Search NASA⌕ Search

SEARCH · Search NASA

Results for “surface complexation”

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 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Relocation of Light and Moderate-Magnitude ( M 4-6) Seismicity Along the Central Mid-Atlantic

In this study, we estimate precise relative epicentroid locations of earthquakes along the Mid-Atlantic Ridge (MAR) between 12°N and 19°N using intermediate-period Rayleigh and Love wave cross-correlation measurements. We relocate 152 earthquakes with magnitudes ranging between 4.0 and 6.0 and when possible use P waveform modeling to estimate centroid depths. We compare surface-wave locations to locations in the U.S. Geological Survey, Global Centroid Moment Tensor, and Pacific Marine Environmental Laboratory hydroacoustic catalogs (Smith et al., 2002, https://doi.org/10.1029/2001GL013912) and demonstrate that surface-wave based relative location techniques provide significant improvement on precision. Our analyses shift locations to more tectonically consistent alignments that correlate strongly with bathymetric features. Relocations along the Fifteen-Twenty and Marathon Fracture Zones (FZs) move to within a few kilometers of the transform bathymetry. Events along ridge segments scatter over a distance of about 10–20 km perpendicular to the local plate boundary and most ridge-segment seismicity clusters spatially. North of the Fifteen-Twenty FZ, ridge events along several segments locate preferentially in the North American Plate, suggesting recent asymmetric seismic strain release and perhaps asymmetric spreading. Along the ridge between 13°N and 14°N, moderate-magnitude seismic strain release concentrates in an area with two active oceanic core complexes (OCC) along the western rift boundary, but the largest events along this segment appear to occur along the eastern boundary rift valley faults and represent deformation opposite the OCC detachment surface processes. Finally, precise moderate-magnitude earthquake epicentroid locations for events that occurred over the last few decades complement the results of temporary seismometer deployments that have imaged microseismic activity along the MAR.

58 GEOSCIENCES↗
DOE OSTI2024

Structure and Dynamics of Aqueous Electrolytes at Quartz (001) and (101) Surfaces

Here, understanding and describing reactivity at mineral-water interfaces such as ion adsorption, the kinetics of dissolution, or surface charge development depends on our ability to improve the accuracy of electrical double layer (EDL) models. While molecular dynamics (MD) simulations are routinely used to investigate the structure and energetics of adsorbed ions comprising the EDL, less attention is paid to their self-diffusion dynamics, which can uniquely inform on coupling to interfacial reactions. Here we use MD to investigate both the organization and diffusion dynamics of water and electrolyte ions (NaCl, KCl, CaCl 2 ) at hydroxylated quartz (001) and (101) surfaces, a comparison which allowed us to assess surface structural effects of corrugation and silanol density. We found that inner- versus outer-sphere complex formation depends on cation size and charge but not necessarily hydration energies. Participation of surface silanols in the hydration spheres of Na + and K + generally indicated their preference for inner-sphere complexation, but this depends strongly on the orientation of the surface considered through its influence over the organization and dynamics of adsorbed water layers. In particular, surface orientation substantially affects the diffusive behavior of the near-surface water. Na + was found to decrease the mobility of water in the first layer, consistent with an increasing frequency of hydrolysis implied by faster quartz dissolution rates observed in experiments via the well known salt effect. Our results are also in good agreement with the observed dissolution rate of quartz vs. surface adsorption strength measure by Dove and Nix. This study sets the stage for a forthcoming paper examining how the dynamics at quartz/electrolyte interfaces are influenced by externally applied electric fields.

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

Holography abhors visible trapped surfaces

We prove that consistency of the holographic dictionary implies a hallmark prediction of the weak cosmic censorship conjecture: that in classical gravity, trapped surfaces lie behind event horizons. In particular, the existence of a trapped surface implies the existence of an event horizon, and that furthermore this event horizon must be outside of the trapped surface. More precisely, we show that the formation of event horizons outside of a strong gravity region is a direct consequence of causal wedge inclusion, which is required by entanglement wedge reconstruction. We make few assumptions beyond the absence of evaporating singularities in strictly classical gravity. We comment on the implication that spacetimes with naked trapped surfaces do not admit a holographic dual, note a possible application to holographic complexity, and speculate on the dual CFT interpretation of a trapped surface.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Nonlinear elasticity with the Shifted Boundary Method

Here, we propose a new unfitted/immersed computational framework for nonlinear solid mechanics, which bypasses the complexities associated with the generation of CAD representations and subsequent body-fitted meshing. This approach allows to speed up the cycle of design and analysis in complex geometry and requires relatively simple computer graphics representations of the surface geometries to be simulated, such as the Standard Tessellation Language (STL format). Complex data structures and integration on cut elements are avoided by means of an approximate boundary representation and a modification (shifting) of the boundary conditions to maintain optimal accuracy. An extensive set of computational experiments in two and three dimensions is included.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Antifouling strategies for protecting bioelectronic devices

Bioelectronic devices are playing an increasingly important role in many areas of our lives. They power a significant portion of medical diagnostics and are becoming more and more important for delivery of therapeutics and monitoring of chronic symptoms. However, surface fouling phenomena, and especially biofouling in complex biological fluids, restricts the performance of these devices and severely reduces their useful lifespan. In this Research Update, we discuss the main principles and strategies that researchers use to prevent fouling and minimize or remove the foulants from bioelectronic device surfaces. We also survey a variety of antifouling approaches that can enhance device performance.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Enhanced Nanostructure Dynamics on Au(111) with Adsorbed Sulfur due to Au–S Complex Formation

Chemisorbed species can enhance the fluxional dynamics of nanostructured metal surfaces which has implications for applications such as catalysis. Scanning tunneling microscopy studies at room temperature reveal that the presence of adsorbed sulfur (S) greatly enhances the decay rate of 2D Au islands in the vicinity of extended step edges on Au(111). This enhancement is already significant at S coverages, θS, of a few hundredths of a monolayer (ML), and is most pronounced for 0.1–0.3 ML where the decay rate is increased by a factor of around 30. For θ S close to saturation at about 0.6 ML, sulfur induces pitting and reconstruction of the entire surface, and Au islands are stabilized. Enhanced coarsening at lower θS is attributed to the formation and diffusion across terraces of Au–S complexes, particularly AuS 2 and Au4S 4 , with some lesser contribution from Au3S4. This picture is supported by density functional theory analysis of complex formation energies and diffusion barriers.

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

Benzene Ring Knitting Achieved by Ambient-Temperature Dehalogenation via Mechanochemical Ullmann-Type Reductive Coupling

The current approaches capable of affording conjugated porous networks (CPNs) still rely on solution-based coupling reactions promoted by noble metal complexes or Lewis acids, on-surface polymerization conducted in ultrahigh-vacuum environment at very high temperatures (>200 °C), or mechanochemical Scholl-type reactions limited to electron-rich substrates. To develop simple and scalable approaches capable of making CPNs under neat and ambient conditions, herein, a novel and complementary method to the current oxidative Scholl coupling processes is demonstrated to afford CPNs via direct aromatic ring knitting promoted by mechanochemical Ullmann-type reactions. The key to this strategy lies in the dehalogenation of aromatic halides in the presence of Mg involving the formation of Grignard reagent intermediates. Products (Ph-CPN-1) obtained via direct C-C bond formation between 1,2,4,5-tetrabromobenzene (TBB) monomer feature high surface areas together with mesoporous architecture. The versatility of this approach is confirmed by the successful construction of various CPNs via knitting of the corresponding aromatic rings (e.g., pyrene and triphenylene), and even highly crystalline graphite product was obtained. The CPNs exhibit good electrochemical performance as the anode material in lithium-ion batteries (LIBs). Overall, this approach expands the frontiers of CPN synthesis and provides new opportunities to their scalable applications.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Tailorable Optical Response of Au-LiNbO 3 Hybrid Metamaterial Thin Films for Optical Waveguide Applications

Photonic integrated circuits require various optical materials with versatile optical properties and easy on–chip device integration. To address such needs, a well–designed nanoscale metal–oxide metamaterial, that is, plasmonic Au nanoparticles embedded in nonlinear LiNbO 3 (LNO) matrix, is demonstrated with tailorable optical response. Specifically, epitaxial and single–domain LNO thin films with tailored Au nanoparticle morphologies (i.e., various nanoparticle sizes and densities), are grown by a pulsed laser deposition method. The optical measurement presents obvious surface plasmon resonance and dramatically varied complex dielectric function because of the embedded Au nanoparticles, and its response can be well tailored by varying the size and density of Au nanoparticles. An optical waveguide structure based on the thin film stacks of a–Si on SiO 2 /Au–LNO is fabricated and exhibits low optical dispersion with an optimized evanescent field staying in the LNO–Au active layer. Furthermore, the hybrid Au–LNO metamaterial thin films provide a novel platform for tunable optical materials and their future on–chip integrations in photonic–based integrated circuits.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Synthesis and properties of carbosilane dendrimers with perfluorohexyl groups in the outer layer of the molecular structure

Branched perfluorohydrosiloxane with CF{sub 3}CF{sub 2}CF{sub 2}C(CF{sub 3}){sub 2}(CH{sub 2}){sub 3} groups at the silicon atom was synthesized by a sequence of chemical reactions. The resulting compound was used as a modifying agent for carbosilane dendrimers of the 3rd and 6th generations. Dendrimers with perfluorohexyl terminal groups in surface layer are characterized by a complex of physicochemical methods. It is demonstrated that due to the branching of perfluoroalkyl terminal groups, obtained carbosilane dendrimers are soluble in organic and inorganic media. Differences in the solubility of small and large dendrimers are caused by the formation of the outer fluoride shell of different densities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

ESI-MS of Cucurbituril Complexes Under Negative Polarity

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool to study host–guest supramolecular interactions. ESI-MS can be used for detailed gas-phase reactivity studies, to clarify the structure, or simply to verify the formation of complexes. Depending on the structure of the host and of the guest, negative and/or positive ESI are used. Here we report the unexpected formation of host–guest complexes between cucurbit[n]urils (n = 7, 8, CB[n]) and amine, styryl pyridine, and styryl pyridine dimer cations, under negative ESI. Non-complexed CB[n] form double charged halide (Br{sup -}, Cl{sup -}, F{sup -}) adducts. Under negative ESI, halide ions interact with CB[n] outer surface hydrogen atoms. One to one host–guest complexes (1:1) of CB[n] with positive charged guests were also observed as single and double charged ions under negative ESI. The positive charge of guests is neutralized by ion-pairing with halide anions. Depending on the number of positive charges guests retain in the gas phase, one or two additional halide ions are required for neutralization. Complexes 1:2 of CB[8] with styryl pyridines retain two halide ions in the gas phase, one per guest. Styryl pyridine dimers form 1:1 complexes possessing a single extra halide ion and therefore a single positive charge. Negative ESI is sensitive to small structural differences between complexes, distinguishing between 1:2 complexes of styryl pyridine-CB[8] and corresponding 1:1 complexes with the dimer. Negative ESI gives simpler spectra than positive ESI and allows the determination of guest charge state of CB[n] complexes in the gas phase. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2017

Thermal-hydraulic performance of metal foam heat exchangers under dry operating conditions

High porosity metal foams with novel thermal, mechanical, electrical, and acoustic properties are being more widely adopted for application. Due to their large surface-area-to-volume ratio and complex structure which induces better fluid mixing, boundary layer restarting and wake destruction, they hold promise for heat transfer applications. In this study, the thermal-hydraulic performance of open-cell aluminum metal foam heat exchanger has been evaluated. The impact of flow conditions and metal foam geometry on the heat transfer coefficient and gradient have been investigated. Metal foam heat exchanger with same geometry (face area, flow depth and fin dimensions) consisting of four different type of metal foams have been built for the study. Experiments are conducted in a closed-loop wind tunnel at different flow rate under dry operating condition. Metal foams with a smaller pore size (40 PPI) have a larger heat transfer coefficient compared to foams with a larger pore size (5 PPI). However, foams with larger pores result in relatively smaller pressure gradients. Current thermal-hydraulic modeling practices have been reviewed and potential issues have been identified. Permeability and inertia coefficients are determined and compared to data reported in open literature. Finally, on the basis of the new experimental results, correlations are developed relating the foam characteristics and flow conditions through the friction factor f and the Colburn j factor.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Extreme fast charge aging: Correlation between electrode scale and heterogeneous degradation in Ni-rich layered cathodes

Extreme fast charging (XFC) is a key requirement for the adoption of battery-based electric vehicles by the transportation sector. However, XFC has been shown to accelerate degradation, causing the capacity, life, and safety of batteries to deteriorate. There are no systematic studies in the open literature regarding aging modes in Ni-rich Li y Ni 0.a Mn 0.b Co 0.c O 2 (NMCabc) cathodes caused by fast charging. Herein, we report the effects of cathode composition and electrode loading in pouch cells containing NMC532, 622 and 811 paired with graphite and cycled under XFC conditions. The relative anisotropic volume change in the unit cell increases with Ni content in low-loading cells, while it levels up for all three NMC cathodes in high-loading cells because of substantial Li plating. The amounts of lithium plating and heterogeneity on the anode, determined by crystallographic phase quantification, were found to be correlated with electrode loading and cathode heterogeneity. The concentrations of the transition metals deposited on the anodes depend on NMCabc composition in a complex way. More particle cracking and surface degradation was found in NMC811. Here, the findings in this work provide a new understanding of the failure mechanisms and their practical implications for compositional tuning of future high-Ni NMCabc cathode materials during fast charging.

25 ENERGY STORAGE↗
DOE OSTI2024

Enabling fast discharge of Li-ion batteries via electrolyte formulations for urban air mobility applications

High-power discharge requirements are critical for lithium-ion batteries (LIBs) used in electric Vertical Takeoff and Landing (eVTOL) vehicles that are increasingly considered in urban mobility. This investigation places a particular emphasis on understanding the impact of electrolytes on discharge processes and rate capability. We aim to compare the discharge behavior of LiBs using a conventional electrolyte (Gen 2: 1.2 M LiPF 6 in EC:EMC) and the dual salt LiTFSI-LiBOB-based electrolyte. Here we carefully examine the profiles of charging and discharging, the behavior during extended cycles, impedance spectroscopy results, and the characteristics of the electrode surface. Our research findings demonstrate the complex relationship between the composition of electrolytes and the specific high-power discharge requirements of electric vertical takeoff and landing (eVTOL) systems. This research highlights the importance of customizing electrolyte compositions to optimize energy storage density while simultaneously enabling higher power extraction to enhance performance in short-range electric aviation.

25 ENERGY STORAGE↗
DOE OSTI2018

STEM and APT characterization of scale formation on a La,Hf,Ti-doped NiCrAl model alloy

A thermally grown scale formed on a cast NiCrAl model alloy doped with lanthanum, hafnium, and titanium was examined after isothermal exposure at 1100 °C for 100 h in dry flowing O 2 to understand the dopant segregation along scale grain boundaries. The complex scale formed on the alloy surface was composed of two types of substrates: phase-dependent, thin (<250 nm) outer layers and a columnar-grained ~3.5 μm inner alumina layer. Two types of oxides formed between the inner and outer scale layers: small (3–15 nm) La 2 O 3 and larger (≤50 nm) HfO 2 oxide precipitates. Nonuniform distributions of the hafnium, lanthanum, and titanium dopants were observed along the inner scale grain boundaries, with hafnium dominating in most of the grain boundaries of α-Al 2 O 3 . The concentration of reactive elements (RE) seemed to strongly depend on the grain boundary structure. The level of titanium grain boundary segregation in the inner scale decreased toward the model alloy (substrate), confirming the fast outward diffusion of titanium. Hafnium was also observed at the metal–scale interface and in the γ' (Ni 3 Al) phase of the alloy. High-resolution scanning transmission electron microscopy (STEM) confirmed the substitution of REs for aluminum atoms at the scale grain boundaries, consistent with both the semiconducting band structure and the site-blocking models. Both STEM and atom probe tomography allowed quantification of REs along the scale grain boundaries across the scale thickness. Analysis of the scale morphology after isothermal exposure in flowing oxygen revealed a myriad of new precipitate phases, RE segregation dependence on grain boundary type, and atomic arrangement along scale grain boundaries, which is expected to influence the scale growth rate, stability, and mechanical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Nanopore networks in colloidal silica assemblies characterized by XCT for confined fluid flow modeling

Fluid flow through nanopore structures has exhibited different behavior than that described by Darcy's law, derived from pore networks of micrometer scale. Here, pressure assemblies of colloidal silica spheres of specified diameters from 94 to 620 nanometers were prepared as model nano-porous media. The smaller silica spheres tended to form random packing, but some substantial ordering was found in the packing of the larger silica spheres. X-ray computed tomography (XCT), with a voxel resolution of 16 nm, was used to characterize the nanopore networks. The porosity of the Nano-XCT pore network (34%) was less than the total porosity of the assemblies as determined by X-ray attenuation (52%), possibly due to the limits of voxel resolution during segmentation. Fluid flow in the nanopore networks was simulated using the single-phase Lattice Boltzmann Method, and the simulated permeability was compared with the empirical and experimental values. Based on our characterization, although a well-ordered packing of silica spheres was not achieved, it was found that the nanopore networks in the colloidal silica assemblies had pore size distributions corresponding to the particle sizes. The simulated permeability was less than the experimental measurement for water flow, but the complex packing of silica spheres and surface chemistry issues need to be considered in future research.

02 PETROLEUM↗
DOE OSTI2024

Competing Radical and Molecular Channels in the Unimolecular Dissociation of Methylformate

The thermal dissociation of methylformate has been characterized by numerous experimental and theoretical studies that all seem to agree that the lowest energetically accessible process is a 3-center H-atom transfer that leads to the molecular products CH3OH 3 OH + CO. However, these literature studies seem to be at odds with regards to the role of other competing molecular eliminations and bond-fission processes and therefore a complete and resolved mechanistic picture of methylformate thermal dissociation still eludes us. In this work, we have performed high-level electronic structure theory calculations to characterize the energetics of other overlooked molecular and radical processes that can originate on the complex CH3OCHO 3 OCHO potential energy surface (PES). The present calculations do indeed confirm that the lowest energy process accessible on this PES is molecular elimination to form CH3OH 3 OH + CO. However, unlike prior theoretical studies, the present calculations reveal that the second lowest energy process is a 5-center concerted elimination process that leads to the direct formation of H2 2 + CH2O 2 O + CO. We also note that HCO2 2 from the lowest-lying bond fission has two energetically comparable electronic states (of 2 B 2 and 2 A 1 symmetry). Furthermore, the barrier for H-atom migration of CH3OCHO 3 OCHO to form the carbene (CH3OCOH) 3 OCOH) is similar to that for the direct 4-center elimination process leading to CH2O 2 O + CH2O 2 O characterized in prior literature studies. Radical and molecular pathways to CH3 3 + HOCO and CH4 4 + CO2 2 can also be facilitated from this carbene. Master equation calculations were performed to characterize the competition between the various molecular and radical processes on this more elaborate CH3OCHO 3 OCHO PES. The results of the present theoretical analyses were used to resolve outstanding questions on the role of secondary radical- initiated reactions in characterizing prior literature experimental studies.

Chemical Kinetics↗
DOE OSTI2018

Cationic Pyridylamido Adsorbate on Brønsted Acidic Sulfated Zirconia: A Molecular Supported Organohafnium Catalyst for Olefin Homo- and Co-Polymerization

Here we report the combined application of high-resolution solid-state 13 C–CPMAS-NMR and FT-IR spectroscopy, elemental analysis, kinetic poisoning/active site counting, variable dielectric constant medium, and DFT computation to characterize the surface chemistry of a pyridylamido hafnium complex (Cat1, L 1 -HfMe 2 , L 1 = 2,6-diisopropyl-N-{(2-isopropylphenyl)[6-(naphthalen-1-yl)pyridin-2-yl]methyl}aniline) adsorbed on Brønsted acidic sulfated zirconia (ZrS). The spectroscopic and DFT results indicate protonolytic formation of organohafnium cations having a largely electrostatic pyridylamido-Hf-CH 3 + ···ZrS - interaction with elongated Hf···OZrS distances of ~ 2.14 Å. High-molecular-weight polyethylenes and ethylene/1-octene copolymers are obtained with this supported catalyst without an activator/cocatalyst. The DFT calculations reveal that the first ethylene insertion into the Hf-methyl bond has a lower barrier than the corresponding insertion into the Hf-aryl bond of this single-site heterogeneous catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Universality and chaoticity in ultracold K+KRb chemical reactions

A fundamental question in the study of chemical reactions is how reactions proceed at a collision energy close to absolute zero. This question is no longer hypothetical: quantum degenerate gases of atoms and molecules can now be created at temperatures lower than a few tens of nanokelvin. Here we consider the benchmark ultracold reaction between, the most-celebrated ultracold molecule, KRb and K. We map out an accurate ab initio ground-state potential energy surface of the K 2 Rb complex in full dimensionality and report numerically-exact quantum-mechanical reaction dynamics. The distribution of rotationally resolved rates is shown to be Poissonian. An analysis of the hyperspherical adiabatic potential curves explains this statistical character revealing a chaotic distribution for the short-range collision complex that plays a key role in governing the reaction outcome.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗