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At least 955 records · Page 53

Argon-40/Argon-39 Age Spectra of Apollo 17 Highlands Breccia Samples by Laser Step Heating and the Age of the Serenitatis Basin

We have obtained high-resolution (21-63 steps) Ar-40/Ar-39 age spectra using a continuous laser system on 19 submilligram samples of melt rocks and clasts from Apollo 17 samples collected from the pre-Imbrian highlands in the easternmost part of the Serenitatis basin. The samples include poikilitic melt rocks inferred to have been formed in the Serenitatis basin-forming impact, aphanitic melt rock whose compositions vary and whose provenance is uncertain, and granulite, gabbro, and melt clasts. Three of the poikilitic melts have similar age spectrum plateau ages (72395,96, 3893 +/- 16 Ma (2sigma); 72535,7, 3887 +/- 16 Ma; 76315,150, 3900 +/- 16 Ma) with a weighted mean age of 3893 +/- 9 Ma, which we interpret as the best age for the Serenitatis basin- forming impact. Published Ar-40/Ar-39 age spectrum ages of Apollo 17 poikilitic melts are consistent with our new age but are much less precise. Two poikilitic melts did not give plateaus and the maxima in their age spectra indicate ages of greater than or equal to 3869 Ma (72558,7) and greater than or equal to 3743 Ma (77135,178). Plateau ages of two poikilitic melts and two gabbro clasts from 73155 range from 3854 +/- 16 Ma to 3937 +/- 16 Ma and have probably been affected by the ubiquitous (older?) clasts and by post- formation heating (impact) events. Plateau ages from two of the aphanitic melt 'blobs' and two granulites in sample 72255 fall in the narrow range of 3850 q 16 Ma to 3869 q 16 Ma with a weighted mean of 3862 +/- 8 Ma. Two of the aphanitic melt blobs from 72255 have ages of 3883 +/- 16 Ma and greater than or equal to 3894 Ma, whereas a poikilitic melt clast (of different composition from the 'Serenitatis' melts) has an age of 3835 +/- 16 Ma, which is the upper limit for the accretion of 72255. These data suggest that either the aphanitic melts vary in age, as is also suggested by their varying chemical compositions, or they formed in the 72255 accretionary event about 3.84-3.85 Ga and older relict material is responsible for the dispersion of ages. In any case the aphanitic melts do not appear to be Serenitatis products. Our age for the Serenitatis impact shows, on the basis of the isotopic age evidence alone, that Serenitatis is greater than 20-25 Ma and probably greatr than 55-60 Ma older than Imbrium (less than or equal to 3870 Ma and probably less than or equal to 3836 Ma (Dalrymple and Ryder, 19931). Noritic granulite sample 78527 has a plateau age of 4146 +/- 17 Ma, representing a minimum age for cooling of this sample in the early lunar crust. So far there is no convincing evidence in the lunar melt rock record for basin-forming impacts significantly older than 3.9 Ga.

Dalrymple, G. Brent↗

Correlating electronic properties with M-site composition in solid solution Ti y Nb 2- y CT x MXenes

High electrical conductivity is desired in MXene films for applications such as electromagnetic interference shielding, antennas, and electrodes for electrochemical energy storage and conversion applications. Due to the acid etching-based synthesis method, it is challenging to deconvolute the relative importance that factors such as chemical composition and flake size contribute to resistivity. To understand the intrinsic and extrinsic contributions to the macroscopic electronic transport properties, a systematic study controlling compositional and structural parameters was conducted with eight solid solutions in the Ti y Nb 2-y CT x system. Here, in particular, we investigated the different roles played by metal (M)-site composition, flake size, and d-spacing on macroscopic transport. Hard x-ray photoemission spectroscopy and spectroscopic ellipsometry revealed changes to electronic structure induced by the M-site alloying. Consistent with the spectroscopic results, the low- and room-temperature conductivities and effective carrier mobility are correlated with the Ti content, while the impact of flake size and d-spacing is most prominent in low-temperature transport. The results provide guidance for designing and engineering MXenes with a wide range of conductivities.

36 MATERIALS SCIENCE↗

Digital alloy contact layers for perovskite solar cells

Thin film optoelectronic devices commonly require an individual material to perform multiple functions, but the physical properties of single-composition materials often cannot be tuned to optimize these diverse requirements. The electron selective contact layer in perovskite solar cells is a prime example. The material must simultaneously have optimal conduction band alignment, facilitate carrier extraction, prevent recombination, and provide a chemically stable interface with the notoriously volatile perovskite semiconductor. The pulse-by-pulse nature of the thin-film deposition method pulsed laser deposition (PLD) provides an opportunity to form material alloys where the chemical composition is controlled at the nanometer scale. These digital alloys may prove to be a powerful materials class to meet some of the multifunctional needs of thin film devices. Using PLD to make electron transport layers from ZnO and MgZnO targets, we demonstrate in this paper that digital alloy gradients can be tuned to significantly outperform either of the parent materials in perovskite solar cells.

36 MATERIALS SCIENCE↗

A statistical-chemical and thermodynamic approach to the study of lunar mineralogy

Principal components analysis is used to study the chemical compositions of pyroxenes of five Apollo 12 specimens. Important correlations are recognized in the variation of oxide weight per cent. These correlations indicating substitutional relationships can be interpreted as representative of stable and metastable trends of crystallization by using crystal-chemical and thermodynamic information. The per cent variance of pyroxene groups with characteristic trends in each specimen can be evaluated and interpreted in terms of history of crystallization. Distribution of Fe and Mg in certain pairs of olivine and pyroxene, which are found in contact in the rock and which may have crystallized simultaneously, is useful in recognizing the tendency towards chemical equilibrium in Fe-Mg distribution during a limited interval in the liquidus or subsolidus stages.

Saxena, S. K.↗

Electron microprobe study of a 'mysterite'-bearing inclusion from the Krymka LL-chrondrite

The black inclusion from the Krymka LL3 chondrite previously found to contain 'mysterite' by Lewis et al. (1979) belongs to a hitherto unknown class of carbonaceous chondrites. Its olivine and pyroxene compositions, Fo 97-99 and En 96, respectively, are characteristic of carbonaceous chondrites and its plagioclase composition. An 100 is characteristic of C3's. It contains a peculiar group of Co-, Cr-rich metal grains whose compositions are similar, but not identical, to those in C2 chondrites. Its weight ratios of total Fe/SiO2 and SiO2/MgO are 0.74 and 1.43, respectively, and its atomic ratio of Si/Al is 10.7, exactly the same as in carbonaceous chondrites. Its bulk chemical composition is very close to that of the Murchison C2 chondrite. The association of mysterite with a special type of carbonaceous chondrite material suggests that mysterite formed by low-temperature condensation in a different region of the nebula from other carbonaceous chondrites.

Grossman, L.↗

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on Earth (1 g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on Earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials.

Day, Delbert E.↗

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one1 of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on earth (1g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials. The classical theories for nucleation and crystal growth for a glass or melt do not contain any parameter that is directly dependent upon the g-value, so it is not readily apparent why glasses prepared in microgravity should be more resistant to crystallization than equivalent glasses prepared on earth. Similarly, the gravity-driven convection in a fluid melt is believed to be the primary force field that is responsible for melt homogenization on earth. Thus, it is not obvious why a glass prepared in space, where gravity-driven convection is ideally absent, would be more chemically homogeneous than a glass identically prepared on earth. The primary objective of the present research is to obtain experimental data for the nucleation rate and crystal growth rate for a well characterized silicate melt (lithium disilicate) processed entirely in space (low gravity) and compare these rates with the nucleation and crystal growth rates for a similar glass prepared identically on earth (1g).

Day, Delbert E.↗

Charge composition and energy spectra of cosmic-ray nuclei at energies above 5 GeV per nucleon

A scintillation-Cerenkov counter telescope, with three gas Cerenkov counters for energy determination between 5 and 90 GeV per nucleon, has been exposed for a net total of 4.5 sq m sr hr in two balloon flights in 1974. The measurement yields the chemical composition and energy spectra of cosmic-ray nuclei in the charge range 5-28. The differential spectral indices of oxygen and of the iron group are measured to be 2.67 plus or minus 0.04 and 2.5 plus or minus 0.08 above 5.4 GeV per nucleon, respectively. The results are interpreted in the context of the 'leaky-box' model of cosmic-ray confinement and propagation.

Caldwell, J. H.↗

Quality control of the tribological coating PS212

PS212 is a self-lubricating, composite coating that is applied by the plasma spray process. It is a functional lubricating coating from 25 C (or lower) to 900 C. The coating is prepared from a blend of three different powders with very dissimilar properties. Therefore, the final chemical composition and lubricating effectiveness of the coatings are very sensitive to the process variables used in their preparation. Defined here are the relevant variables. The process and analytical procedures that will result in satisfactory tribological coatings are discussed.

Sliney, Harold E.↗

A two-phase restricted equilibrium model for combustion of metalized solid propellants

An Eulerian-Lagrangian two-phase approach was adopted to model the multi-phase reacting internal flow in a solid rocket with a metalized propellant. An Eulerian description was used to analyze the motion of the continuous phase which includes the gas as well as the small (micron-sized) particulates, while a Lagrangian description is used for the analysis of the discrete phase which consists of the larger particulates in the motor chamber. The particulates consist of Al and Al2O3 such that the particulate composition is 100 percent Al at injection from the propellant surface with Al2O3 fraction increasing due to combustion along the particle trajectory. An empirical model is used to compute the combustion rate for agglomerates while the continuous phase chemistry is treated using chemical equilibrium. The computer code was used to simulate the reacting flow in a solid rocket motor with an AP/HTPB/Al propellant. The computed results show the existence of an extended combustion zone in the chamber rather than a thin reaction region. The presence of the extended combustion zone results in the chamber flow field and chemical being far from isothermal (as would be predicted by a surface combustion assumption). The temperature in the chamber increases from about 2600 K at the propellant surface to about 3350 K in the core. Similarly the chemical composition and the density of the propellant gas also show spatially non-uniform distribution in the chamber. The analysis developed under the present effort provides a more sophisticated tool for solid rocket internal flow predictions than is presently available, and can be useful in studying apparent anomalies and improving the simple correlations currently in use. The code can be used in the analysis of combustion efficiency, thermal load in the internal insulation, plume radiation, etc.

Sabnis, J. S.↗

In Operando XANES Imaging of High Capacity Intermetallic Anodes for Lithium Ion Batteries

In operando 2D X-ray absorption near edge structure (XANES) imaging was performed near the Cu K-edge during cycling of Cu 6 Sn 5 composite anodes for lithium ion batteries. Galvanostatic lithiation and delithiation with intermittent constant voltage holds near reaction plateaus show evolution of absorption spectra for active material particles. XANES spectra obtained from images taken during cycling were compared to standard spectra for Cu, Cu 6 Sn 5 , and Li 2 CuSn. Chemical composition was assessed for Cu-containing phases. Distinct Cu, Cu 6 Sn 5 , and Li 2 CuSn regions were identified for each voltage plateau. Mechanical degradation, electrode particle fracture and expansion were observed during delithiation. Furthermore, movement of particles during cycling suggests that expansion also impacts the supporting secondary phases and the transport networks therein. These results demonstrate that spectroscopic X-ray imaging methods can clearly distinguish chemically distinct phases in alloy electrodes and have the versatility to observe the evolution of these phases during lithiation and delithiation.

25 ENERGY STORAGE↗

Recent Developments in Revealing the Impact of Complex Metal Oxide Reconstruction on Catalysis

Surface reconstruction of complex metal oxides refers to the alterations of the topmost catalyst surface, relative to the bulk structure, following exposure to pretreatment or reaction conditions during heterogeneous catalysis. (1) This structural and electronic transformation may involve (1) changes of the exposed crystallographic facets, (2) changes in chemical composition, such as the enrichment of specific elements, and, (3) morphological variations, including surface roughness and defects (Scheme 1). Beyond relaxation, surface reconstruction here also encompasses disruptions to the periodicity of the sublayers and changes to its stoichiometry. This change significantly influences the chemical properties of the catalyst surface, such as redox sites, (2) acid/base pairs, hydroxyl groups, (3) and surface defects. Surface reconstruction occurs due to the thermodynamic drive to lower the surface energy of the catalyst under the surrounding environment (e.g., temperature, chemical potential of species present). In addition to the treatment or reaction conditions, the extent of reconstruction also depends on the elements in the metal oxide structure. For instance, annealing ABO 3 perovskites (SrTiO 3 , BaTiO 3 , and BaZrO 3 ) at high temperatures (500 °C) in O 2 has a very different impact on the A/B ratio at the surface (ranging from 0.9 to 2.5), depending on the identity of A and B. (4) Metal oxide surface reconstruction under an electric field and exposure to acidic and alkaline media has recently gained increased attention in electrocatalysis, such as in the oxygen evolution reaction (OER); (5,6) however, in this Viewpoint we focus on the impact of surface reconstruction on thermal catalysis, a critical enduring research theme with ongoing challenges. Here, we start showcasing approaches to characterize surface reconstruction at the topmost surface layer, such as low-energy ion scattering (LEIS), discussing advantages and limitations. Next, we connect characterization of surface reconstruction to site-specific kinetic analysis, enabled via steady-state isotopic transient kinetic analysis (SSITKA), and we express our viewpoint on building structure–performance relationships by deeply understanding reconstructed surfaces. Later, we comment on the potential of tuning surface reconstruction to enhance catalytic performance. Finally, we explore the interplay between surface reconstruction and the “intelligent behavior”.

alcohol conversion↗

Lunar Science Conference, 6th, Houston, Tex., March 17-21, 1975, Proceedings. Volume 2 - Chemical and isotopic studies

The chemical compositions of lunar rocks and soils are examined, taking into account sulfur abundances and distributions in mare basalts and their source magmas, lithophile trace and major elements in Apollo 16 and 17 lunar samples, the role of vaporization processes in lunar rock formation, chemical studies of the lunar regolith with emphasis on zirconium and hafnium, a model for the lunar anorthositic gabbro, and trace-element chemistry and reducing capacity of size fractions from the Apollo 16 regolith. Other topics considered are related to lunar chronology, volatile meteoritic elements, isotopic studies, light element geochemistry, and agglutinates and regolith processes. Attention is given to meteoritic material in four terrestrial meteorite craters, the state of meteoritic material on the moon, volatile elements in Allende inclusions, oxygen isotope fractionation in Apollo 17 rocks, cosmogenic isotope production in Apollo deep-core samples, and the effects of exposure conditions on cosmic-ray records in lunar rocks.

Merrill, R. B.↗

Analytical, Experimental, and Modelling Studies of Lunar and Terrestrial Rocks

The goal of our research has been to understand the paths and the processes of planetary evolution that produced planetary surface materials as we find them. Most of our work has been on lunar materials and processes. We have done studies that obtain geological knowledge from detailed examination of regolith materials and we have reported implications for future sample-collecting and on-surface robotic sensing missions. Our approach has been to study a suite of materials that we have chosen in order to answer specific geologic questions. We continue this work under NAG5-4172. The foundation of our work has been the study of materials with precise chemical and petrographic analyses, emphasizing analysis for trace chemical elements. We have used quantitative models as tests to account for the chemical compositions and mineralogical properties of the materials in terms of regolith processes and igneous processes. We have done experiments as needed to provide values for geochemical parameters used in the models. Our models take explicitly into account the physical as well as the chemical processes that produced or modified the materials. Our approach to planetary geoscience owes much to our experience in terrestrial geoscience, where samples can be collected in field context and sampling sites revisited if necessary. Through studies of terrestrial analog materials, we have tested our ideas about the origins of lunar materials. We have been mainly concerned with the materials of the lunar highland regolith, their properties, their modes of origin, their provenance, and how to extrapolate from their characteristics to learn about the origin and evolution of the Moon's early igneous crust. From this work a modified model for the Moon's structure and evolution is emerging, one of globally asymmetric differentiation of the crust and mantle to produce a crust consisting mainly of ferroan and magnesian igneous rocks containing on average 70-80% plagioclase, with a large, mafic, trace-element-rich geochemical province, and a regolith that globally contains trace-element-rich material distributed from this province by the Imbrium basin-forming impact. This contrasts with earlier models of a concentrically zoned Moon with a crust of ferroan anorthosite overlying a layer of urKREEP overlying ultramafic cumulates. From this work, we have learned lessons useful for developing strategies for studying regolith materials that help to maximize the information available about both the evolution of the regolith and the igneous differentiation of the planet. We believe these lessons are useful in developing strategies for on-surface geological, mineralogical, and geochemical studies, as well. The main results of our work are given in the following brief summaries of major tasks. Detailed accounts of these results have been submitted in the annual progress reports.

Haskin, Larry A.↗

The case for at least three mare basalt magmas at the Luna 24 landing site

Petrographic and electron microprobe studies have been carried out for 1230 particles from the Luna 24 drill core. At least three mare basalts were distinguished on the basis of major and minor element chemical compositions of pyroxenes. Mg-rich monomineralic particles of olivine and pyroxene defined one major type. The other two magmas were identified by the Ti/(Ti + Cr) ratio at constant Fe/(Fe + Mg) ratio in pyroxenes derived from polymineralic igneous lithic fragments. Whole rock chemical analyses for V and Cr also provided evidence for these distinct magmas.

Nielsen, R. L.↗

Laser remote sensing of the atmosphere

Laser beams can be used as long-range spectroscopic probes of the chemical composition and physical state of the atmosphere. The spectroscopic, optical, and laser requirements for atmosphheric laser remote sensing are reviewed, and the sensitivity and limitations of the technique are described. A sampling of recent measurements includes the detection of urban air pollution and toxic chemicals in the atmosphere, the measurement of global circulation of volcanic ash in the upper atmosphere, and the observation of wind shear near airports.

Killinger, Dennis K.↗