reconstruction layer while the surfaces that did not have contact with the electrolyte showed no such reconstructions. In addition, the critical role of oxygen in reconstruction of grain boundaries is demonstrated, and the unexpected oxygen depletion at twin boundaries result in severe phase transitions. The present work provides further insights into phase transitions at solid-solid and solid-liquid interfaces within secondary cathode particles and suggests strategies for mitigating surface/interfacial degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Structural features of ISG borosilicate nuclear waste glasses revealed from high-energy X-ray diffraction and molecular dynamics simulations

Vitrification is a widely accepted method to immobilize nuclear waste. Detailed structural information is critical to understand the physical and chemical behaviors, including the long-term chemical durability of these glasses that are to be stored in geological storage sites. High-energy X-ray diffraction studies are used to obtain accurate structural information of the International Simple Glass (ISG), a six-component borosilicate model nuclear waste glass with a composition (mol%) of 60.2SiO 2 -16.0B 2 O 3 -12.6Na 2 O-3.8Al 2 O 3 -5.7CaO-1.7ZrO 2 . Classical molecular dynamics (MD) simulations with recently developed effective potentials are utilized to generate structural models of the ISG glasses to provide interpretation of the high-energy X-ray structural data and additional short and medium range structural details. The atomic structure model generated from MD simulations shows an excellent agreement with high-energy X-ray diffraction, measured for the first time for ISG, with an R x value of 5.5%. Systematic investigations of the medium-range structural features of ISG are performed, built upon recent study of the short-range structure. In particular, the glass former cation oxygen polyhedral analysis show that [SiO 4 ]-[SiO 4 ] and [BO 4 ]-[SiO 4 ] connections are the most abundant while [ZrO 6 ] octohedra having higher probability to connect to another [SiO 4 ], [BO 4 ] and [BO 3 ]. Moreover, we have studied the ISG surface structure using MD simulations. Noticeable differences in terms of both chemical compositions and structural features between the bulk and surface are observed. There exist increased small-sized rings, under coordinated Si species, high 3-coordinated boron content (86.5%) on the surface. Very importantly, sodium ions are found to be enriched on the glass surface, consistent with recent experimental results. Furthermore, both bulk and surface structural information are discussed in terms of the dissolution and corrosion mechanisms of ISG and related nuclear waste glasses.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Stabilization of MgAl 2 O 4 spinel surfaces via doping

Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl 2 O 4 ) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y 3+ , Gd 3+ , La 3+ ) and one tetravalent dopant (Zr 4+ ) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Measurement of electronic structure and surface reconstruction in the superionic Cu 2-x Te

Recently, layered copper chalcogenides Cu 2 X family (X=S, Se, Te) has attracted tremendous research interests due to their high thermoelectric performance, which is partly due to the superionic behavior of mobile Cu ions, making these compounds "phonon liquids."Here, we systematically investigate the electronic structure and its temperature evolution of the less studied single crystal Cu 2-x Te by the combination of angle resolved photoemission spectroscopy (ARPES) and scanning tunneling microscope/spectroscopy (STM/STS) experiments. While the band structure of the Cu 2-x Te shows agreement with the calculations, we clearly observe a 2×2 surface reconstruction from both our low temperature ARPES and STM/STS experiments which survives up to room temperature. Interestingly, our low temperature STM experiments further reveal multiple types of reconstruction patterns, which suggests the origin of the surface reconstruction being the distributed deficiency of liquidlike Cu ions. Our findings reveal the electronic structure and impurity level of Cu 2 Te, which provides knowledge about its thermoelectric properties from the electronic degree of freedom.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Structure determination of a multilayer with an island-like overlayer using hard x-ray photoelectron spectroscopy

We use hard X-ray photoelectron spectroscopy (HAXPES) to obtain the surface structure of a multilayer Au/SiO{sub 2}/Si substrate sample with an island-like overlayer. Photoelectron intensities are measured as a function of incident photon energy (PE) and take-off angle (TOA, measured from the sample surface). The Au layer coverage and Au and SiO{sub 2} layer thicknesses are obtained by the PE dependence, and are used for the following TOA analysis. The Au island lateral width in the cross section is obtained by the TOA dependence, including information about surface roughness, in consideration of the island shadowing at small TOAs. In both cases, curve-fitting analysis is conducted. The surface structure, which consists of layer thicknesses, overlayer coverage and island width, is determined nondestructively by a combination of PE and TOA dependent HAXPES measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗