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At least 757 records · Page 42

Surface Temperature and the Compositional Effects of Electron Bombardment on Dione

Saturn’s icy moons are composed of mostly water ice with minor “contaminants,” such as CO2 ice, and a dark component thought to be organics, hematite and/or metallic Fe [1]. The space weathering process of electron bombardment is expected to be particularly important on the surfaces of Saturn’s inner moons (Mimas, Tethys, Dione, and Rhea), as they orbit within the extended plasma sheet of Saturn’s magnetosphere. Terrains exhibiting thermal anomalies (i.e., colder temperatures in the day and warmer temperatures at night than surrounding areas) correspond to regions of high energy electron bombardment [2; 3]. Energetic electrons impact the surfaces, fracturing ice particles into sub-micron sized grains, and this process becomes more effective for increasing particle energies [4]. In addition to alteration of ices, the dark material may also be modified or generated within icy surfaces by interaction with solar UV radiation, cosmic rays, or by particles trapped in Saturn’s magnetic field [5]. CO2 could be sourced from irradiation of dark organic material [7]. Many of these alterations should be observable in Visible and Infrared Mapping Spectrometer (VIMS) spectra [8]. We used surface temperatures derived from Cassini’s Composite Infrared Spectrometer (CIRS) to help isolate areas where space weathering due to electron bombardment is more predominant and investigated the subtle changes in VIMS spectra using machine learning techniques. We present our results here for Dione. On ocean worlds, space weathering products would be present along with any potential indications of life. We will need to understand the manifestation of space weathering in the data to separate the two processes.

Cindy Lee Young↗

MCML: Combining physical constraints with experimental data for a multi-purpose meta-generalized gradient approximation

The predictive power of density functional theory for materials properties can be improved without increasing the overall computational complexity by extending the generalized gradient approximation (GGA) for electronic exchange and correlation to density functionals depending on the electronic kinetic energy density in addition to the charge density and its gradient, resulting in a meta-GGA. Here, we propose an empirical meta-GGA model that is based both on physical constraints and on experimental and quantum chemistry reference data. Overall, the resulting optimized meta-GGA MCML yields improved surface and gas phase reaction energetics without sacrificing the accuracy of bulk property predictions of existing meta-GGA approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning Intermediate Bands of Protective Coatings to Reach the Bulk-Recombination Limit of Stable Water-Oxidation GaP Photoanodes

Stable photoelectrochemical solar fuel production requires protective coatings to achieve effective charge separation, transport, and injection at the semiconductor–liquid interfaces, implying that the coating should energetically align its intermediate band (IB) with both the photoabsorber's band edge and co-catalyst's potentials. Yet approaches to adjust coating IB positions to accommodate various semiconductor light absorbers for constructing efficient and stable photoelectrodes have not been developed. In this report, three types of transition metal (M = Mn 2+ , Mn 3+ , and Cr 3+ ions) alloyed TiO2 coatings are discovered using atomic layer deposition (ALD). The IB energetics of these coatings are characterized by X-ray photoelectron spectroscopy and are found to be tunable inside the TiO 2 bandgap, through varying ALD growth conditions. By applying these coatings to n-type GaP and integrating with IrO x co-catalysts, the water-oxidation J–E performance is comparable to an uncoated corroding GaP photoanode. It reaches the bulk recombination limit of the GaP and achieves ≈28% absorbed photon to current efficiency under 475-nm light excitation (6.48 mW cm -2 ) and 100-h stable water oxidation. The outstanding performance and stability are attributed to the efficient charge separation and hole transport, as allowed by the energy alignment of the coating IB and the GaP valence band edge.

36 MATERIALS SCIENCE↗

Entropy Stabilization Effects and Ion Migration in 3D “Hollow” Halide Perovskites

A recently discovered new family of 3D halide perovskites with the general formula (A) 1–x (en) x (Pb) 1–0.7x (X) 3–0.4x (A = MA, FA; X = Br, I; MA = methylammonium, FA = formamidinium, en = ethylenediammonium) is referred to as “hollow” perovskites owing to extensive Pb and X vacancies created on incorporation of en cations in the 3D network. The “hollow” motif allows fine tuning of optical, electronic, and transport properties and bestowing good environmental stability proportional to en loading. To shed light on the origin of the apparent stability of these materials, we performed detailed thermochemical studies, using room temperature solution calorimetry combined with density functional theory simulations on three different families of “hollow” perovskites namely en/FAPbI 3 , en/MAPbI 3 , and en/FAPbBr 3 . We found that the bromide perovskites are more energetically stable compared to iodide perovskites in the FA-based hollow compounds, as shown by the measured enthalpies of formation and the calculated formation energies. The least stable FAPbI 3 gains stability on incorporation of the en cation, whereas FAPbBr 3 becomes less stable with en loading. This behavior is attributed to the difference in the 3D cage size in the bromide and iodide perovskites. Configurational entropy, which arises from randomly distributed cation and anion vacancies, plays a significant role in stabilizing these “hollow” perovskite structures despite small differences in their formation enthalpies. With the increased vacancy defect population, we have also examined halide ion migration in the FA-based “hollow” perovskites and found that the migration energy barriers become smaller with the increasing en content.

36 MATERIALS SCIENCE↗

Probing the Kinetic Origin of Varying Oxidative Stability of Ethyl- vs. Propyl-spaced Amines for Direct Air Capture

Amine-based adsorbents are promising for direct air capture of CO 2 , yet oxidative degradation remains a key unmitigated risk hindering wide-scale deployment. Borrowing wisdom from the basic auto-oxidation scheme, insights are gained into the underlying degradation mechanisms of polyamines by quantum chemical, advanced sampling simulations, adsorbent synthesis, and accelerated degradation experiments. The reaction kinetics of polyamines are contrasted with that of typical aliphatic polymers and they elucidate for the first time the critical role of aminoalkyl hydroperoxide decomposition in the oxidative degradation of amino-oligomers. The experimentally observed variation in oxidative stability of polyamines with different backbone structures is explained by the relationship between the local chemical structure and the free energy barrier of aminoalkyl hydroperoxide decomposition, suggesting that its energetics can be used as a descriptor to screen and design new polyamines with improved stability. In conclusion, the developed computational capability sheds light on radical-induced degradation chemistry of other organic functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical radiation from the interaction of energetic atoms, ions, electrons, and photons with surfaces

Heavy particle, electron, and UV photon bombardment of solid surfaces has been recently observed to result in the emission of infrared, visible, and ultraviolet radiation. This effect occurs over a wide range of incident projectile energies. Line radiation arising from transitions between discrete atomic or molecular levels may be attributed to the decay of excited particles which have been sputtered or electronically/chemically desorbed from the surface. Broadband continuum radiation, which is also observed, is believed to arise either from fluorescence of the near surface bulk or from the radiative decay of desorbed excited clusters. Spacecraft, in the ambient near Earth environment, are subject to such bombardment. The dynamics of energetic particle and photon beam interactions with surfaces which lead to surface erosion and glow phenomena will be treated. In addition, projected experimental and theoretical studies of oxygen and nitrogen beam surface interactions on materials characteristic of spacecraft surfaces will be discussed.

Tolk, N. H.↗

Recruiting Perovskites to Degrade Toxic Trinitrotoluene

Everybody knows TNT, the most widely used explosive material and a universal measure of the destructiveness of explosions. A long history of use and extensive manufacture of toxic TNT leads to the accumulation of these materials in soil and groundwater, which is a significant concern for environmental safety and sustainability. Reliable and cost-efficient technologies for removing or detoxifying TNT from the environment are lacking. Despite the extreme urgency, this remains an outstanding challenge that often goes unnoticed. We report here that highly controlled energy release from explosive molecules can be accomplished rather easily by preparing TNT–perovskite mixtures with a tailored perovskite surface morphology at ambient conditions. These results offer new insight into understanding the sensitivity of high explosives to detonation initiation and enable many novel applications, such as new concepts in harvesting and converting chemical energy, the design of new, improved energetics with tunable characteristics, the development of powerful fuels and miniaturized detonators, and new ways for eliminating toxins from land and water.

36 MATERIALS SCIENCE↗

Probing basal planes and edge sites in polygranular nuclear graphite by gas adsorption: Estimation of active surface area

Polygranular nuclear graphite, manufactured at 2800–3000 °C from a carbonized filler and binder mix, has high graphitization degree, crystalline structure close to perfect graphite, and about 20% porosity. The pore surfaces expose large regions of rough, defective prismatic edges of graphite crystallites which are the locus of graphite materials surface sites active for oxidation, chemisorption, and electron transfer. However, we show that high-resolution N 2 and Kr first monolayer adsorption on polygranular graphite (P/P 0 < 0.015) occurs in many ways like adsorption on graphitized carbon blacks. This proves the presence of energetically homogeneous basal planes domains in graphite porosity, which was not fully acknowledged before. Using classical analysis methods (Langmuir, Hill-de Boer, adsorption potential distribution) we quantity the basal plane area (BPA) of several polygranular graphite types and correlate it with their microstructure. Finally, we propose that gas adsorption is uniquely positioned to reliably estimate the active surface area of graphite by subtracting BPA from the BET total surface area. Direct estimation based on adsorption is preferable to indirect calculations based on microstructural information.

36 MATERIALS SCIENCE↗

Quantifying the role of the lattice in metal–insulator phase transitions

Many materials exhibit phase transitions at which both the electronic properties and the crystal structure change. Some authors have argued that the change in electronic order is primary, with the lattice distortion a relatively minor side-effect, and others have argued that the lattice distortions play an essential role in the energetics of the transition. In this paper, we introduce a formalism that resolves this long-standing problem. The methodology works with any electronic structure method that produces solutions of the equation of state determining the electronic order parameter as a function of lattice distortion. We use the formalism to settle the question of the physics of the metal–insulator transitions in the rare-earth perovskite nickelates (RNiO 3 ) and Ruddlesden–Popper calcium ruthenates (Ca 2 RuO 4 ) in bulk, heterostructure, and epitaxially strained thin film forms, finding that electron-lattice coupling is key to stabilizing the insulating state in both classes of materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

All-alumina quarter-wave plate coatings fabricated by glancing angle deposition using serial bideposition

Anisotropic phase retarders, used in high power laser facilities to perform polarization smoothing, can be obtained by the glancing angle deposition (GLAD) coating process. Due to its high laser resistance, the coatings are mainly made of silica. Therefore, limited attention has been given to other dielectric materials. Here we present a study on alumina GLAD anisotropic coatings; a material with high laser resistance, higher birefringence and lower environmental sensitivity than silica. Since the anisotropy is related to the coatings microstructure through the deposition angle, samples were coated at angles varying from ± 68° to ± 82° using the serial bideposition technique. They were characterized by ellipsometry, polarimetry, spectrophotometry and electron microscopy. We showed that the highest birefringence is obtained at a deposition angle of ± 76° with an in-plane value of 0.053. Based on these results, a quarter-wave plate at 351 nm was designed as a multilayer with seven pairs of anisotropic layers deposited at ± 76° and isotropic layers deposited at 0°. The fabricated coating exhibited a uniform retardance of 88.51 ± 0.45 nm. The alumina GLAD wave plates presented here, open the door to new possibilities in the laser field and especially in the field of fusion energy.

36 MATERIALS SCIENCE↗

Interlayer exciton landscape in WS 2 /tetracene heterostructures

The vertical stacking of two-dimensional materials into heterostructures gives rise to a plethora of intriguing optoelectronic properties and presents an unprecedented potential for technological development. While much progress has been made combining different monolayers of transition metal dichalcogenides (TMDs), little is known about TMD-based heterostructures including organic layers of molecules. In this work, we present a joint theory–experiment study on a TMD/tetracene heterostructure demonstrating clear signatures of spatially separated interlayer excitons in low temperature photoluminescence spectra. Here, the Coulomb-bound electrons and holes are localized either in the TMD or in the molecule layer, respectively. We reveal both in theory and experiment signatures of the entire intra- and interlayer exciton landscape in the photoluminescence spectra. In particular, we find both in theory and experiment a pronounced transfer of intensity from the intralayer TMD exciton to a series of energetically lower interlayer excitons with decreasing temperature. In addition, we find signatures of phonon-sidebands stemming from these interlayer exciton states. Our findings shed light on the microscopic nature of interlayer excitons in TMD/molecule heterostructures and could have important implications for technological applications of these materials.

36 MATERIALS SCIENCE↗

Effects of 2D filler on rheology of additive manufacturing polymers: Simulation and experiment on polyetherketoneketone-mica composites

Polymeric composites have attracted increasing interest in fundamental studies and industrial applications due to their often-superior characteristics over conventional pure polymers. In this work, we studied the relationship between the rheological properties, critical in processing methods such as additive manufacturing, and the structure of a polymer-2D filler system by experiment and simulation methods. Considering the high performance polymer polyetherketoneketone (PEKK) with 2D filler (mica) composite as an example, the effects of filler size, filler content, surface chemistry and shear rate were systematically investigated. Here, it is demonstrated that the interaction between the polymer and 2D filler brings two different consequences on tuning the viscosity of polymer-filler composite. The stronger interaction increases the shear stress of the polymer-2D filler composite system, leading to higher viscosity. On the other hand, the stronger interaction can promote more absorption of polymer chains on the surface, which makes the local polymer network disentangled and decreases the continuous viscosity from the polymer network. This work provides a fundamental understanding on the relationship between macroscopic rheological properties and the structural properties and energetics at molecular level of polymer-2D filler composite.

36 MATERIALS SCIENCE↗

Probing Electronic and Structural Transformations during Thermal Reduction of the Promising Water Splitting Perovskite BaCe 0.25 Mn 0.75 O 3

Here, in this report, we investigate the thermal reduction of the octahedral perovskite BaCe 0.25 Mn 0.75 O 3 (BCM) using in situ electron energy loss spectroscopy (EELS) in an aberration-corrected transmission electron microscope (TEM). The 12R-polytype of BCM is known to demonstrate high solar thermochemical hydrogen production capacity. In situ EELS measurements show that Mn is the active redox cation in BCM, undergoing thermal reduction from Mn 4+ to Mn 3+ during heating to 700 °C inside the TEM under a high vacuum. The progressive reduction of Mn 4+ during oxygen vacancy (O v ) formation was monitored as a function of temperature. Additionally, atomic-resolution scanning transmission electron microscopy identified two different types of twin boundaries present in the oxidized and reduced form of 12R-BCM, respectively. These two types of twin boundaries were shown, via computational modeling, to modulate the site-specific O v formation energies in 12R-BCM. It is concluded that these types of atomic defects provide sites more energetically favorable for O v formation during thermal reduction.

36 MATERIALS SCIENCE↗

Effects of Ligand Chemistry on Ion Transport in 2D Hybrid Organic–Inorganic Perovskites

2D hybrid organic–inorganic perovskites are potentially promising materials as passivation layers that can enhance the efficiency and stability of perovskite photovoltaics. The ability to suppress ion transport is proposed as a stabilization mechanism, yet an effective characterization of relevant modes of halide diffusion in 2D perovskites is nascent. In light of this knowledge gap, molecular dynamics simulations with enhanced sampling and experimental validation to systematically characterize how ligand chemistry in seven (R-NH 3 ) 2 PbI 4 systems impacts halide diffusion, particularly in the out-of-plane direction is combined. It is found that increasing stiffness and length of ligands generally inhibits ion transport, while increasing ligand polarization generally enhances it. Structural and energetic analyses of the migration pathways provide quantitative explanations for these trends, which reflect aspects of the disorder of the organic layer. Overall, this mechanistic analysis greatly enhances the current understanding of halide migration in 2D hybrid organic–inorganic perovskites and yields insights that can inform the design of future passivation materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Local Site Disorder and Distortion in Pyrochlore High-Entropy Oxides

High-entropy oxides (HEOs) have attracted great interest in diverse fields because of their inherent opportunities to tailor and combine materials functionalities. The control of local order/disorder in the class is by extension a grand challenge toward realizing their vast potential. In this paper, we report the first examples of pyrochlore HEOs with five M-site cations, for Nd 2 M 2 O 7 , in which the local structure has been investigated by neutron diffraction and pair distribution function (PDF) analysis. The average structure of the pyrochlores is found to be orthorhombic Imma, in agreement with radius-ratio rules governing the structural archetype. The computed PDFs from density functional theory relaxed special quasirandom structure models are compared with real space PDFs in this work to evaluate M-site order/disorder. Reverse Monte Carlo combined with ab initio molecular dynamics and Metropolis Monte Carlo simulations demonstrates that Nd 2 (Ta 0.2 Sc 0.2 Sn 0.2 Hf 0.2 Zr 0.2 ) 2 O 7 is synthesized with its M-site local to nanoscale order highly randomized/disordered, while Nd 2 (Ti 0.2 Nb 0.2 Sn 0.2 Hf 0.2 Zr 0.2 ) 2 O 7+x exhibits a strong distortion of the TiO 6 octahedron and small degree of Ti chemical short-range order (SRO) on the subnanometer scale. Calculations suggest that this may be intrinsic, energetically favored SRO rather than due to sample processing. These results offer an important demonstration that the engineered variation of participating ions in HEOs, even among those with very similar radii, provides richly diverse opportunities to control local order/disorder motifs—and therefore materials properties for future designs. This work also hints at the exquisite level of detail that may be needed in computational and experimental data analysis to guide structure–property tuning in the emerging HEO materials class.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗