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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 217 records · Page 12

Organic Signature of Dust from the Interstellar Medium (ISM)

Dust in the ISM carries an "organic" signature in form of a distinct group of C-H stretching bands, both in emission and absorption, around 3.4 micrometers. These bands agree with the symmetrical and asymmetrical C-H stretching vibrations of aliphatic -CH2- entities and are thought to be associated with organic molecules on the surface of dust grains. We show that this interpretation is inconsistent with laboratory experiments. Synthetic MgO and natural olivine single crystals, grown from a CO/CO2/H2O-saturated melt, exhibit the same C-H stretching bands but those bands are clearly associated with C-H entities inside the dense mineral matrix. The multitude of C-H stretching bands suggests that the C-H bonds arise from polyatomic C(sub n) entities. We heated the MgO and olivine crystals to temperatures between 550-1000 K to pyrolyze the C-H bonds and to cause the C-H stretching bands to disappear. Upon annealing at moderate temperatures between 300-390 K the C-H stretching bands reappear within a few days to weeks. The C-H stretching band intensity increases linearly with the square root of time. Thus, while the pyrolysis broke the C-H bonds and caused the H to disperse in the mineral matrix, the H atoms (or H2 molecules) are sufficiently mobile to return during annealing and reestablish the C-H bonds. Dust grains that condense in a gas-laden environment (outflow of late-stage stars or in dense molecular clouds) probably incorporate the same type of Cn-H entities. Imbedded in and in part bonded to the surrounding mineral matrix, the Cn-H entities display C-H stretching bands in the 3.4 micrometer region, but their lower frequency librational modes are so strongly coupled to the lattice modes that they broaden excessively and thus become unobservable.

Freund, Friedemann↗

Theoretical Investigation of Solvent Effects on the Hydrodeoxygenation of Propionic Acid over a Ni(111) Catalyst Model

The effect of two solvents, liquid water and 1,4-dioxane, has been studied from first principles on the hydrodeoxygenation of propionic acid over a Ni (111) catalyst surface model. A mean-field microkinetic model was developed to investigate these effects at a temperature of 473 K. Under all reaction conditions, a decarbonylation mechanism is favored significantly over a decarboxylation pathway. Although no significant solvent effects were observed on the decarbonylation rate, a substantial solvent stabilization of two key surface intermediates in the decarboxylation mechanism, CH 3 CCOO and CH 3 CHCOO, lead to a notable increase of the decarboxylation rate by two orders of magnitude in liquid water and by one order of magnitude in liquid 1,4-dioxane. Furthermore, a significant solvent stabilization of the transition state of C-H bond cleavage of the α-carbon of CH 3 CHCO, relative to the stabilization of the C-C bond cleavage of the α-carbon of CH 3 CHCO, leads to a change in dominant pathway in the liquid phase environments. Finally, a sensitivity analysis shows that the C-OH bond cleavage of propionic acid and C-C bond cleavage of the α-carbon of CH 3 CHCO are the most rate controlling states in the gas phase. In contrast, in solvents the dehydrogenation of CH 3 CHCO becomes the most influential step. This shift in rate controlling state is attributed to the solvent effect on the dehydrogenation of CH 3 CHCO, which is facilitated in aqueous phase. Altogether, it is likely that the investigated (111) facet of Ni is not active for the hydrodeoxygenation of propionic acid in neither the gas nor liquid phase and other Ni facets or phases must be responsible for the experimentally observed kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aluminum/SmCo 5 composites for structural and magnetic applications

Metal-bonded magnetic composites (MBMCs) present a promising alternative to dense sintered magnets, particularly for intricate components. Compared to polymer-based bonded magnets, MBMCs have wider applicability in harsh environments. In this paper, we demonstrate a solid-state shear-based manufacturing technique to introduce localized magnetization into a paramagnetic aluminum matrix by embedding SmCo5 permanent magnet particles. Our magnetic composites display hard magnetic behavior with a coercivity of 13 kOe and a remanent magnetization of 4.32 emu/g. In addition to magnetization, we also report a 9% improvement in Young’s modulus. Despite the local temperature rise during processing, the magnetic phases didn’t decompose into unwanted phases, preserving the composite's hard magnetic properties. Creation of an interfacial metallurgical bond with the matrix ensured the suitability of the composites for structural applications. Our study investigates the mechanical, and functional properties of composites, paving the way for lightweight structural magnetic composites with a transformative potential in the aerospace, nuclear, and automotive applications. This work underscores the potential for further optimization and development to drive innovations in magnet and equipment design.

36 MATERIALS SCIENCE↗

Kinetic Monte Carlo Simulations of Oxygen Diffusion in Environmental Barrier Coating Materials

Ceramic Matrix Composite (CMC) materials are of interest for use in next-generation turbine engine components, offering a number of significant advantages, including reduced weight and high operating temperatures. However, in the hot environment in which such components operate, the presence of water vapor can lead to corrosion and recession, limiting the useful life of the components. Such degradation can be reduced through the use of Environmental Barrier Coatings (EBCs) that limit the amount of oxygen and water vapor reaching the component. Candidate EBC materials include Yttrium and Ytterbium silicates. In this work we present results of kinetic Monte Carlo (kMC) simulations of oxygen diffusion, via the vacancy mechanism, in Yttrium and Ytterbium disilicates, along with a brief discussion of interstitial diffusion. An EBC system typically includes a bond coat located between the EBC and the component surface. Bond coat materials are generally chosen for properties other than low oxygen diffusivity, but low oxygen diffusivity is nevertheless a desirable characteristic, as the bond coat could provide some additional component protection, particularly in the case where cracks in the coating system provide a direct path from the environment to the bond coat interface. We have therefore performed similar kMC simulations of oxygen diffusion in this material.

Good, Brian S.↗

Elucidating the Role of Hydrogen Bonding in the Optical Spectroscopy of the Solvated Green Fluorescent Protein Chromophore: Using Machine Learning to Establish the Importance of High-Level Electronic Structure

Hydrogen bonding interactions with chromophores in chemical and biological environments play a key role in determining their electronic absorption and relaxation processes, which are manifested in their linear and multidimensional optical spectra. For chromophores in the condensed phase, the large number of atoms needed to simulate the environment has traditionally prohibited the use of high-level excited-state electronic structure methods. By leveraging transfer learning, we show how to construct machine-learned models to accurately predict the high-level excitation energies of a chromophore in solution from only 400 high-level calculations. Here, we show that when the electronic excitations of the green fluorescent protein chromophore in water are treated using EOM-CCSD embedded in a DFT description of the solvent the optical spectrum is correctly captured and that this improvement arises from correctly treating the coupling of the electronic transition to electric fields, which leads to a larger response upon hydrogen bonding between the chromophore and water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical bonding technology for terrestrial photovoltaic modules

Encapsulated photovoltaic modules must hold together for 20 years, reliably resisting delamination and separation of any of the component materials. Delamination of encapsulation materials from each other, or from solar cells and interconnects, can create voids for accumulation of water, promoting corrosive failure. Delamination of silicone elastomers from unprimed surfaces was a common occurrence with early modules, but the incidences of silicone delamination with later modules decreased when adhesion promoters recommended by silicone manufacturers were used. An investigation of silicone delamination from unprimed surfaces successfully identified the mechanism, which was related to atmospheric oxygen and moisture. This early finding indicated that reliance on physical bonding of encapsulation interfaces for long life in an outdoor environment would be risky. For long outdoor life, the material components of a module must therefore be held together by weather-stable adhesion promoters that desirably form strong, interfacial chemical bonds.

Coulter, D. R.↗

Determining bonding, thickness, and density via thermal wave impedance NDE

Bonding, density, and thickness of coatings have a vital effect on their performance in many applications. Pioneering development work on thermal wave nondestructive evaluation (NDE) methods during the past 25 years has resulted in an array of useful techniques for performing bonding, density, and thickness measurements in a practical shop environment. The most useful thermal wave methods for this purpose are based on thermal wave surface impedance measurement or scanning. A pulse of heat from either a thermal transducer or a hot gas pulse is projected onto the surface, and the resulting temperature response is analyzed to unfold the bonding, density, and thickness of the coating. An advanced emissivity independent infrared method was applied to detect the temperature response. These methods were recently completely computerized and can automatically provide information on coating quality in near real-time using the proper equipment. Complex shapes such as turbine blades can be scanned. Microscopic inhomogeneities such as microstructural differences and small, normal, isolated voids do not cause problems but are seen as slight differences in the bulk thermal properties. Test objects with rough surfaces can be effectively nondestructively evaluated using proper thermal surface impedance methods. Some of the basic principles involved, as well as metallographic results illustrating the ability of the thermal wave surface impedance method to detect natural nonbonds under a two-layer thermally sprayed coating, will be presented.

Green, D. R.↗

Synergistic Enhancement of Lead and Selenate Uptake at the Barite (001)–Water Interface

The interactions of heavy metals with minerals influence the mobility and bioavailability of toxic elements in natural aqueous environments. The sorption of heavy metals on covalently bonded minerals is generally well described by surface complexation models (SCMs). However, understanding sorption on sparingly soluble minerals is challenging because of the dynamically evolving chemistry of sorbent surfaces. The interpretation can be even more complicated when multiple metal ions compete for sorption. In the present study, we observed synergistically enhanced uptake of lead and selenate on the barite (001) surface through two sorption mechanisms: lattice incorporation that dominates at lower coverages and two-dimensional monolayer growth that dominates at higher coverages. Further, we also observed a systematic increase in the sorption affinity with increasing co-sorbed ion coverages, different from the assumption of invariant binding constants for individual adsorption processes in classical SCMs. Computational simulations showed thermodynamically favorable co-incorporation of lead and selenate by simultaneously substituting for barium and sulfate in neighboring sites, resulting in the formation of molecular clusters that locally match the net dimension of the substrate lattice. These results emphasize the importance of ion–ion interactions at mineral–water interfaces that control the fate and transport of contaminants in the environment.

54 ENVIRONMENTAL SCIENCES↗

NR-150B2 adhesive development

Adhesive based polyimide solutions which are more easily processed than conventional aromatic polyimide systems and show potential for use for extended times at 589K are discussed. The adhesive system is based on a solution containing diglyme as the solvent and 2,2 bis(3',4'-dicarboxyphenyl)hexafluoropropane, paraphenylenediamine, and oxydianiline. The replacement of N-methylpyrrolidone with diglyme as the solvent was found to improve the adhesive strengths of lap shear samples and simplify the processing conditions for bonding both titanium and graphite fiber/polyimide matrix resin composites. Information was obtained on the effects of various environments including high humidity, immersion in jet fuel and methylethylketone on aluminum filled adhesive bonds. The adhesive was also evaluated in wide area bonds and flatwise tensile specimens using titanium honeycomb and composite face sheets. It was indicated that the developed adhesive system has the potential for use in applications requiring long term exposure to at least 589K (600 F).

Blatz, P. S.↗

Effects of simulated space environment on Skylab parasol material

A material consisting of ripstop nylon bonded to the Mylar side of aluminized Mylar film was used to construct the first Skylab parasol. The mechanical properties of elongation and tensile strength and the radiative properties of solar absorptance and thermal emittance were measured before and after exposure to simulated solar radiation at intensities of 1.0 and 3.5 solar constants for exposure times as long as 947 hours or 3316 equivalent solar hours. The accelerated testing indicated more severe degradation than was experienced in the real-time test (1 solar constant). The results predicted that this material could have given satisfactory performance throughout the planned lifetime of the Skylab workshop.

Slemp, W. S.↗

Real-Space Local Dynamics in 1,2,3-Triazole Using Inelastic Neutron Scattering

Enhancing proton transport in polymer electrolytes is crucial for advancing next-generation solid-state batteries, yet our understanding of proton conductivity in nonaqueous environments remains limited due to a lack of atomic-scale insights. Here, in this study, we investigated the atomic-scale dynamics of 1,2,3-triazole, a small molecule capable of dynamic hydrogen bonding, as a model system for proton hopping in nonaqueous environments. Using the real-space correlation function determined by the double Fourier transformation of inelastic neutron scattering spectra, we identified that the self-motion of protons and intermolecular dynamics occur on comparable time scales. Furthermore, we observed that the activation energy associated with the intermolecular dynamics matches the energy barrier for molecular rotations determined through Density Functional Theory calculations. These findings underscore the importance of controlling molecular dynamics at the atomic scale to control proton transport. Additionally, we demonstrated that intermolecular dynamics in systems involving protons can be studied using inelastic neutron scattering even without deuteration, thereby providing a broader avenue for studying atomic-scale dynamics in soft matter systems.

Shinohara, Yuya [Oak Ridge National Laboratory (OR↗

Size and Structure Effects of Carbon-Supported Ruthenium Nanoparticles on Waste Polypropylene Hydrogenolysis Activity, Selectivity, and Product Microstructure

Hydrogenolysis of plastic waste using Ru-based catalysts is promising for deconstructing polyolefins into lower molecular weight products. Yet, the effect of catalyst atomic structure and size on activity and product selectivity is poorly understood. Herein, we expose the effect of metal particle size and atomic structure on isotactic-polypropylene (i-PP) hydrogenolysis over Ru supported on carbon. Despite similar molecular weight distributions of solid and liquid products, their physical properties are distinct due to different chain regio-irregular CH3 sequences of steric pentads containing racemo configurations. We propose that i-PP hydrogenolysis entails an interplay of C–C bond scission and stereoisomerization. The active site’s local electronic environment and structure dictate the former, whereas polymer–catalyst surface interactions creating suitable polymer conformations control the latter. C–C scission and stereoisomerization are structure-sensitive. Small, disordered nanoclusters are effective in C–C bond scission, whereas larger metal nanoparticles promote stereoisomerization. Finally, we hypothesize that a heterogeneous distribution of metal active sites is essential for deconstruction and product (lubricant base oil) quality control.

36 MATERIALS SCIENCE↗

Ligand effects on electronic structure and bonding in U(iii) coordination complexes: a combined MCD, EPR and computational study

The trivalent oxidation state of uranium has been shown to undergo unique reactivity, from its ability to activate a variety of small molecules to its role in the catalytic reduction of ethene to ethane amongst others. Central to this unique reactivity and ability to rationally design ligands for isotope separation is the underlying uranium electronic structure. While electronic structure studies of U(IV), U(V), and U(VI) have been extensive, by comparison, analogous studies of more reduced oxidation states such as U(III) remains underdeveloped. Herein we report a combined MCD and EPR spectroscopic approach along with density functional theory and multireference wavefunction calculations to elucidate the effects of ligand perturbation in three uranium(III) Tp* complexes. Overall, the experimental and computational insight suggests that the change in ligand environment across this series of U(III) complexes resulted in only minor perturbations in the uranium electronic structure. This combined approach was also used to redefine the electronic ground state of a U(III) complex with a redox non-innocent Bipy - ligand. Overall, these studies demonstrate the efficacy of the combined experimental and theoretical approach towards evaluating electronic structure and bonding in U(III) complexes and provide important insight into the challenges in altering ligand environments to modify bonding and reactivity in uranium coordination chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heat Shield Employing Cured Thermal Protection Material Blocks Bonded in a Large-Cell Honeycomb Matrix

A document describes a new way to integrate thermal protection materials on external surfaces of vehicles that experience the severe heating environments of atmospheric entry from space. Cured blocks of thermal protection materials are bonded into a compatible, large-cell honeycomb matrix that can be applied on the external surfaces of the vehicles. The honeycomb matrix cell size, and corresponding thermal protection material block size, is envisioned to be between 1 and 4 in. (.2.5 and 10 cm) on a side, with a depth required to protect the vehicle. The cell wall thickness is thin, between 0.01 and 0.10 in. (.0.025 and 0.25 cm). A key feature is that the honeycomb matrix is attached to the vehicle fs unprotected external surface prior to insertion of the thermal protection material blocks. The attachment integrity of the honeycomb can then be confirmed over the full range of temperature and loads that the vehicle will experience. Another key feature of the innovation is the use of uniform-sized thermal protection material blocks. This feature allows for the mass production of these blocks at a size that is convenient for quality control inspection. The honeycomb that receives the blocks must have cells with a compatible set of internal dimensions. The innovation involves the use of a faceted subsurface under the honeycomb. This provides a predictable surface with perpendicular cell walls for the majority of the blocks. Some cells will have positive tapers to accommodate mitered joints between honeycomb panels on each facet of the subsurface. These tapered cells have dimensions that may fall within the boundaries of the uniform-sized blocks.

Zell, Peter↗

Investigation of coverage dependence of the stretching frequency of CO adsorbed on Pd surfaces at low coverage limits

The stretching frequency of the C—O bond is a sensitive probe of the local environment of a surface-bound CO molecule, including the adorption site and density, i.e. surface coverage. In this work, we extend our analysis beyond the frequency shift due to differences in adsorption configurations. Using density functional theory (DFT) calculations, we directly explore the correlations between surface coverage and the stretching frequency of adsorbed CO on Pd surfaces. Here we also perform constant pressure infrared reflection absorption measurements of CO on Pd(111) and use existing relations between pressure and coverage to derive coverage dependency. Both results are compared to previously reported experimental data. Our derived correlations of peak frequency and area with surface coverage can help interpret experimental IR spectra in real time and extract time-dependent concentration data from transient kinetic experiments.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Liquid Structure and Transport Properties of the Deep Eutectic Solvent Ethaline

A range of techniques including physical property measurements, neutron scattering experiments, ab initio molecular dynamics, and classical molecular dynamics simulations are used to probe the structural, thermodynamic, and transport properties of a deep eutectic solvent comprised of a 1:2 molar ratio of choline chloride and ethylene glycol. This mixture, known as Ethaline, has many desirable properties for use in a range of applications, and therefore, understanding its liquid structure and transport properties is of interest. Simulation results are able to capture experimental densities, diffusivities, viscosities, and structure factors extremely well. Here, the solvation environment is dynamic and dominated by different hydrogen bonding interactions. Dynamic heterogeneities resulting from hydrogen bonding interactions are quantified. Rotational dynamics of molecular dipole moments of choline and ethylene glycol are computed and found to exhibit a fast and slow mode.

25 ENERGY STORAGE↗

Surface Hydration and Hydroxyl Configurations of Gibbsite and Boehmite Nanoplates

Discontinuation of the bulk structure at the interface between metal oxide particles and water leads to altered bonding characteristics and unique facet-dependent molecular environments. Surface hydration and consequent hydroxylation adds further complexity to the interface, details that for metal (oxy)hydroxides are especially difficult to isolate from the background signal of bulk structural hydroxyls. Here we probe for the first time the hydroxylation and hydration structures on basal surfaces of gibbsite (?-Al(OH)3) and boehmite (?-AlOOH) nanoplates at ambient conditions, using the interface-sensitive technique vibrational sum frequency generation spectroscopy (VSFG). Hydroxyl stretching modes at the interfaces with adsorbed water layers compared directly to Raman and infrared bulk modes show that while gibbsite surface frequencies were sharp and nearly identical to those in the bulk, boehmite surface hydroxyls displayed a very different broad spectrum of states. Ab initio molecular dynamics simulations of both basal surfaces with and without hydration waters reveal that gibbsite surface hydroxyls interact only weakly with overlying hydration waters remaining essentially unperturbed, whereasthose on boehmite can interact more strongly facilitated by higher configurational degrees of freedom at the interface. The findings clearly unveil substantial differences in the hydrated interfacial dynamics of these two otherwise similar materials, with implications for their interfacial chemistry and wettability.

Sassi, Michel JPC↗