Search NASA⌕ Search

SEARCH · Search NASA

Results for “chemical trends”

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

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Strain‐Induced Orbital Contributions to Oxygen Electrocatalysis in Transition‐Metal Perovskites

Abstract Epitaxial strain has been shown to produce dramatic changes to the orbital structure in transition metal perovskite oxides and, in turn, the rate of oxygen electrocatalysis therein. Here, epitaxial strain is used to investigate the relationship between surface electronic structure and oxygen electrocatalysis in prototypical fuel cell cathode systems. Combining high‐temperature electrical‐conductivity‐relaxation studies and synchrotron‐based X‐ray absorption spectroscopy studies of La 0.5 Sr 0.5 CoO 3 and La 0.8 Sr 0.2 Co 0.2 Fe 0.8 O 3 thin films under varying degrees of epitaxial strain reveals a strong correlation between orbital structure and catalysis rates. In both systems, films under biaxial tensile strain simultaneously exhibit the fastest reaction kinetics and lowest electron occupation in the d z 2 orbitals. These results are discussed in the context of broader chemical trends and electronic descriptors are proposed for oxygen electrocatalysis in transition metal perovskite oxides.

Fernandez, Abel↗
DOE OSTI2026

The solubility and speciation of REE phosphate endmembers (CePO 4 and YPO 4 ) in Cl-rich aqueous fluids from 350 to 450 °C and implications for natural systems

The rare earth elements (REE) are important metals used increasingly in advanced technologies. Within the crust, the elements Ce and Y are commonly more abundant compared to other lanthanides and comprise important end-member constituents of REE-bearing minerals. Specifically, Ce is part of the light (L) REE which have larger ionic radii than the heavy (H) REE, which are grouped together with Y. These differences in ionic radius can lead to important physico-chemical trends within the lanthanide group. Despite a recent increase in experimental and thermodynamic data for the REE at high temperature and pressure, there is still a significant lack of these data at supercritical conditions. In this study we conducted batch-type experiments to measure the solubility of REE phosphates (CePO 4 and YPO 4 ) at varying starting pH (1.5–10), and salinity (0.01–1.4 mol/kg NaCl) at 350 and P sat , and from 400 to 450 °C at 700 bar. Results show that the solubility of Ce (33–0.14 ppb) is generally higher than Y (13–0.13 ppb) and that Ce complexes more strongly with both chloride and hydroxyl ligands compared to Y. The solubilities of both REE phosphates are highly pH-dependent and, to a lesser extent, depend on salinity at the studied conditions. The solubility data from this study were implemented into the GEMSFITS program to optimize the thermodynamic properties of Ce and Y hydroxyl and chloride species. The updated standard partial molal Gibbs energies of formation (Δ f G 0 T,P ) are used within the experimental temperature and pressure range to accurately predict the CePO 4 and YPO 4 solubility and Ce and Y speciation behavior. Based on the updated thermodynamic properties we also provide formation constants (log β n Cl,OH ) for Ce and Y hydroxyl and chloride species. Updated thermodynamic properties are applied to model REE-apatite dissolution and REE mobility based on the Pea Ridge iron oxide apatite deposit in Missouri, USA. The apatite dissolution model replicates natural observations including the replacement of monazite and xenotime after apatite and is an example of the utility of the new thermodynamic constants applied to supercritical crustal fluids. Furthermore, the findings of this study advance the predictive capabilities of geochemical models, our understanding of the behavior of individual REE, and permit modeling the overarching fractionation trends between LREE and HREE in supercritical crustal fluids.

58 GEOSCIENCES↗
DOE OSTI2021

Composition and Configuration Dependence of Glass-Transition Temperature in Binary Copolymers and Blends of Polyhydroxyalkanoate Biopolymers

Polyhydroxyalkanoates (PHAs), a promising class of biomaterials, have gained considerable attention to replace petroleum-based plastics owing to their excellent biocompatibility and biodegradability. Homopolymers of PHA suffer from poor tunability in thermal and mechanical properties. Going from homopolymers to copolymers, the design space can be substantially enhanced by combining two or more monomers in different compositions (i.e., relative ratios of the different monomers) and configurations (i.e., relative positions of the different monomers in the polymer backbone) leading to a substantially large chemical space where application-specific optimization for the targeted functionality can be performed. However, this composition and configuration dependence of properties in the vast PHA copolymer chemical space remains largely unexplored. In this contribution, further building on our past work with PHA homopolymers, we systematically explore these chemical trends for glass-transition temperature (Tg) in PHA copolymers and blends. Overall, our molecular dynamics simulations, utilizing a previously validated force field for PHAs, suggest that these trends are largely governed not only by the homopolymer Tg values but also configuration-dependent interchain interactions in the copolymer system. In particular, our results indicate that the configuration-dependent variation in the target property at a fixed composition can be significant in the presence of hydrogen-bond-forming monomers. These qualitative observations are further rationalized by quantitatively analyzing various closely related atomic level descriptors of copolymers and blends such as monomer mobility, number of hydrogen bonds, and pair correlation functions. The findings presented in this work help to develop a deeper atomistic-level understanding of thermomechanical behavior of PHA-based copolymers and can potentially guide the rational design of biopolymers as environmental-friendly functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Chemical templates of the Central Molecular Zone

Context . The Central Molecular Zone (CMZ) of the Milky Way exhibits extreme conditions, including high gas densities, elevated temperatures, enhanced cosmic-ray ionization rates, and large-scale dynamics. This makes it a perfect laboratory for astrochemical studies. With large-scale molecular surveys revealing increasing chemical and physical complexity in the CMZ, it is essential to develop robust methods to decode the chemical information embedded in this extreme region. Aims . A key step to interpreting the molecular richness found in the CMZ is building chemical templates tailored to its diverse conditions. In particular, understanding how CMZ environments affect shock and protostellar chemistry is crucial. The combined impact of high ionization, elevated temperatures, and dense gas remains insufficiently explored for observable tracers. Methods . For this study, we utilized UCLCHEM , a gas-grain time-dependent chemical model, to link physical conditions with their corresponding molecular signatures and identify key tracers of temperature, density, ionization, and shock activity. To achieve this, we ran a grid of models of shocks and protostellar objects representative of typical CMZ conditions, focusing on 24 species, including complex organic molecules. Results . Shocked and protostellar environments show distinct evolutionary timescales (≲10 4 vs. ≳10 4 years); 300 K emerges as a key temperature threshold for chemical differentiation. We find that cosmic-ray ionization and temperature are the main drivers of chemical trends. HCO + , H 2 CO, and CH 3 SH trace ionization, while HCO, HCO + , CH 3 SH, CH 3 NCO, and HCOOCH 3 show consistent abundance contrasts between shocks and protostellar regions over similar temperature ranges. Conclusions . We characterized the behavior of 24 species in protostellar and shock-related environments. While our models underpredict some complex organics in shocks, they reproduce observed trends for most species, supporting scenarios involving a need for recurring shocks in Galactic Center clouds and enhanced ionization toward Sgr B2(N2). Future work should assess the role of shock recurrence and metallicity in shaping chemistry.

Galaxy: center↗
DOE OSTI2020

Machine learning substitutional defect formation energies in ABO 3 perovskites

Perovskite oxides are a promising material platform for use in a wide range of technological applications including electronics, sensors, fuel cells, and catalysis. This is owing to the extraordinary tunability of their physical and chemical properties via defect engineering. The feasibility and the stability of a defect, such as a substitutional dopant, in the host lattice is usually obtained via experiments and/or through detailed quantum mechanical calculations. Both of these conventional routes are expensive and time consuming. An alternative is a data-driven machine learning (ML)-based approach. In this work, we have applied ML techniques to identify the factors that influence defect formation energy, which is an important measure of the stability of the defects, in perovskite oxides. Using 13 elemental properties as features and random forest regression, we demonstrate a systematic approach to down-selecting from the larger set of features to those that are important, establishing a framework for accurate predictions of the defect formation energy. We quantitatively show that the most important factors that control the dopant stability are the dopant ionic size, heat of formation, effective tolerance factor, and oxidation state. Our work reveals previously unknown correlations, chemical trends, and the interplay between stability and underlying chemistries. Hence, these results showcase the efficacy of ML tools in identifying and quantifying different feature-dependencies and provide a promising route toward dopant selection in the perovskites. Herein, we have developed a framework that itself is general and can be potentially applied to other material classes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Efficient computational design of two-dimensional van der Waals heterostructures: Band alignment, lattice mismatch, and machine learning

Here, we develop a computational database, website applications (web-apps), and machine-learning (ML) models to accelerate the design and discovery of two-dimensional (2D) heterostructures. Using density functional theory (DFT) based lattice parameters and electronic band energies for 674 nonmetallic exfoliable 2D materials, we generate 226 779 possible bilayer heterostructures. We classify these heterostructures into type-I, -II, and -III systems according to Anderson’s rule, which is based on the relative band alignments of the noninteracting monolayers. We find that type II is the most common and type III the least common heterostructure type. We subsequently analyze the chemical trends for each heterostructure type in terms of the Periodic Table of constituent elements. The band alignment data can also be used for identifying photocatalysts and high-work-function 2D metals for contacts. We validate our results by comparing them to experimental data as well as hybrid-functional predictions. Additionally, we carry out DFT calculations of a few selected systems (MoS 2 /WSe 2 , MoS 2 /h-BN, and MoSe 2 /CrI 3 ), to compare the band-alignment description with the predictions from Anderson’s rule. We develop web-apps to enable users to virtually create combinations of 2D materials and predict their properties. Additionally, we use ML tools to predict band-alignment information for 2D materials. The web-apps, tools, and associated data will be distributed through the JARVIS-HETEROSTRUCTURE website. Our analysis, results, and the developed web-apps can be applied to the screening and design applications, such as finding alternative photocatalysts, photodetectors, and high-work-function (WF) 2D-metal contacts.

2-dimensional systems↗
DOE OSTI2022

The Milky Way Revealed by Variable Stars. I. Sample Selection of RR Lyrae Stars and Evidence for Merger History

In order to study the Milky Way, RR Lyrae (RRL) variable stars identified by Gaia, ASAS-SN, and ZTF sky survey projects have been analyzed as tracers in this work. Photometric and spectroscopic information of 3417 RRLs including proper motions, radial velocity, and metallcity are obtained from observational data of Gaia, LAMOST, GALAH, APOGEE, and RAVE. Precise distances of RRLs with typical uncertainties less than 3% are derived by using a recent comprehensive period–luminosity–metallicity relation. Our results from kinematical and chemical analysis provide important clues for the assembly history of the Milky Way, especially for the Gaia–Sausage ancient merger. The kinematical and chemical trends found in this work are consistent with those of recent simulations that indicated that the Gaia–Sausage merger had a dual origin in the Galactic thick disk and halo. As recent similar works have found, the halo RRL sample in this work contains a subset of radially biased orbits besides a more isotropic component. This higher orbital anisotropy component amounts to β ≃ 0.8, and it contributes between 42% and 83% of the halo RRLs at 4 < R( kpc) < 20.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1977

Transportation concepts for space industrialization

Space shuttle and heavy lift launch vehicle concepts are described with attention to transportation cost trends. Chemical (LOX/LH2), nuclear, and electric propulsion systems are considered. Suggested space shuttle projects include the support of manned geosynchronous missions and the transfer of bulk cargo and large-delicate space structures from fabrication/assembly orbits to their operational locations. It is thought that development of the space shuttle will stimulate interest in space industrialization.

Murphy, J. T.↗
NASA NTRS1978

Tungsten in iron meteorites

Tungsten concentrations have been determined by instrumental neutron activation in 104 iron meteorites, and range from 0.07 to 5 microg/g. In individual groups, concentrations vary by factors of between 1.5 and 8, but there are negative W-Ni correlations in 8 groups: IAB, IC, IIAB, IID, IIE, IIIAB, IIICD, and IIIF. The lowest W concentrations are found in groups IAB and IIICD, which also have the smallest slopes on a W-Ni plot. Eighteen anomalous irons have W concentrations between 5 microg/g (Butler) and 0.11 microg/g (Rafrueti). The distribution of W in irons shows similarities to that of other refractory sideophilic elements (except Mo), but is closest to the distribution of Ru and Pt. Assuming that chemical trends in group IIIAB were produced by fractional crystallization, a value of 1.6 can be deduced for the distribution coefficient of W between solid and liquid metal, as compared with 0.89 for Mo. Experimental evidence in support of these values is tenuous.

Scott, E. R. D.↗
NASA NTRS1977

Experimental study of pyroxene-liquid interaction in quartz-normative basalt 15597

Equilibrium and controlled cooling rate experiments on a synthetic analog of Apollo 15 quartz normative basalt 15597 are reported. While the partitioning of the major elements Ca, Mg, and Fe between pyroxene and liquid is rate independent, the K sub D parameter for Fe/Mg, which is calculated for low-Ca pyroxene, is temperature dependent. It is suggested that chemical trends observed in lunar pyroxenes are a consequence of three rate processes. The processes are (1) rate-dependent suppression of crystallization of other phases until lower temperature alters liquid composition and, therefore, the composition of the pyroxene that crystallizes; (2) the efficiency of fractional crystallization and the extent of crystal zoning are rate dependent; and (3) the partitioning of Al2O3, TiO2, and Cr2O3 between pyroxene and liquid depends on cooling rate.

Grove, T. L.↗
NASA NTRS1975

Lunar petrogenesis in a well-stirred magma ocean

The principal group of low-KREEP highlands rocks as indicated by quartz-olivine-anorthite pseudoternary phase diagrams shows chemical trends which violate the Bowen reaction principle, in that the greater the concentration of magnesian and mafic minerals, the more sodic the coexisting plagioclase tends to be. It is suggested that this trend was established during the primary differentiation of the lunar crust and is a result of crystallization in a vigorously convecting (well-stirred) system. Under these conditions all plagioclase crystals, all pyroxene crystals, and all of the residual liquid remain fairly uniform in composition until advanced crystallization immobilizes the system. The rock suite then established would vary continuously from anorthositic types at the top to ultramafic types at the bottom.

Wood, J. A.↗
NASA NTRS1981

Chemical studies of L-chondrites. I - A study of possible chemical sub-groups

Radiochemical neutron activation analysis of Ag, As, Au, Bi, Co, Cs, Ga, In, Rb, Sb, Te, Tl and Zn and major element data in 14 L4-6 and 3 LL5 chondrites indicates that the L-group is unusually variable and may represent at least 2 sub-groups differing in formation history. Chemical trends in the S/Fe-rich sub-group support textural evidence indicating late loss of a shock-formed Fe-Ni-S melt; the S/Fe-poor sub-group seemingly reflects nebular fractionation only. Highly mobile In and Zn apparently reflect shock-induced loss from L-chondrites. Data for L5 chondrites suggest higher formation temperatures and/or degrees of shock than for LL5 chondrites.

Neal, C. W.↗
NASA NTRS1982

Regional chemical setting of the Apollo 16 landing site and the importance of the Kant Plateau

Orbital X-ray data from the Apollo 16 region indicate that physiographic units identified before the lunar mission can be classified as chemical units as well. The Descartes Mountains, however, appear to be an extension of the Kant Plateau composition that is unusually anorthositic and resembles farside terra. The Cayley Plains have closer affinities to basaltic materials than terra materials, physically, spectrally and chemically. The Theophilus impact, 330 km east of the landing site, excavated magnesium-rich basalts from below less-magnesian flows in Mare Nectaris; but, mafic ejecta was substantially blocked from the Apollo 16 site by the Kant Plateau that rises 5 km above the level of the mare. Apollo 16 soil samples from stations selected to collect either Descartes Mountains material or Cayley Plains material were surprisingly similar. However, they do, indeed, show the chemical trends indicative of the two units as defined by the orbiting geochemistry detectors. The Kant Plateau and Descartes Mountains material may be among the rare nearside examples of a plagioclase-rich cumulate of the primordial magma ocean.

Andre, C. G.↗
NASA NTRS1987

Copper and nickel partitioning in iron meteorites

Trace element analyses using proton induced X-ray emission and synchrotron X-ray fluorescence have been made on metal and troilite from nine iron meteorites representing five geochemical groups. Nickel and copper distribution coefficients D (troilite/metal) vary by factors of 600 and 20, respectively, correlate positively with kamacite bandwidth and correlate negatively with bulk nickel content. Meteorites with bulk Ni of less than 10 percent have Cu-enriched troilite while those with Ni greater than 10 percent have Cu-depleted troilite. Since magmatic evolution and partial melting will produce Cu-enriched troilite only, the observation of Cu-depleted troilite in Ni-rich meteorites is evidence for subsolidus reequilibration, a process which reduces D(Cu) by transfer of Cu to exsolving metal. Elemental redistribution may have played an important role in establishing the present chemical trends in iron meteorites.

Sutton, S. R.↗
NASA NTRS1990

Investigation of new semiinsulating behavior of III-V compounds

The investigation of defect interactions and properties related to semiinsulating behavior of III-V semiconductors resulted in about twenty original publications, six doctoral thesis, one masters thesis and numerous conference presentations. The studies of new compensation mechanisms involving transition metal impurities have defined direct effects associated with deep donor/acceptor levels acting as compensating centers. Electrical and optical properties of vanadium and titanium levels were determined in GaAs, InP and also in ternary compounds InGaAs. The experimental data provided basis for the verification of chemical trends and the VRBE method. They also defined compositional range for III-V mixed crystals whereby semiinsulating behavior can be achieved using transition elements deep levels and a suitable codoping with shallow donor/acceptor impurities.

Lagowski, Jacek↗
NASA NTRS1991

Composition of chondrule silicates in LL3-5 chondrites and implications for their nebular history and parent body metamorphism

The composition of 75 type-IA and type-II porphyritic olivine chondrules from nine LL type 3 to type 5 chondrites was determined and was compared with that of chondrules from the Semarkona type 3.0 meteorite. Chemical data for silicates in the LL3.3-5 chondrites indicated that porphyritic olivine chondrules in these chondrites could be derived from chondrules similar to those from the Semarkona LL3.0, the least metamorphosed one of the known LL chondrites. It is shown that the chemical trends defined by the minerals of type-IA and type-II chondrules can be satisfactorily accounted for by the process of solid-state diffusive equilibration between minerals in chondrules and the opaque matrix rather than by changes in conditions during chondrule crystallization.

Mccoy, Timothy J.↗
NASA NTRS1993

Chemical fractionations in group IIIAB iron meteorites - Origin by dendritic crystallization of an asteroidal core

Results of an investigation of the crystallization history of the asteroidal core that produced nearly 200 iron meteorites of group IIIAB are presented. The accuracy of the published distribution of coefficients between solid and liquid metal for seven elements and their dependence on the concentrations of S and P are critically assessed to develop a nonideal fractional crystallization model that reproduces all of the major features of the overall chemical trends in group IIIAB. It is suggested that the apparent distribution coefficient of S was was much higher than its equilibrium value (not greater than 0.01) and that it increased during crystallization. In the present preferred model the apparent distribution coefficient for S increases from 0.6 to 0.8, while the S concentration of the liquid increases from 6 to 13 wt pct. It is inferred that light S-rich liquid accumulates preferentially at the top of the core and in structural traps formed by the advancing solid.

Haack, Henning↗
NASA NTRS1993

Electronic characterization of defects in narrow gap semiconductors

The study of point defects in semiconductors has a long and honorable history. In particular, the detailed understanding of shallow defects in common semiconductors traces back to the classic work of Kohn and Luttinger. However, the study of defects in narrow gap semiconductors represents a much less clear story. Here, both shallow defects (caused by long range potentials) and deep defects (from short range potentials) are far from being completely understood. In this study, all results are calculational and our focus is on the chemical trend of deep levels in narrow gap semiconductors. We study substitutional (including antisite), interstitial and ideal vacancy defects. For substitutional and interstitial impurities, the efects of relaxation are included. For materials like Hg(1-x)Cd(x)Te, we study how the deep levels vary with x, of particular interest is what substitutional and interstitial atoms yield energy levels in the gap i.e. actually produce deep ionized levels. Also, since the main technique utilized is Green's functions, we include some summary of that method.

Patterson, James D.↗