Search NASA⌕ Search

SEARCH · Search NASA

Results for “surface effect”

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 199 records · Page 11

Selectivity in gas–liquid interactions: Molecular beam scattering of CD 4 and ND 3 from an aqueous flat liquid jet

The dynamics of polar and nonpolar molecules colliding with an aqueous surface are characterized by scattering molecular beams of deuterated methane and ammonia, CD 4 and ND 3 (E i = 28.9 and 30.3 kJ mol −1 , respectively), from a flat liquid jet of cold salty water (8 m LiBr, 230 K). Translational energy distributions of scattered species collected as a function of collision geometry probe both impulsive scattering (IS) and thermal desorption (TD) mechanisms. Here, we find that CD 4 scattering is dominated by IS and exhibits a super-specular angular distribution. The fraction of TD scattering events is notably smaller for cold salty water than for dodecane, consistent with a higher free energy of solvation for CD 4 in the water jet. In contrast, no scattering signal is seen for ND 3 from the water jet, a result attributed to the high solubility and efficient protonation of ND 3 in liquid water. The IS channel for CD 4 was analyzed using a soft-sphere model, yielding a higher internal energy (E int ) and lower effective surface mass (m eff ) than was seen for Ne/water; the higher value of E int is attributed to rotational excitation of the scattered CD 4 . These findings demonstrate that the outcomes of a gas–liquid collision—scattering trajectory, surface adherence, and energy transfer—are directed at the molecular level by both the gaseous scatterer and liquid surface.

Foreman, Madison M. [University of California, Ber↗

Full characterization of ultrathin 5-nm low-k dielectric bilayers: Influence of dopants and surfaces on the mechanical properties

Ultrathin films and multilayers, with controlled thickness down to single atomic layers, are critical for advanced technologies ranging from nanoelectronics to spintronics to quantum devices. However, for thicknesses less than 10 nm, surfaces and dopants contribute significantly to the film properties, which can differ dramatically from that of bulk materials. Therefore, for amorphous films being developed as low dielectric constant interfaces for nanoelectronics, the presence of surfaces or dopants can soften films and degrade their mechanical performance. Here we use coherent short-wavelength light to fully and nondestructively characterize the mechanical properties of individual films as thin as 5 nm within a bilayer. In general, we find that the mechanical properties depend both on the amount of doping and the presence of surfaces. In very thin (5-nm) silicon carbide bilayers with low hydrogen doping, surface effects induce a substantial softening - by almost an order of magnitude - compared with the same doping in thicker (46-nm) bilayers. These findings are important for informed design of ultrathin films for a host of nano- and quantum technologies, and for improving the switching speed and efficiency of next-generation electronics.

36 MATERIALS SCIENCE↗

High‐Order Nonlinear Frequency Conversion in Transparent Conducting Oxide Thin Films

The study of conductive oxides has gained momentum within the photonics community due to their unique linear and nonlinear optical properties. Despite recent experiments reporting on high harmonic generation from thin films, the optical/electronic behavior of these compounds at the nanoscale is still not fully understood due to the lack of a suitable theoretical model. In the present work, aluminum zinc oxide is excited near its epsilon-near-zero crossing point using incident femtosecond pulses having peak power densities in the 1 TW cm −2 range. A relatively efficient frequency up-conversion including even and odd harmonics up to the seventh order is observed. A hydrodynamic-Maxwell theoretical approach is adopted, capable of simultaneously taking into account linear and nonlinear dispersions, nonlocal effects, surface, magnetic, and bulk nonlinearities in a spectral region that spans over two and a half octaves from the UV to the NIR region. The study enables a deeper understanding of the fundamental material parameters regulating optical nonlinearities, providing important insights to engineer this class of materials for applications in sensing, ultra-fast physics, and spectroscopy.

material modeling↗

Polymorphic Metastability in Colloidal Semiconductor Nanocrystals

Metastable polymorphs of inorganic solids often possess material properties not present in the corresponding thermodynamic polymorphs, making them targets for the development of new functional materials. In contrast with isolating metastable bulk materials, syntheses of metastable polymorphs on the nanoscale are aided by fast non-equilibrium reaction kinetics and the favorable thermodynamic influence of surface energies, giving rise to greater ease of access to metastable high-temperature polymorphs and, in some cases, new polymorphs that do not exist in the bulk. The syntheses of metastable semiconductor nanocrystals are of interest for their potentially unique optoelectronic and physicochemical properties. However, in many material systems, synthesizing nanocrystalline products away from thermodynamic equilibrium in a predictable manner remains an outstanding challenge. This review outlines direct synthetic methodologies that have been developed to enable control over the nucleation and growth of metastable polymorphs of semiconductor nanocrystals by tailoring reaction conditions, precursor kinetics, ligand and surface effects, and other synthetic levers. The case studies reviewed herein expound on the direct syntheses of metastable ZnSe, Cu 2 SnSe 3 , CuInSe 2 , Ag 2 Se, and AgInSe 2 nanocrystals, and although there remain numerous examples of metastable nanocrystal syntheses outside of these metal chalcogenide systems, the concepts discussed are of general utility to the field of metastable nanocrystal syntheses as a whole. Explicit examples in which new functional properties are afforded by metastable polymorphs of the aforementioned material systems are presented within the context of applications for solar cells, photonics, and optical sensing. Finally, the factors that affect the kinetic persistence of metastable nanocrystalline polymorphs are discussed at length for these material systems.

36 MATERIALS SCIENCE↗

A Review of Local-to-Nonlocal Coupling Methods in Nonlocal Diffusion and Nonlocal Mechanics

Local-to-nonlocal (LtN) coupling refers to a class of methods aimed at combining nonlocal and local modeling descriptions of a given system into a unified coupled representation. This allows to consolidate the accuracy of nonlocal models with the computational expediency of their local counterparts, while often simultaneously removing nonlocal modeling issues such as surface effects. The number and variety of proposed LtN coupling approaches have significantly grown in recent years, yet the field of LtN coupling continues to grow and still has open challenges. This review provides an overview of the state of the art of LtN coupling in the context of nonlocal diffusion and nonlocal mechanics, specifically peridynamics. Furthermore, we present a classification of LtN coupling methods and discuss common features and challenges. The goal of this review is not to provide a preferred way to address LtN coupling but to present a broad perspective of the field, which would serve as guidance for practitioners in the selection of appropriate LtN coupling methods based on the characteristics and needs of the problem under consideration.

97 MATHEMATICS AND COMPUTING↗

Breaking the passivation barrier via d-p orbital optimization for stable hydrogen production and sulfion upgrading

The development of energy-efficient hydrogen production technologies represents a critical pathway toward achieving global carbon neutrality objectives. This work provides fundamental insights into overcoming catalyst passivation challenges in sulfide oxidation reaction (SOR)-coupled hydrogen evolution reaction (HER) systems through precise orbital hybridization engineering. Our theoretical simulations reveal that sulfur-passivated ruthenium surfaces can effectively modulate d-p orbital hybridization, significantly reduce d-electron activity while stabilizing long-chain S 8 species and decreasing intermediate adsorption energies. Furthermore, metal carbides/ruthenium heterostructure (MC/Ru, M = V, Mo, W) was designed to achieve simultaneous optimization of both HER (∆G H* = −0.11 eV) and SOR (∆G RDS = 1.51 eV) via work-function-mediated interfacial electron transfer, which effectively tailors surface electronic states. Guided by theoretical predictions, we successfully synthesized a series of metal carbides/ruthenium/nitrogen-doped carbon catalysts based on a solid-phase reaction and designated as MC/Ru@NC (M = V, Mo, W). The optimized VC/Ru@NC catalyst exhibits exceptional performance in a membrane-free two-electrode system, achieving an ultralow cell voltage of 0.76 V at 200 mA cm −2 with outstanding stability over 1600 h, while maintaining 97.5 % Faradaic efficiency for hydrogen production and 73.8 % sulfur recovery efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Upcycling linear low-density polyethylene waste to turbostratic graphene for high mass loading supercapacitors

Linear low-density polyethylene (LLDPE) waste is difficult to upcycle into more valuable carbon materials because it tends to completely decompose into small molecules during thermal processing. In this work, LLDPE is upcycled into a high quality turbostratic graphene using a pre-treatment step to oxidatively crosslink the polymer with the assistance of solid additives (KCl and K 2 CO 3 ) that improve crosslinking by increasing the effective surface area of the polymer melt during processing. After this pretreatment step, the crosslinked polymer could then be carbonized and catalytically graphenized between 400–950°C without decomposition of the polymer feedstock. The LLDPE derived graphene (LLDPE-G) obtained from this process has a Brunauer–Emmett–Teller (BET) specific surface area, up to 1800m 2 g -1 and average Raman I D /I G and I 2D /I G ratios of 0.85 and 0.57, respectively, indicating high quality graphene. When used as an electrode material in symmetric supercapacitors, LLDPE-G possesses a specific capacitance up to 175Fg -1 at a mass loading of 20mgcm -2 , which is two times the commercial requirement, yielding an areal capacitance of 3.5 Fcm -2 . Moreover, LLDPE-G exhibits exceptional cycling stability with a capacitance retention of 95.8 % after 100,000 cycles at a current density of 4.0 Ag -1 . Additionally, the KCl and K 2 CO 3 solids are recycled and reused over 3 complete reaction cycles to make new LLDPE-G with the material quality and electrocapacitive performance retained and verified after each cycle. Our approach creates new opportunities for upcycling waste LLDPE and other varieties of polyethylene into a higher value graphene used for electrochemical energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanism of ion pairing–induced co-ion penetration into the stern layer

In classical electric double layer (EDL) theory, co-ions—ions carrying the same charge as the electrode—are assumed to be excluded from the Stern layer because of electrostatic repulsion. However, ion pairing with adsorbed counterions may enable co-ions to access the EDL, a phenomenon that remains underexplored. Key questions therefore remain unresolved, including how deeply co-ions penetrate, how ion-specific properties govern them, and how ion pairing within the EDL differs from bulk solution. Here, in this study, we employ molecular dynamics simulations combined with well-tempered metadynamics to quantify co-ion penetration and ion-pairing thermodynamics at positively charged Mg-Al layered double hydroxide interfaces (σ = +20.6 μC/cm 2 ) in aqueous chloride electrolytes across 0.005–3 M range. We reveal a concentration-driven crossover: at dilute conditions, counterion–co-ion contact ion pairing (CIP) is thermodynamically unfavorable or only weakly favorable (ΔG CIP = +0.12 kcal/mol for Li + to −0.42 kcal/mol for K + ), leading to co-ion exclusion. As concentration increases (≥0.5 M), enhanced screening reduces surface repulsion and stabilizes CIP thermodynamics (ΔG CIP = −0.89 kcal/mol for Li + to −1.05 kcal/mol for K + at 3 M), enabling monovalent co-ions to penetrate the Stern layer following the hydration hierarchy K + > Na + > Li + , while divalent co-ions (Mg 2+ , Ca 2+ ) remain in the diffuse layer, forming only solvent-separated pairs. Comparison with bulk solution shows interfacial ion pairing is suppressed at low concentrations but converges to bulk-like thermodynamics at high concentrations, indicating surface effects vanish under strong screening. These results establish a quantitative framework linking ion-pairing thermodynamics to co-ion penetration and providing strategies to design electrochemical interfaces.

Co-ion penetration↗

Atomistic thermodynamics and kinetics of dicalcium silicate dissolution

Low-temperature cement manufacturing has garnered academic and industrial attention for its low environmental footprints. However, the sluggish hydration kinetics of the resultant cement affects their early-age strength development. This motivates fundamental studies to unravel the mechanistic picture of the dissolution process and discover science-informed pathways to accelerate hydration. Standard atomistic simulations seldomly exceed a microsecond making them impractical to study slow dissolution processes. We are using rare event sampling techniques, we provide the mechanistic picture of Ca 2+ ion dissolution from a kink site on the dicalcium silicate surface. The Ca 2+ ion dissolution is comprised of two sequential stages: breaking restraints from the kink sites to form a ledge adatom and detaching from the ledge/terrace adatom sites into the solution. The first and second stages feature free energy barriers of ~63 kJ/mol and ~ 29 kJ/mol respectively, making the first stage the rate-limiting step of the entire Ca 2+ dissolution kinetics. Using the reactive flux method, the rate and equilibrium constants for each reaction step are calculated, which yield the Ca 2+ ion activity of ~1.03 × 10 -5 . The diffusion calculations indicate that the surface effects lower the self-diffusion coefficient of Ca 2+ ions at the solid-water interface.

36 MATERIALS SCIENCE↗

A classical molecular dynamics simulation method for the formation of “dry” gels from boro-aluminosilicate glass structures

In contact with water, glass transforms into amorphous and porous structures called gels. A simulation method based on classical molecular dynamics is proposed here to mimic “dry” gels forming from initial oxide glass structures. Six glass compositions were investigated. Two behaviours were evidenced depending on the initial glass composition, and in particular on the quantity of elements removed. If a large quantity of soluble elements (B, Na) was removed, it induced an increase in the average pore size within the gels, and the time needed to stabilise the gel structure increased because more local atomic rearrangements occurred. The gel network displayed a higher proportion of Si-Q4 at the expense of Si-Q3 and a lower average ring size compared to the glass network, irrespective of the glass composition. Surface effects were also highlighted in the dry gels, such as the presence of 3-coordinated Al and a decrease in the average angle Si-O-Si and Al-O-Al. Our findings will be compared to both wet gels and experimental data in further studies, to help find the best procedure to simulate such structures.

36 MATERIALS SCIENCE↗

Perturbing the spin state and conduction of Fe (II) spin crossover complexes with TCNQ

In this study, we investigated modifications driven by 7,7,8,8-tetracyanoquinodimethane (TCNQ) to the spin state configuration of [Fe(3-bpp) 2 ](TCNQ) 2 co-crystal and both spin state and electric conductivity of [Fe{H 2 B(pz) 2 } 2 (bipy)] and TCNQ mixtures. The Fe 2+ site in the [Fe(3-bpp) 2 ](TCNQ) 2 co-crystal has a sizable orbital moment. During X-ray absorption measurements, the iron ion is partially excited to the high spin state and strong surface effects are indicated. Mixing TCNQ with the [Fe{H 2 B(pz) 2 } 2 (bipy)] spin crossover complex leads to a molecular combination with increased conductivity and drift carrier lifetimes. [Fe{H 2 B(pz) 2 } 2 (bipy)] thin films with TCNQ, grown using dimethylformamide (DMF), are to great extent locked mainly in the low spin (LS) state across a broad temperature range and exhibit drift carrier lifetimes approaching 0.5 s. When deposited onto a ferroelectric polyvinylidenefluoride-hexafluoropropylene thin film substrate, [Fe{H 2 B(pz) 2 } 2 (bipy)], shows enhanced transistor carrier mobility, likely associated with the increasing cationic character of [Fe{H 2 B(pz) 2 } 2 (bipy)] thin films with TCNQ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Underlying mechanism of structural transformation between GaSb and GaAs response to intense electronic excitation

Ion irradiation of semiconductors has emerged as a promising approach for fabricating self-organized nanosystems with high atomic precision, despite often being accompanied by undesirable phenomena. Exploring the mechanisms underlying structural transformations is crucial for assessing nanostructure array types under complex irradiation environments. By quantitatively calculating the thermodynamically driven processes and analyzing the impact of intrinsic structural parameters, distinct structural transformations in response to intense electronic excitation are systematically investigated in gallium antimonide (GaSb) and gallium arsenide (GaAs) systems. In high-energy regimes, the nanofibers layer of GaSb exhibits intriguing structural discrepancy, characterized by partial nanofibers with coherent boundaries, interspersed nanopores accompanied by antisite defects and Ga precipitates, distinguishing to a series of discontinuous latent tracks that emerged within cylindrical trajectories in GaAs. Furthermore, significant diffusion behaviors of the nanohillocks are discovered in GaAs, with higher average roughness than GaSb, driven by the gradient stress distribution influenced by the free-surface effects. The deposition energy for melting phase formation, Gibbs free energy, and Ga diffusion coefficients contribute to the distinctive structural features, evidencing relatively stable morphological configurations and higher irradiation resistance in GaAs. Consequently, special optoelectronic properties associated with structural discrepancies facilitate the design and optimization of material functionalities by irradiation technologies.

36 MATERIALS SCIENCE↗

Direct, efficient and selective capture of low concentration of CO 2 from natural gas flue gas using a high temperature tubular carbon capture membrane

Natural gas (NG) fired power plants emit low concentration (4–5%) of CO 2 , which presents additional technical and economic challenges to the current benchmark amine absorption technology. The newly emerged high-temperature multiphase membranes operated on molten carbonate (MC) chemistry for CO 2 capture/separation/conversion have been demonstrated with great potential to meet this challenge. In this study, we report on the CO 2 capture performance of such a membrane in tubular geometry from a mockup NG flue gas. The membrane is comprised of a mixture of Gd 0.20 Ce 0.80 O 1.95 (GDC) and MC, in which GDC forms a porous skeleton to contain MC. Here, we show that the membrane with a dimension of 6.1 mm in outer diameter, 5.1 mm in inner diameter and 5 cm in effective length (resulting in 4cm 2 effective surface area) can achieve a CO 2 flux density of 0.46–0.55 mL/min·cm 2 at 650°C, capturing 97% pure CO 2 at a rate of 37–42% from 5%CO 2 –N 2 using moistened Ar as the sweep gas. The level of performance demonstrated by this study suites the membrane well for stationary CO 2 capture from NG power plants.

03 NATURAL GAS↗

Grain subdivision and structural modifications by high-energy heavy ions in UO 2 with different initial grain size

Irradiation with 84 MeV Xe ions at peak fluence above 7 × 10 17 ions/cm 2 has been carried out on two UO 2 samples with different initial grain sizes at 300 °C and 500 °C. Characterization of both grain structure and bubble morphology has been performed using transmission electron microscopy, image analysis and precession electron diffraction. The bubble size in the large-grained sample was smaller than that in the standard-grain sample, confirming fission gas precipitation resistance in the former. The ion irradiation in the high electronic energy deposition range has caused formation of a large density of dislocations which resulted in grain polygonization for the sample with standard grain size, which was observed in multiple lamellas extracted next to each other at peak dose. The sample with large grains showed inconsistent behavior. In one case, dislocation pile-up occurred, but no sub-grain formation was observed. An adjacent location showed sub-grain formation, even if to less extent compared to the standard grain-size sample. Furthermore, these findings suggest a limited polygonization resistance in large-grained UO 2 compared to standard-grain UO 2 . Recrystallization of both sample surfaces was present, leaving unclear if this is a surface effect or a consequence of the highest energy deposition rate in this area.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Sensitivity analysis of thermal contact conductance modeling to inform MiniFuel irradiation capsule designs

The MiniFuel irradiation platform has been developed by Oak Ridge National Laboratory as a flexible, high-throughput separate effects testing capability within the High Flux Isotope Reactor (HFIR). Finite element thermal models are relied upon to design MiniFuel experiments to achieve a specific time-averaged irradiation temperature for experimental objectives. A previous study identified that uncertainty in the component heat generation rates and thermal contact conductance (TCC) model are the most significant contributors to predicted fuel temperature variance. To address both sources of uncertainty, this work performs sensitivity analysis on the TCC model to identify high-impact, high-uncertainty parameters that contribute to fuel temperature variance. The TCC model is analyzed in increasing detail, first using a standalone Python code, then again after coupling Python to the BISON fuel performance code. Furthermore, the parameters with the largest contributions to fuel temperature variance which can be reduced through design changes are identified as the initial subcapsule gas pressure, contact pressure between the fuel and dish, and the effective surface roughness of the interface. A set of design recommendations for future capsule designs has been established and applied to reduce the previously quantified average fuel temperature uncertainty ranges of ± 40 °C in the HFIR vertical experiment facilities (VXF) and ± 80 °C in the removable beryllium (RB) reflector to approximately ± 32 °C and ± 53 °C, respectively. This equates to a 21 % and 33 % reduction in the uncertainty range of the average fuel temperature for VXF and RB, respectively.

BISON↗

OC7 phase I: CFD investigation of viscous forces on rectangular members of semisubmersibles

In Phase I of the Offshore Code Comparison Collaboration 7 (OC7) project, we aim to address key questions related to the modeling of viscous hydrodynamic loads on floating platforms. Here, this paper presents results from a collaborative effort within Phase I of the OC7 project. We investigate viscous forces acting on the rectangular members of semisubmersible platforms using high-fidelity computational fluid dynamics (CFD) simulations. The parametric CFD analyses include two-and-a-half-dimensional (2.5D) simulations of pontoon sections of two different semisubmersible platform designs (the VolturnUS-S and the INO WINDMOOR) and full three-dimensional (3D) structure simulations of the VolturnUS-S platform. We extract both the added mass and drag coefficients that are typically used in engineering-level hydrodynamic models from the 2.5D forced oscillation simulations with various Keulegan-Carpenter numbers and compare them to the coefficients from the 3D forced oscillation simulations. We observe consistent variation of the coefficients along the pontoon legs due to 3D platform and free-surface effects. With the breadth of the simulations and component-level detailed analyses, this work establishes a useful database and several empirical formulas for selecting hydrodynamic coefficients when modeling semisubmersible platforms in engineering tools.

13 HYDRO ENERGY↗

Oil miscible phosphonium-phosphate ionic liquid as novel antiwear and antipitting additive for low-viscosity rear axle lubricants

Here we explored the feasibility of using a phosphonium phosphate ionic liquid as a candidate anti-wear and anti-pitting additive for rear axle lubricant. This particular IL was first added to a VHVI8 base oil at 2–3% concentration and demonstrated effective surface protection for wear and micro-cracking under rolling-sliding contacts. The promising results directed to a step further to produce a series of IL-containing low-viscosity (about a half of SAE 75W-90) fully formulated gear oils. Selected IL-containing experimental oils showed superior mitigation of rolling contact fatigue to a commercial SAE 75W-90 gear oil in bench-scale rolling-sliding tests. Full-scale hub dynamometer tests were then conducted and demonstrated more than 3% power output and torque generation for an IL-containing low-viscosity gear oil benchmarked against commercial baselines.

36 MATERIALS SCIENCE↗

Using Nanofiller Assemblies to Control the Crystallization Kinetics of High-Density Polyethylene

Polyethylene-grafted nanoparticles (NPs) are organized into a variety of assemblies in a polydisperse polyethylene melt by tailoring the graft density and molecular weights of the graft chains. Under these conditions we systematically vary NP assemble state and study is consequences on crystal nucleation and growth rates. We find that the nucleation rate is suppressed below that of the unfilled polymer for good NP spatial dispersion. However, poorer dispersion, which leads to the formation of NP assemblies, can accelerate nucleation likely by providing multiple heterogenous sites due to topographical features. We find that a key parameter, the chain overcrowding in the brush, can predict these nucleation trends – in this language, the most enhanced nucleation rate is found when the grafts are the most overcrowded, and hence the least interpenetrated with the matrix chains. This result is consistent with one other literature result which utilized short crystallizable polyethylene glycol grafts in short PEO matrices. The growth kinetics were retarded for all nanocomposites, their temperature dependences were essentially equal to that for the pure polymer (in the absence of NPs) – the NPs thus do not affect secondary nucleation, indicating that the transport of the matrix to the growth front is the rate determining step. Thus, evidently the increase in matrix viscosity, or reduction in growth rates, is directly determined by the agglomeration state of the NPs. These results are consistent with past works with bare silica NPs in PEO, and with silica NPs grafted with amorphous chains in a PEO matrix, suggesting that growth kinetics in these systems apparently follow “universal” behavior. Additionally, there are initial hints that the ratio of the effective surface area of the NP clusters per unit matrix volume provides a unified description of the NP induced confinement that slows growth kinetics. Furthermore, our work thus shows that there is an evolving understanding of the role of NPs on crystallization kinetics, in particular crystal growth where trends appear to be independent of the grafts ability to crystallize.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗