Search NASA⌕ Search

SEARCH · Search NASA

Results for “solution phase”

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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Alloys for shaped charge liners method for making alloys for shaped charge liners

One embodiment of the invention provides an alloy with a density greater than 10 g/cm3, the alloy comprising a single phase solution of tungsten, nickel, and iron. Also provided is a cone liner for use in shaped charges, the liner comprised of a tungsten, nickel, iron alloy having a single phase microstructure. Substantially no precipitates or second phases exist in the alloy. One embodiment of the invention further provides a method for producing a single phase alloy, the method comprising establishing a melt of iron and nickel; dissolving tungsten in the melt to form a solution; wherein the atomic percents of the nickel, tungsten and iron range from between approximately Ni-7%W-0%Fe, Ni-18%W-0%Fe, and Ni-8%W-24%Fe, wherein Ni is the remainder, maintaining the solution at a first temperature sufficient to create a homogeneous mixture; allowing the homogeneous mixture to solidify; and thermochemically treating the solidified mixture for a time to dissolve any second phases or microstructure within the mixture.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Alkali triel chalcogenide nanocrystals: a molecular reactivity approach to ternary phase selectivity

Alkali-metal-based materials are promising building blocks for energy conversion and storage technologies. Here, we use a molecular reactivity-based solution-phase approach to selectively synthesize multiple phases and specific polymorphs of lithium- and sodium-containing triel chalcogenide nanocrystals, LiTrCh 2 , NaTrCh 2 , and NaTr 3 Ch 5 , where Tr = Ga and In and Ch = S, Se, and Te. Analogous to the case of binary II–VI and III–V tetrahedral semiconductors, where the two commonly isolated zinc blende and wurtzite polymorphs are separated by only 1–50 meV f.u. −1 , we find that LiTrCh 2 nanocrystals easily adopt tetragonal (chalcopyrite) and orthorhombic polymorphs separated by only 2.7–6.2 meV f.u. −1 Because of this small energy difference, soft colloidal synthesis succeeds in accessing either one of these polymorphs, depending on the specific dichalcogenide precursor used. Highly reactive diethyl diselenide favors the thermodynamically more stable tetragonal I$\bar{4}2$d phase, whereas mildly reactive diphenyl diselenide favors the kinetic, metastable orthorhombic Pna2 1 phase. Density functional theory calculations confirm the relative energies among multiple LiTrCh 2 polymorphs and also model the observed powder X-ray diffraction pattern of a new C2 NaIn 3 Te 5 phase. 7 Li, 69 Ga, and 77 Se solid-state NMR spectra are consistent with phase-pure ternary LiGaSe 2 nanocrystals. A majority of the nanocrystal compositions are visible-light emitters. This work opens the door to new Li/Na-based ternary triel chalcogenide nanostructures for energy storage and conversion applications.

Pavel, Md Riad Sarkar [Iowa State Univ., Ames, IA ↗
DOE OSTI2019

Influence of Interligand Interactions and Core-Charge Distribution on Gold Cluster Stability: Enthalpy vs Entropy

Understanding the formation and stability of ligated gold clusters is necessary to direct the scalable solution-phase synthesis of atomically-precise clusters with predetermined properties. Gas-phase studies provide molecular-level insight into ligandgold cluster interactions that control ligand exchange and growth/etching reactions in solution. Here we report a joint experimental and theoretical study of a series of eight gold atom, mixed phosphine, di-cationic clusters using time- and energy-resolved surface induced dissociation (SID) experiments and high-level calculations. Gold clusters were prepared by reduction of a gold salt precursor containing triphenylphosphine (PPh3). Subsequent ligand exchange reactions with methyldiphenylphosphine (MePPh2) generated a distribution of mixed-phosphine gold clusters. Experimentally-derived ligand binding energies and activation entropies for the mixed-ligand gold clusters were compared with ligand removal energies obtained from theoretical calculations. The results show that the exchange ligand, MePPh2, has a lower binding energy to the gold core than PPh3. In addition, both ligands are more strongly bound to the mixed-ligand clusters than to any of the pure PPh3-ligated gold clusters. Larger ligand binding energies in the mixed-ligand clusters are associated with large activation entropies, which become a competing factor determining cluster stability. This study reveals, for the first time, that ligand-ligand Van der Waals interactions contribute substantially to gold cluster stability and may be partially responsible for the large ligand dissociation entropies observed in SID experiments. We propose that ligand-ligand interactions in conjunction with changes in the charge distribution of the gold cores upon ligand removal bring about kinetically-driven fragmentation pathways, which may be responsible for the fast ligand exchange reactions observed in solution. These findings have broad implications for understanding what factors determine the stability of ligated metal clusters as certain ligands may have similar enthalpic and entropic components contributing to overall cluster stability.

Ligare, Marshall R.↗
DOE OSTI2022

Selective Detection of Diglycolamide Diastereomers By Metal-Ligand Cluster Formation

Introduction (120 words): Differentiation of isomers using mass spectrometry is a challenge, as these species tend to produce ions of identical mass-to-charge ratio. Therefore, separation with mass spectrometry must rely on chemical differences between isomeric species. Separation of stereoisomers is especially challenging, as these species often have very similar chemistry. However, recent investigations of the solvent extraction behavior of diastereomers of diglycolamide molecules have shown that different stereoisomers can have significantly different lanthanide extraction efficiencies. These studies showed that the R,S stereoisomer of 2,2'-oxybis(N,N-dioctylpropanamide efficiently extracts lanthanides, while the S,S stereoisomer does not. Thus, gas-phase metal complexation may provide a pathway for differentiating these species using mass spectrometry. Methods (120 words): Europium, samarium, and holmium clusters with the R,S, and the S,S diastereomers of 2,2'-oxybis(N,N-didecylpropanamide (trivially tetradecyl diglycolamide, or mTDDGA) were generated in gas-phase using the electrospray ionization source of a Bruker (Billerica, MA, USA) micrOTOF-Q II quadrupole time-of-flight mass spectrometer. Solutions of aqueous lanthanide nitrate and diglycolamide ligands in 2-propanol were added to 50%:50% by volume acetonitrile:2-propanol to generate the spray solutions. Ligand concentration was maintained at approximately 6 µM, while lanthanide concentration was maintained at either 6 µM or 30 µM . High resolution, high mass accuracy spectra were recorded using the time-of-flight. Mass accuracy was ensured using external calibration with Agilent (Santa Clara, CA, USA) ESI-L Low Concentration tuning mix. Preliminary data (300 words): Electrospray of solutions containing only R,S-mTDDGA or S,S-m-TDDGA yield abundant peaks at m/z= 721.7, corresponding to [mTDDGA+H]+1, m/z = 743.7, corresponding to [mTDDGA+Na]+1, and m/z = 1464.4, corresponding to the sodium-bound dimer, [Na(mTDDGA)2]+1. Spray of solutions containing 6 µM europium (Eu) with 3 µM R,S-mTDDGA produced an abundant cluster ion with an isotopic envelope centered at m/z=772.0, corresponding to [Eu(R,S-mTDDGA)3]3+. Europium-containing cluster ions with isotopic envelopes apexing at m/z = 1012.3 and 1189.0 correspond to the [Eu(R,S-mTDDGA)4]3+ and [Eu(R,S-mTDDGA)5]3+ cluster ions, respectively. Protonated and sodiated R,S-mTDDGA are present as well, along with the sodium-bound dimer. In contrast, spray of solutions containing 6 µM europium (Eu) with 3 µM S,S-mTDDGA diastereomer yielded only protonated and sodiated ligand ions; no Eu- S,S-mTDDGA ions were present. This mirrors the solution-phase behavior, where the S,S diestereomer extracts lanthanides with significantly less efficiency than the R,S diestereomer. Experiments with holmium and samarium yielded the same results. Increasing the lanthanide concentration to 30 µM resulted in limited formation of lanthanide-S,S-mTDDGA clusters. However, the abundance of the [Ln(S,S-mTDDGA)3]3+ clusters remained low compared to the abundance of the protonated and sodiated ligand. Additionally, the abundance of the [Ln(R,S-mTDDGA)3]3+ cluster ion was significantly higher than that of the protonated and sodiated ligand in experiments with spray solutions containing 30 µM lanthanide with R,S-mTDDA, supporting the hypothesis that R,S-mTDDGA has a higher intrinsic affinity for the lanthanides than S,S-mTDDGA. Thus, the intrinsic complexation with lanthanides appears to offer a route to differentiate diglycolamide diestereomers in the gas-phase. Novelty (20): Stereoisomers can be differentiated in the gas phase by exploitation of differences in metal complexation chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Supporting Data for "Pitfalls in Parameters: Practical Process Development in Chemical Vapor Processing of SiC"

CALculation of PHAse Diagrams (CALPHAD) was used to produce equilibrium phase diagrams of the MTS/H2 system. These were calculated in FactSage 8.2 using a combination of the FactPS and SGTE Solutions 2022 databases. Equilibrium was calculated for 185 gas species, 36 pure liquids, 8 pure solids, 1 liquid solution, and 22 solid solutions. Phase diagrams were calculated with 25 °C steps in temperature from 700 to 1325 °C and 10 torr steps in pressure from 20 to 760 torr.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Tuning Optical and Electrical Properties of Vanadium Oxide with Topochemical Reduction and Substitutional Tin

Vanadium oxides are widely tunable materials, with many thermodynamically stable phases suitable for applications spanning catalysis to neuromorphic computing. The stability of vanadium in a range of oxidation states enables mixed-valence polymorphs of kinetically accessible metastable materials. Low-temperature synthetic routes to, and the properties of, these metastable materials are poorly understood and may unlock new optoelectronic and magnetic functionalities for expanded applications. In this work, we demonstrate topochemical reduction of α-V 2 O 5 to produce metastable vanadium oxide phases with tunable oxygen vacancies (>6%) and simultaneous substitutional tin incorporation (>3.5%). The chemistry is carried out at low temperature (65 °C) with solution-phase SnCl 2 , where Sn 2+ is oxidized to Sn 4+ as V 5+ sites are reduced to V 4+ during oxygen vacancy formation. Despite high oxygen vacancy and tin concentrations, the transformations are topochemical in that the symmetry of the parent crystal remains intact, although the unit cell expands. Band structure calculations show that these vacancies contribute electrons to the lattice, whereas substitutional tin contributes holes, yielding a compensation doping effect and control over the electronic properties. The SnCl 2 redox chemistry is effective on both solution-processed V 2 O 5 nanoparticle inks and mesoporous films cast from untreated inks, enabling versatile routes toward functional films with tunable optical and electronic properties. The electrical conductance rises concomitantly with the SnCl 2 concentration and treatment time, indicating a net increase in density of free electrons in the host lattice. This work provides a valuable demonstration of kinetic tailoring of electronic properties of vanadium–oxygen systems through top-down chemical manipulation from known thermodynamic phases.

36 MATERIALS SCIENCE↗
DOE OSTI2022

On the Sintering Behavior of Nb2O5 and Ta2O5 Mixed Oxide Powders

A mixed oxide system consisting of Nb2O5 and Ta2O5, was subjected to annealing in air/hydrogen up to 950 °C for 1–4 h to study its sintering behavior. The thermogravimetric–differential scanning calorimetry (TGA–DSC) thermograms indicated the formation of multiple endothermic peaks at temperatures higher than 925 °C. Subsequently, a 30% Ta2O5 and 70% Nb2O5 (mol%) pellet resulted in good sintering behavior at both 900 and 950 °C. The scanning electron microscope (SEM) images corroborated these observations with necking and particle coarsening. The sintered pellets contained a 20.4 and 20.8% mixed oxide (Nb4Ta2O15) phase, along with Ta2O5 and Nb2O5, at both 900 and 950 °C, indicating the possibility of the formation of a solid solution phase. In situ high-temperature X-ray diffraction (XRD) scans also confirmed the formation of the ternary oxide phase at 6 and 19.8% at 890 and 950 °C, respectively. The Hume–Rothery rules could explain the good sintering behavior of the Ta2O5 and Nb2O5 mixed oxides. An oxide composition of 30% Ta2O5 and 70% Nb2O5 (mol%) and a sintering temperature of 950 °C appeared adequate for fabricating well-sintered oxide precursors for subsequent electrochemical polarization studies in fused salts.

36 MATERIALS SCIENCE↗
NASA NTRS1987

Nondestructive ultrasonic characterization of two-phase materials

The development of ultrasonic methods for the nondestructive characterization of mechanical properties of two phase engineering materials are described. The primary goal was to establish relationships between the nonlinearity parameter and the percentage of solid solution phase in two phase systems such as heat treatable aluminum alloys. The acoustoelastic constant was also measured on these alloys. A major advantage of the nonlinearity parameter over that of the acoustoelastic constant is that it may be determined without the application of stress on the material, which makes the method more applicable to inservice nondestructive characterization. The results obtained on the heat treatable 7075 and the work hardenable 5086 and 5456 aluminum alloys show that both the acoustoelastic constant and the acoustic nonlinearity parameter change considerable with the volume fraction of second phase precipitates in these aluminum alloys. A mathematical model was also developed to relate the effective acoustic nonlinearity parameter to volume fraction of second phase precipitates in an alloy. The equation is approximated to within experimental error by a linear expression for volume fractions up to approx. 10%.

Salama, Kamel↗
DOE OSTI2022

Polymer infiltration synthesis of inorganic nanoporous coatings: Does polymer template affect their properties?

Synthesis of all-inorganic metal oxide architectures using polymer templates offers control over their thickness, porosity, and composition. Here, in this study, we provide insights into the synthesis of nanoporous zinc oxide films as a model system via infiltration of polymers that have different mechanisms of interaction with metal oxide precursors such as a polymer of intrinsic microporosity (PIM-1) and representative of the block-copolymers family (polystyrene-polyvinyl pyridine block copolymer). We investigated polymer infiltration process with both gas (diethyl zinc, DEZ, and water vapors) and solution (zinc acetylacetonate, Zn(acac) 2 , dissolved in ethanol) phase precursors. Using quartz crystal microbalance (QCM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses, we systematically studied the effect of polymer template and the form of the metal oxide precursors on the properties of synthesized metal oxide thin coatings. We demonstrate that the infiltration of polymer templates can be efficiently achieved using both gas phase and solution phase precursors. We show that the crystallinity of the synthesized 200 nm ZnO films is mainly affected by the state of the precursor (gas or solution phase) and does not depend on the polymer template type. In turn, the polymer type affects the surface termination of ZnO films. We demonstrate that the surface of porous ZnO coatings synthesized with BCP (here PS-P4VP) is more accessible than the surface of ZnO synthesized with PIM; however, despite the lower surface accessibility for ethanol molecules, ZnO synthesized via infiltration of PIM-1 with solution-phase precursors demonstrates the largest change in resistivity upon its exposure to ethanol vapor at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2021

DFTTK: Density Functional Theory ToolKit for high-throughput lattice dynamics calculations

In this work, we present a software package in Python for high-throughput first-principles calculations of thermodynamic properties at finite temperatures, which we refer to as DFTTK (Density Functional Theory ToolKit). DFTTK is based on the atomate package and integrates our experiences in the last decades on the development of theoretical methods and computational softwares. It includes task submissions on all major operating systems and task executions on high-performance computing environments. Furthermore, the distribution of the DFTTK package comes with examples of calculations of phonon density of states, heat capacity, entropy, enthalpy, and free energy under the quasi-harmonic phonon scheme for the stoichiometric phases of Al, Ni, Al 3 Ni, AlNi, AlNi 3 , Al 3 Ni 4 , and Al 3 Ni 5 , and the fcc solution phases treated using the special quasirandom structures at the compositions of Al 3 Ni, AlNi, and AlNi 3 .

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Structural and magnetic transitions of CoFeMnNiAl high-entropy alloys caused by composition and annealing

Tailoring magnetic behavior by composition and annealing is an effective way. The phase transition from the face-centered-cubic (FCC) to B2 structure influenced by the Al content on the CoFeMnNiAl x alloys leads to the enhanced magnetization. However, the excessive Al addition in the B2-structured alloys impairs the magnetization. The phase transformation caused by annealing also indicates that the saturation magnetization of the alloy depends on the volume fraction of the B2 phase, and a higher content of the B2 phase is beneficial to the large saturation magnetization. Ab initio calculations are used to explain the magnetic behavior of the present HEAs and the effects of phase structures on magnetic characteristics. The phase stability of the CoFeMnNiAl x alloy is thoroughly studied by both the existing phase-formation empirical criteria and annealing. Here, the existing empirical criteria used to predict the phase formation are not universal. However, combining the ΔH mix -δ relation and the φ value, whether the single disordered solid-solution phase is formed can be preliminarily predicted.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Influence of concentration polarization and thermodynamic non-ideality on salt transport in reverse osmosis membranes

The classic Merten and Lonsdale transport model for reverse osmosis membranes was reformulated to explicitly demonstrate the effects of concentration polarization and solution phase thermodynamic non-idealities on salt transport. A framework presented here accounts for the concentration dependence of ion activity coefficients in salt solutions, which was not explicitly included in the classic model. This approach was applied to four salt solutions, NaCl, MgCl 2 , CaCl 2 , and Na 2 SO 4 , tested in cross-flow conditions for a commercial RO membrane, Dow Filmtec™ BW30XFR. Salt transport coefficients corrected for concentration polarization and non-ideal thermodynamic effects, B a , were calculated as a function of permeate flux and compared with apparent salt transport coefficients, B . Finally, these corrections were significant, resulting in B a values greater than B values by a factor of 1.3–2.1 for 2:1 and 1:2 salts (i.e., MgCl 2 , CaCl 2 , and Na 2 SO 4 ). B a values for NaCl (a 1:1 salt), however, were similar to or somewhat smaller than B values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Metadynamics investigation of lanthanide solvation free energy landscapes and insights into separations energetics

Lanthanide ion solvation chemistry in nonaqueous phases is key to understanding and developing effective separation processes for these critical materials. Due to the complexity and inherent disorder of the solution phase, a comprehensive picture of the solvated metal ion is often difficult to generate solely from conventional spectroscopic approaches and electronic structure calculations, particularly in the extractant phase. In this work, we use classical molecular dynamics (MD) simulation with an advanced sampling technique, metadynamics, supplemented by experimental spectroscopy and speciation analysis, to measure lanthanide solvation free energy landscapes. We define coordination-based collective variables to probe the entire range of solvation configurations in the organic phase of lanthanum (La), europium (Eu), and lutetium (Lu) nitrate salts bound with a commonly used extractant, N,N′-dimethyl, N,N′-dioctylhexylethoxymalonamide (DMDOHEMA). The known lanthanide extraction trend of La ≈ Eu > Lu is readily explained by the measured free energy surfaces, which show consistent DMDOHEMA coordination from La to Eu, followed by loss of DMDOHEMA coordination from Eu to Lu. These simulations suggest how ligand crowding at the metal center can control selectivity, in this case resulting in the opposite extraction trend as observed with other conventional extractants, where the enthalpic contribution from increasing lanthanide charge density across the series dominates the extraction energetics. We also find that the presence of inner-sphere water, verified by time-resolved fluorescence, diversifies the accessible solvation structures. As a result, understanding solvation requires consideration of an entire thermodynamic ensemble, rather than the single dominant lowest-energy structure, as is often considered out of necessity in interpretation of spectroscopic data or in electronic structure-based ligand design approaches. In general, we demonstrate how metadynamics uniquely enables investigation of complex, multidimensional solvation energetic landscapes, and how it can explain selectivity trends where extraction is controlled by more complex mechanisms than simple charge density-based selectivity.

Wang, Xiaoyu↗
DOE OSTI2025

Development of a Multi-Robot System for Autonomous Inspection of Nuclear Waste Tank Pits

This paper introduces the overall design plan, development timeline, and preliminary progress of the Autonomous Pit Exploration System project. This project aims to develop an advanced multi-robot system for the efficient inspection of nuclear waste-storage tank pits. The project is structured into three phases: Phase 1 involves data collection and interface definition in collaboration with Hanford Site experts and university partners, focusing on tank riser geometry and hardware solutions. Phase 2 includes the selection of sensors and robot components, detailed mechanical design, and prototyping. Phase 3 integrates all components into a cohesive system managed by a master control package which also incorporates digital twin and surrogate models, and culminates in comprehensive testing and validation at a simulated tank pit at the Idaho National Laboratory. Additionally, the system’s communication design ensures coordinated operation through shared data, power, and control signals. For transportation and deployment, an electric vehicle (EV) is chosen to support the system for a full 10 h shift with better regulatory compliance for field deployment. A telescopic arm design is selected for its simple configuration and superior reach capability and controllability. Preliminary testing utilizes an educational robot to demonstrate the feasibility of splitting computational tasks between edge and cloud computers. Successful simultaneous localization and mapping (SLAM) tasks validate our distributed computing approach. More design considerations are also discussed, including radiation hardness assurance, SLAM performance, software transferability, and digital twinning strategies.

Nuclear waste management↗
DOE OSTI2021

Reduction of Vanadium(V) by Iron(II)-Bearing Minerals

Fe(II)-bearing minerals (magnetite, siderite, green rust, etc.) are common products of microbial Fe(III) reduction, and they provide a reservoir of reducing capacity in many subsurface environments that may contribute to the reduction of redox active elements such as vanadium; which can exist as V(V), V(IV), and V(III) under conditions typical of near-surface aquatic and terrestrial environments. To better understand the redox behavior of V under ferrugenic/sulfidogenic conditions, we examined the interactions of V(V) (1 mM) in aqueous suspensions containing 50 mM Fe(II) as magnetite, siderite, vivianite, green rust, or mackinawite, using X-ray absorption spectroscopy at the V K-edge to determine the valence state of V. Two additional systems of increased complexity were also examined, containing either 60 mM Fe(II) as biogenic green rust (BioGR) or 40 mM Fe(II) as a mixture of biogenic siderite, mackinawite, and magnetite (BioSMM). Within 48 h, total solution-phase V concentrations decreased to <20 µM in all but the vivianite and the biogenic BiSMM systems; however, >99.5% of V was removed from solution in the BioSMM and vivianite systems within 7 and 20 months, respectively. The most rapid reduction was observed in the mackinawite system, where V(V) was reduced to V(III) within 48 h. Complete reduction of V(V) to V(III) occurred within 4 months in the green rust system, 7 months in the siderite system, and 20 months in the BioGR system. Vanadium(V) was only partially reduced in the magnetite, vivianite, and BioSMM systems, where within 7 months the average V valence state stabilized at 3.7, 3.7, and 3.4, respectively. The reduction of V(V) in soils and sediments has been largely attributed to microbial activity, presumably involving direct enzymatic reduction of V(V); however the reduction of V(V) by Fe(II)-bearing minerals suggests that abiotic or coupled biotic–abiotic processes may also play a critical role in V redox chemistry, and thus need to be considered in modeling the global biogeochemical cycling of V.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Time-resolved cryogenic electron tomography for the study of transient cellular processes

Cryogenic electron tomography (cryo-ET) is the highest resolution imaging technique applicable to the life sciences, enabling sub-nanometer visualization of specimens preserved in their near native states. The rapid plunge freezing process used to prepare samples lends itself to time-resolved studies, which researchers have pursued for in vitro samples for decades. Here, we focus on developing a freezing apparatus for time-resolved studies in situ. The device mixes cellular samples with solution-phase stimulants before spraying them directly onto an electron microscopy grid that is transiting into cryogenic liquid ethane. By varying the flow rates of cell and stimulant solutions within the device, we can control the reaction time from tens of milliseconds to over a second prior to freezing. In a proof-of-principle demonstration, the freezing method is applied to a model bacterium, Caulobacter crescentus, mixed with an acidic buffer. Through cryo-ET we resolved structural changes throughout the cell, including surface-layer protein dissolution, outer membrane deformation, and cytosolic rearrangement, all within 1.5 seconds of reaction time. This new approach, Time-Resolved cryo-ET (TR-cryo-ET), enhances the capabilities of cryo-ET by incorporating a sub-second temporal axis and enables the visualization of induced structural changes at the molecular, organelle, or cellular level.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Actinide N-Donor Thermodynamics: Expanding the f-element Covalency Dialogue. Final report

Resolving the chemistry and physics of f-electrons is one of the grand challenges of science for energy technology. A central component of this challenge is describing covalency in actinide-ligand interactions. Crystallography, x-ray spectroscopy and computational techniques have provided reasonable, and in some cases remarkable, support for covalency in actinide-ligand interactions. Courtesy the quality of the results obtained, a significant portion of the covalency dialogue has been forwarded through solid-state and computational studies of the more stable actinides (Th, U, Pu, Np). However; recent reports have questioned whether covalency in actinide interactions increases or decreases across the series. Examination of less-stable trans-actinides (Am, Cm, Bk, Cf and Es) by the aforementioned approaches can be rapidly limited due to material availability, radiological hazards and experimental data to validate computational models. Furthermore, limited thermodynamic data exists to confirm covalency in actinide solution phase interactions that are highly relevant to the remediation and reprocessing of used nuclear fuel. The best-defined interactions of actinides with soft donors in aqueous solutions involve (poly)aminopolycarboxylate (APC) ligands. The chelate effect and binding affinity with the acetic acid APCs subgroups encourages amine interactions with the actinide metal center. In the absence of these factors, amine interactions with actinides are too weak to overcome the protective hydration shell of the dissolved ion. The ability for APCs to force actinide interactions with soft nitrogen donors (as defined by Pearson’s Hard Soft Acid Base theory) encourages the application of these ligands in a variety of processes for actinide recovery from nearly chemically identical lanthanides. The ability to functionalize the amine center of the ligand in a variety of capacities (adding additional amine groups, exchanging the conventional acetate group for an acetate group, etcetera), allows for the APC ligand to serve as a thermodynamic probe for actinide-nitrogen interactions. Perhaps the single most significant breakthrough during the previous funding cycle was the observation that covalency for the transplutonium part of the actinide series can be increasingly influenced with energy degeneracy driven covalency as the actinides become heavier. This was observed most predominantly with dipicolinic acid, but extensions of f-orbital degeneracy were found to affect aliphatic aminopolycarboxylate-actinide complexes through einsteinium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Characterization of Iridium Coated Rhenium Used in High-Temperature, Radiation-Cooled Rocket Thrusters

Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high-temperatures and oxidizing environments. While combustion efficiency is optimized at high temperatures, many refractory metals are unsuitable for thruster applications due to rapid material loss from the formation of volatile oxides. This process occurs during thruster operation by reaction of the combustion products with the material surface. Aerojet Technical Systems has developed a thruster cone chamber constructed of Re coated with Ir on the inside surface where exposure to the rocket exhaust occurs. Re maintains its structural integrity at high temperature and the Ir coating is applied as an oxidation barrier. Ir also forms volatile oxide species (IrO2 and IrO3) but at a considerably slower rate than Re. In order to understand the performance limits of Ir-coated Re thrusters, we are investigating the interdiffusion and oxidation kinetics of Ir/Re. The formation of iridium and rhenium oxides has been monitored in situ by Raman spectroscopy during high temperature exposure to oxygen. For pure Ir, the growth of oxide films as thin as approximately 200 A could be easily detected and the formation of IrO2 was observed at temperatures as low as 600 C. Ir/Re diffusion test specimens were prepared by magnetron sputtering of Ir on Re substrates. Concentration profiles were determined by sputter Auger depth profiles of the heat treated specimens. Significant interdiffusion was observed at temperatures as low as 1000 C. Measurements of the activation energy suggest that below 1350 C, the dominant diffusion path is along defects, most likely grain boundaries, rather than bulk diffusion through the grains. The phases that form during interdiffusion have been examined by x ray diffraction. Analysis of heated test specimens indicates that the Ir-Re reaction produces a solid solution phase of Ir dissolved in the HCP structure of Re.

Stulen, R. H.↗