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At least 307 records · Page 17

Fermi surface studies of the low-temperature structure of sodium

Sodium is the most abundant alkali-metal element and has one of the simplest electronic structures of any metal. At ambient conditions, sodium forms a body-centered-cubic lattice. However, during cooling, it undergoes a partial martensitic phase transition to a complex mixture of rhombohedral polytypes commencing from 36 K. Although the Fermi surface (FS) of bcc sodium has been extensively studied, not much attention has been given to the FS of the martensite structure. Here we report results for the Fermi surface and quantum oscillation (QO) frequencies of several energetically favorable crystal structures of Na at low temperature from first-principles calculations. Interestingly we find that despite drastic differences in the crystal structures of the candidate low-temperature phases of sodium, for all these phases the strongest quantum oscillation peak is centered at 28 kT. Our theoretical results are accompanied by experimental data of QO on a multigrain sodium sample at T = 0.3 K and B max = 18 T exhibiting a sharp peak at 28 kT, independent of the sample orientation. The persistence of this peak even in the presence of the structural transitions has an implication for using the quantum oscillations of polycrystalline sodium for high magnetic field calibration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Advanced nanoscale characterization of aluminum nanoparticles with modified surface morphology via atmospheric helium and carbon monoxide plasmas

Aluminum nanoparticles (nAl) have the potential as energetic additives in explosive/propellant formulations. Scalable methodologies must be pursued to mitigate the inactive amorphous alumina shell surrounding the active aluminum (Al) core with modified surface morphology and chemistry for increased combustion effects. This work explores the feasibility of making reactive core/shell nAl with thinned oxide shells and modified surface coatings via a two-step atmospheric plasma surface treatment process in a custom dielectric barrier discharge plasma reactor. The commercial nAl of nominal average size similar to 40-60nm was first treated with helium (He) followed by He/carbon monoxide (CO) plasmas for different durations. The resultant samples were characterized via high-resolution transmission electron microscopy (HRTEM) and Fourier transform IR (FTIR) spectra. HRTEM images revealed sporadic patchy gamma -alumina deposits on particle surfaces and in gaps among particles for all samples, suggesting the non-uniform plasma effects of the He/CO glow. Nanoscale chemical analyses via scanning transmission electron microscopy elemental mapping and x-ray energy dispersive spectroscopy were further performed. Although no carbon-associated structure appeared in electron energy loss spectroscopy (EELS) spectra, the presence of carbonaceous materials was confirmed as a thin dispersive layer evenly distributed on the nAl surface suggesting either its amorphous nature or is present at a level insufficient to generate satisfactory EELS spectra. The trend of intensity profiles for key elements acquired by drawing lines across a single particle on the elemental maps confirmed that carbonaceous materials only existed on the surface and they were most likely carboxylates that increased with increased He/CO treatment duration, as evident by FTIR results. Finally, this work demonstrated the success of atmospheric plasma-treated reactive nAl with comprehensively characterized surface features via advanced microscopy and spectroscopy.

36 MATERIALS SCIENCE↗

Dispersion of surface-modified, aggregated, fumed silica in polymer nanocomposites

Surface modification of model silica to enhance compatibility in nanocomposites has been widely studied. In addition to model spherical silica, several authors have investigated the impact of surface conditions on compatibility in commercial aggregated carbon black and silica. Here, dispersion is investigated for a series of nanocomposites produced from commercially modified fumed silica mixed with styrene butadiene rubber, polystyrene, and polydimethylsiloxane. Surface modification includes variation in surface hydroxyl content, siloxane, and silane treatment. Qualitatively, hydroxyl groups on the silica surface are considered incompatible with non-polar polymers, while methyl groups are compatible with oleophilic polymers. X-ray scattering was used to analyze the filler aggregate structure before and after dispersion, and the second virial coefficient was used to quantify nanodispersion. The content of surface moieties was determined from Fourier-transform infrared spectroscopy. It is observed that modified silica can display mean field or specific interactions as reflected by the presence of a correlation peak in x-ray scattering. For systems with specific interactions, a critical ordering concentration is observed related to the free energy change for structuring. A van der Waals model was used to model the second virial coefficient as a function of accumulated strain, yielding the excluded volume and an energetic term. The excluded volume could be predicted from the structural information, and the bound polymer layer was directly related to the surface methyl content, whereas the energetic term was found to synergistically depend on both the methyl and hydroxyl surface content.

36 MATERIALS SCIENCE↗

Modeling Framework to Predict Melting Dynamics at Microstructural Defects in TNT-HMX High Explosive Composites

Many high explosive (HE) formulations are composite materials whose microstructure is understood to impact functional characteristics. Interfaces are known to mediate the formation of hot spots that control their safety and initiation. Here, to study such processes at molecular scales, we developed all-atom force fields (FFs) for Octol, a prototypical HE formulation comprised of TNT (2,4,6-trinitrotoluene) and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine). We extended a FF for TNT and recasted it in a form that can be readily combined with a well-established FF for HMX. The resulting FF was extensively validated against experimental results and density functional theory calculations. We applied the new combined TNT-HMX FF to predict and rank surface and interface energies, which indicate that there is an energetic driver for coarsening of microstructural grains in TNT-HMX composites. Finally, we assess the impact of several microstructural environments on the dynamic melting of TNT crystal under ultrafast thermal loading. We find that both free surfaces and planar material interfaces are effective nucleation points for TNT melting. However, MD simulations show that TNT crystal is prone to superheating by at least 50 K on subnanosecond time scales and that the degree of superheating is inversely correlated with surface and interface energy. The modeling framework presented here will enable future studies on hot spot formation processes in accident scenarios that are governed by strong coupling between microstructural interfaces, material mechanics, momentum and energy transport, phase transitions, and chemistry.

36 MATERIALS SCIENCE↗

Theoretical characterization of the potential energy surface for NH + NO

The potential energy surface (PES) for NH + NO was characterized using complete active space self-consistent field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration interaction (CCI) calculations to refine the energetics. The present results are in qualitative accord with the BAC-MP4 calculations, but there are differences as large as 8 kcal/mol in the detailed energetics. Addition of NH to NO on a (2)A' surface, which correlated with N2 + OH or H + N2O products, involves barriers of 3.2 kcal/mol (trans) and 6.3 kcal/mol (cis). Experimental evidence for these barriers is found in earlier works. The (2)A' surface has no barrier to addition, but does not correlate with products. Surface crossings between the barrierless (2)A' surface and the (2)A' surface may be important. Production of N2 + OH products is predicted to occur via a planar saddle point of (2)A' symmetry. This is in accord with the preferential formation of II(A') lambda doublet levels of OH in earlier experiments. Addition of NH (1)delta to NO is found to occur on an excited state surface and is predicted to lead to N2O product as observed in earlier works.

Walch, Stephen P.↗

Europa Surface Radiation Environment for Lander Assessment

The Jovian magnetospheric particle environment at Europa's surface is critical to assessment of landed astrobiological experiments in three respects: (1) the landing site must be chosen for the best prospects for detectable organic or inorganic signs of Life, e.g. regions of freshly emergent flows from the subsurface; (2) lander systems must reach the surface through the Jovian magnetospheric environment and operate long enough on the surface to return useful data; (3) lander instrumentation must be capable of detecting signs of life in the context of the local environmental radiation and associated chemistry. The Galileo, Voyager, and Pioneer missions have provided a wealth of data on energetic particle intensities throughout the Jovian magnetosphere including from many flybys of Europa. cumulative radiation dosages for spacecraft enroute to Europa can be well characterized, but knowledge of the surface radiation environment is very limited. Energetic electrons should primarily impact the trailing hemisphere with decreasing intensity towards the center of the leading hemisphere and are the most significant radiation component down to meter depths in the surface regolith due to secondary interactions. Observed surface distribution for sulfates is suggestive of electron irradiation but may have alternative interpretations. Having much-larger magnetic gyroradii than electrons, energetic protons and heavier ions irradiate more of the global surface. The particular orientations of electron, proton, and ion gyromotion would project into corresponding directional (e.g., east-west) anisotropies of particle flu into the surface. Particular topographic features at the landing site may therefore offer shielding from part of the incident radiation.

Cooper, John F.↗

Plasmon-Assisted Electrochemical Epoxidation using Water as an Oxidant

Olefin epoxidation, an important industrial reaction, often uses hazardous oxidants, causing challenges in waste disposal. Here, we demonstrate the use of water as an oxidant by a plasmon-assisted electrochemical strategy. The electrocatalyst is comprised of a hybrid of a water oxidation catalyst, manganese oxide, and plasmonic gold nanoparticles. Visible-light irradiation of the electrocatalyst enhanced the epoxidation of 4-styrenesulfonate 5-fold as compared to dark conditions at the same temperature. From electrochemical analyses conducted under plasmon excitation conditions, complemented by real-time time-dependent density functional tight binding simulations, it is found that the plasmonic boost of the electrochemical styrene epoxidation is due to energetic holes generated by the excitation of localized surface plasmon resonances of gold nanoparticles. These photogenerated holes activate adsorbed water for oxidation and enhance the binding of 4-styrenesulfonate at interfacial sites. Here, this work demonstrates a proof of concept and establishes the mechanistic basis for plasmon-assisted activation of water as an O atom source for electrochemical epoxidations.

Gold↗

Space platforms and meteorological applications

The use of Shuttle launched and tended space platforms (SP) for research and earth observations in LEO are examined. SPs will accommodate instruments for extended time periods, requiring a Shuttle visit for maintenance and package exchange once every six months. Designs have included off-the-shelf hardware to reduce cost, and comprise instruments for studies of cosmic rays, solar physics, materials processing, space plasma physics, and environmental observations. Solar cell power arrays are detailed, along with thermal control, data management, and attitude control subsystems. Meteorological applications are discussed in terms of the Lower Atmospheric Research Satellite (LARS), for research into coupling of radiative, chemical, and dynamical processes, interactions between the earth's surface, boundary layer, and troposphere, and dynamic and energetic relationships between lower atmospheric processes. Flight configurations and add-on concepts for the SP to lead to a manned space station are indicated.

Mitchell, K. L.↗

Structure and energetics of model amphiphilic molecules at the water liquid-vapor interface - A molecular dynamics study

A molecular dynamics study of adsorption of p-n-pentylphenol at infinite dilution at the water liquid-vapor interface is reported. The calculated free energy of adsorption is -8.8 +/- 0.7 kcal/mol, in good agreement with the experimental value of -7.3 kcal/mol. The transition between the interfacial region and the bulk solution is sharp and well-defined by energetic, conformational, and orientational criteria. At the water surface, the phenol head group is mostly immersed in aqueous solvent. The most frequent orientation of the hydrocarbon tail is parallel to the interface, due to dispersion interactions with the water surface. This arrangement of the phenol ring and the alkyl chain requires that the chain exhibits a kink. As the polar head group is being moved into the solvent, the chain length increases and the tail becomes increasingly aligned toward the surface normal, such that the nonpolar part of the molecule exposed to water is minimized. The same effect was achieved when phenol was replaced by a more polar head group, phenolate.

Pohorille, Andrew↗

H2O-Silicate Microphysics in Ascending Volcanic Plumes on Mars

Physical adsorption of water vapor plays a much more significant role in eruptive plume energetics on Mars than on Earth. The total surface area in martian plumes is likely comparable to terrestrial ash, while the erupting magma and ambient atmosphere are drier. Plumes cool rapidly during ascent, and a limited population of H2O molecules find adsorption sites to be increasingly stable. Release of latent heat of condensation and the onset of moist convection are diminished, delayed, or even prevented by adsorptive interaction We have developed a 5-component numerical model of the behavior of water in eruptive plumes under Mars-like conditions. We have used the model to study the fate of both juvenile and ambient atmospheric water in the eruption column. Here we investigate the adsorptive interaction of water and silicates as they effect plume dynamics and the partitioning and distribution of H2O to the martian environment. Our focus is on the role of adsorption in scavenging H2O from the ascending eruption column, and the possibility that adsorptive scavenging depresses the vapor pressure in the column below the level considered in most eruptive models.

A P Zent↗

The Ionizing Radiation Environment on the Moon

The ionizing radiation environment on the moon that contributes to the radiation hazard for astronauts consists of galactic cosmic rays, solar energetic particles and albedo particles from the lunar surface. We will present calculations of the absorbed dose and the dose equivalent to various organs in this environment during quiet times and during large solar particle events. We will evaluate the contribution of solar particles other than protons and the contributions of the various forms of albedo. We will use the results to determine which particle fluxes must be known in order to estimate the radiation hazard.

J. H. Adams Jr.↗

Sources of Sodium in the Lunar Exosphere: Modeling Using Ground-Based Observations of Sodium Emission and Spacecraft Data of the Plasma

Observations of the equatorial lunar sodium emission are examined to quantify the effect of precipitating ions on source rates for the Moon's exospheric volatile species. Using a model of exospheric sodium transport under lunar gravity forces, the measured emission intensity is normalized to a constant lunar phase angle to minimize the effect of different viewing geometries. Daily averages of the solar Lyman alpha flux and ion flux are used as the input variables for photon-stimulated desorption (PSD) and ion sputtering, respectively, while impact vaporization due to the micrometeoritic influx is assumed constant. Additionally, a proxy term proportional to both the Lyman alpha and to the ion flux is introduced to assess the importance of ion-enhanced diffusion and/or chemical sputtering. The combination of particle transport and constrained regression models demonstrates that, assuming sputtering yields that are typical of protons incident on lunar soils, the primary effect of ion impact on the surface of the Moon is not direct sputtering but rather an enhancement of the PSD efficiency. It is inferred that the ion-induced effects must double the PSD efficiency for flux typical of the solar wind at 1 AU. The enhancement in relative efficiency of PSD due to the bombardment of the lunar surface by the plasma sheet ions during passages through the Earth's magnetotail is shown to be approximately two times higher than when it is due to solar wind ions. This leads to the conclusion that the priming of the surface is more efficiently carried out by the energetic plasma sheet ions.

Sarantos, Menelaos↗

Tutorial on Atomic Oxygen Effects and Contamination

Atomic oxygen is the most predominant specie in low Earth orbit (LEO) and is contained in the upper atmosphere of many other planetary bodies. Formed by photo-dissociation of molecular oxygen, it is highly reactive and energetic enough to break chemical bonds on the surface of many materials and react with them to form either stable or volatile oxides. The extent of the damage for spacecraft depends a lot on how much atomic oxygen arrives at the surface, the energy of the atoms, and the reactivity of the material that is exposed to it. Oxide formation can result in shrinkage, cracking, or erosion which can also result in changes in optical, thermal, or mechanical properties of the materials exposed. The extent of the reaction can be affected by mechanical loading, temperature, and other environmental components such as ultraviolet radiation or charged particles. Atomic oxygen generally causes a surface reaction, but it can scatter under coatings and into crevices causing oxidation much farther into a spacecraft surface or structure than would be expected. Contamination can also affect system performance. Contamination is generally caused by arrival of volatile species that condense on spacecraft surfaces. The volatiles are typically a result of outgassing of materials that are on the spacecraft. Once the volatiles are condensed on a surface, they can then be fixed on the surface by ultraviolet radiation andor atomic oxygen reaction to form stable surface contaminants that can change optical and thermal properties of materials in power systems, thermal systems, and sensors. This tutorial discusses atomic oxygen erosion and contaminate formation, and the effect they have on typical spacecraft materials. Scattering of atomic oxygen, some effects of combined environments and examples of effects of atomic oxygen and contamination on spacecraft systems and components will also be presented.

Earth orbital environments↗

Atomic Oxygen Environments, Effects, and Mitigation

Atomic oxygen is the most predominant specie in low Earth orbit (LEO) and is contained in the upper atmosphere of many other planetary bodies. Formed by photo-dissociation of molecular oxygen, it is highly reactive and energetic enough to break chemical bonds on the surface of many materials and react with them to form either stable or volatile oxides. The extent of the damage for spacecraft depends a lot on how much atomic oxygen arrives at the surface, the energy of the atoms, the reactivity of the material that is exposed to it and other constituents in the atmosphere. Oxide formation can result in shrinkage, cracking, or erosion which can also result in changes in optical, thermal, or mechanical properties of the materials exposed. The extent of the reaction can be affected by mechanical loading, temperature, and other environmental components such as ultraviolet radiation or charged particles. Atomic oxygen generally causes a surface reaction, but it can scatter under coatings and into crevices causing oxidation much farther into a spacecraft surface or structure than would be expected. Atomic oxygen effects for LEO atomic oxygen compared to atomic oxygen effects in a Mars environment, effects atomic oxygen can have on typical spacecraft materials, and mitigation techniques will be presented.

Oxygen atoms↗

Monthly mean forecast experiments with the GISS model

The GISS general circulation model was used to compute global monthly mean forecasts for January 1973, 1974, and 1975 from initial conditions on the first day of each month and constant sea surface temperatures. Forecasts were evaluated in terms of global and hemispheric energetics, zonally averaged meridional and vertical profiles, forecast error statistics, and monthly mean synoptic fields. Although it generated a realistic mean meridional structure, the model did not adequately reproduce the observed interannual variations in the large scale monthly mean energetics and zonally averaged circulation. The monthly mean sea level pressure field was not predicted satisfactorily, but annual changes in the Icelandic low were simulated. The impact of temporal sea surface temperature variations on the forecasts was investigated by comparing two parallel forecasts for January 1974, one using climatological ocean temperatures and the other observed daily ocean temperatures. The use of daily updated sea surface temperatures produced no discernible beneficial effect.

Spar, J.↗

A Warm Garage for a Lunar Rover

Approach: One approach to heating a rover during the lunar night is the so-called thermal wadis concept [1]. This involves heating the regolith with solar concentrators and placing the rover on the heated surface for the night. Since the regolith is heated by a relatively weak heat flux, a high thermal conductivity is required for heating a sufficiently large mass of regolith. However, lunar regolith has a low thermal conductivity. Therefore, the concept involves increasing the conductivity by sintering the regolith, which requires a significant energy input and complex procedures. Here we propose an alternative approach where the low thermal conductivity of regolith is an advantage. Specifically, we propose to use a highly exothermic combustible mixture for heat generation. The mixture pellets are placed in the surface layer of regolith and ignited. The combustion forms condensed products and releases heat, which then slowly spreads to the surrounding regolith. Heat can also be transferred, for example, by heat pipes, into radiant heating surfaces installed on the ground. A greenhouse that transmits sunlight during the day and decreases the radiative heat losses during the night can also be installed. Selection of the Heat-generating Mixture: The reactive mixture should have a high specific energy and generate only condensed products since gases could disturb the regolith layer, carry enthalpy out of the system, and lead to an explosion. There are mixtures, (sometimes called pyrolants) that possess very high specific energies. One example is magnesium-Teflon-Viton mixtures used in flares. However, they produce gases and may cause explosions. Other mixtures that include magnesium cannot be used either because of the high vapor pressure of Mg at temperatures well below the combustion temperature. Recently, mixtures that involve lithium peroxide (Li2O2) have been proposedfor using in space power systems [2]. However, they produce lithium oxide (Li2O), which boils at 2800 K at 1 atm and hence at a lower temperature in vacuum. Fortunately, there exist many mixtures that release a lot of heat and form only condensed products during the combustion. Many such mixtures have been used for self-propagating high-temperature synthesis (SHS) of various materials [3, 4]. For the application discussed here, t itanium/boron (1:2 mole ratio) mixture appears to be particularly promising. The specific energy is 4.0 MJ/kg (1.1 kWh/kg), the adiabatic flame temperature is about 3200 K, and the reaction forms solid titanium diboride (TiB2, melting point: 3500 K). The mixture can be ignited easily with a heated tungsten wire, and it has been used widely as a booster to ignite the main mixture in the SHS process.Estimates: Assuming that specific heat of regolith is 500 J/(kg∙K) [5] and all generated heat is transferred to regolith, 12.5 kg of the Ti/B mixture would increase the temperature of 1000 kg of regolith by 100 K. To evaluate the rate of heat transfer in the regolith, a spherical model was analyzed where the heat released by a 12.5 kg Ti/B core propagates by thermal conduction through a 1000 kg regolith shell with no heat loss from its outer surface. At a bulk density of 1500 kg/m3 [5], the radius of the shell was 54 cm, while the radius of the core was about 11 cm. The calculations were conducted using Thermal Desktop SINDA/FLUINT (Cullimore and Ring Technologies) software at two constant values of bulk thermal conductivityk of the regolith: 0.001 and 0.01 W/(m∙K). The results show that after 14.5 days the core lost 31% of the released heat at the lower k and 77% at the higher k. At a distance of 20 cm from the core surface, the temperature of the regolith increased by only 1 K at the lower k and by 132 K at the higher k. In reality, the regolith near the heat source will be melted, so its thermal conductivity will increase significantly. Nevertheless, the conducted estimates indicate that combustion-based heat generators, placed directly in the regolith, could provide heat during a rather long period such as the lunar night.Conclusion: Heat generators based on gasless combustion of highly energetic reactive mixtures could be installed directly in the surface layer of lunar regolith. Because of the low thermal conductivity of the regolith, such generators would keep thermal energy for days and gradually supply heat to a rover/lander.Acknowledgment: The material presented in this work is based upon the work supported by National Aeronautics and Space Administration (NASA) under Grant #80NSSC20K0293.References: [1] Balasubramaniam R. et al. (2011) J. Thermophys. Heat Trans., 25,130−139. [2] Blair R.G. and Vasu S.S. (2022) Conf. Advanced Power Systems for Deep Space Exploration. [3] Varma A. et al. (1998) Adv. Chem. Eng., 24,79−226. [4] Levashov E.A. et al. (2017) Int. Mater. Rev., 62,203−239. [5] Wood-Robinson R. et al. (2019) J. Geophys. Res. Planets, 124, 1989−2011.

lunar↗

Equivalent crystal theory of alloys

Equivalent Crystal Theory (ECT) is a new, semi-empirical approach to calculating the energetics of a solid with defects. The theory has successfully reproduced surface energies in metals and semiconductors. The theory of binary alloys to date, both with first-principles and semi-empirical models, has not been very successful in predicting the energetics of alloys. This procedure is used to predict the heats of formation, cohesive energy, and lattice parameter of binary alloys of Cu, Ni, Al, Ag, Au, Pd, and Pt as functions of composition. The procedure accurately reproduces the heats of formation versus composition curves for a variety of binary alloys. The results are then compared with other approaches such as the embedded atom and lattice parameters of alloys from pure metal properties more accurately than Vegard's law is presented.

Bozzolo, Guillermo↗

Ab initio quantum dynamics of plasmonic charge carriers

Surface plasmons respond strongly to electric fields and generate energetic (hot) charge carriers that can be used in optoelectronic devices. However, utilization of hot carriers has to outcompete fast carrier relaxation in metals. Often, the reported efficiencies of nanoscale devices based on plasmon excitations are low and the mechanisms of device operation remain inconsistent within the field. Further developments hinge on fundamental understanding of the nature and kinetics of plasmon decay processes. In this work, we provide an overview of time domain ab initio modeling of hot carrier dynamics, demonstrating that atomistic details of the surface structure of plasmonic materials, and their chemical interaction with semiconducting and molecular charge acceptors and substrates, play key roles in governing the dynamics pathways. Considered case studies represent various dynamics channels and illustrate solar energy and optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗