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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
NASA NTRS1976

The project scientist's role in scientific spacecraft project management

The project scientists is in a position which rates very high in terms of behavioral study recommendations. His influence over objectives is generally considered to be important. He is highly autonomous in a moderately coordinated environment. He has diverse managerial and technical functions and the performance of these functions require him to grow beyond his role as an experimenter. However, the position within the line organization for those interviewed is also very stimulating, rating almost as high by the same criteria. The role of project scientist may not be the dominant means of professional growth for the experienced scientific investigators. The influence which the project scientist exerts on the project and the stimulation of that position for him are determined largely by his position outside the defined project scientist role. The role of the project scientist is changing because the environment of those who become project scientists is changing.

Eller, E. L.↗
NASA NTRS1983

Spectral chemistry of green glass-bearing 15426 regolith

The detection of appreciable concentrations of ferric iron in a synthetic green glass equilibrated at an oxygen fugacity of 10 to the -11th atm prompted a Moessbauer spectral study of pristine emerald-green glass spherules carefully handpicked from regolith sample 15426. No Fe(3+) ions were detected in this lunar sample or in a synthetic green glass simulant equilibrated at fO2 = 10 to the -14th atm, suggesting that the green glass clods in rock 15426 formed under conditions of correspondingly low oxygen fugacities. The Moessbauer spectra indicated the presence of olivine crystallites in the lunar emerald green glass spherules. Measurements of homogeneous and partially devitrified synthetic silicate glasses revealed that significant changes of coordination environment about Fe(2+) ions in the glass structure occur during crystallization of olivine crystals from the melt.

Burns, R. G.↗
NASA NTRS1986

Investigation of the effects of cobalt ions on epoxy properties

The effects of Co(acac)sub x complexes on MY-720 epoxy properties have been investigated. It appears that Co2(+) ions form antibonding or nonbonding orbitals which increase the free volume and also reduce the cohesiveness of the host epoxy. The effects of Co2(+) ions, on the other hand, seem to result in increased Cohesiveness of the epoxy. The experimental values of magnetic moments of both types of ions in MY-720 suggest that the orbital momentum contributions of the (3d) electrons are partially conserved, though the effect is more pronounced for Co2(+) ions. The coordination environment of the cobalt ions in the host epoxy does not appear to be uniquely defined. These results indicate that the effects of metal ions on resin properties cannot be easily predicted on the basis of ligand field theory argument alone. Complex interactions between metal ions and host epoxy molecular structure suggest the desirability of parallel experimental investigations of electronic, magnetic, and mechanical properties of metal ion-containing epoxy samples for comparison with theory.

Singh, J. J.↗
NASA NTRS1987

Hisingerite and iddingsite on Mars: Degradation of iron-rich basalts

Paragenetic evidence that indicates that hisingerite may have formed during the evolution of Martian regolith is summarized. Hisingerite was once regarded as poorly crystalline iron-rich smectite or nontronite. However, recent electron microscopy and X-ray studies have revealed hisingerite to have an amorphous or gel structure containing a disordered array of (FeO6) octahedra and (SiO4) tetrahedra. It is just this coordination environment and degree of crystallinity that matches materials simulating the spectral properties of the bright regions of Mars. Therefore, hisingerite and basic ferric sulfate minerals appear to be major contributers to remote sensed reflectance spectral profiles of Mars.

Burns, Roger G.↗
NASA NTRS2016

Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

microscopy↗
DOE OSTI2021

Aminopolycarboxylates in trivalent f-element separations

Aminopolycarboxylate reagents strongly bind a variety of metal ions. Trivalent f-elements are no exception. The formed complexes are very stable, especially when aminopolycarboxylate structure contains multiple aminoacetate groups. The efficient coordination of trivalent f-elements by these reagents prompted decades of research and development efforts devoted to separation and purification of f-block metal ions. This chapter overviews the fundamental and applied aspects of aminopolycarboxylate use in trivalent f-element separations. First, a brief synopsis on how the chemical properties of 4f and 5f metal ions determine their similar solution behavior is followed by a discussion of aqueous complexation as means to perturb it. The synthetic methodologies for preparation of aminopolycarboxylate complexants are discussed next. Fundamental features of trivalent f-element complexation by aminopolycarboxylates are summarized, focusing on a variety of structure-function relationships demonstrated for this class of chelators and theoretical efforts to accurately describe such coordination environments. Finally, historical accounts of aminopolycarboxylate use in 4f and 5f element separations are supplemented by recent advances in those research fields.

Jansone-Popova, Santa↗
DOE OSTI2024

Comparison of Gas Phase Fragmentation Behaviors of Nuclear Fuel Cycle Ligands in Lanthanide and Americium Metal Ligand Nitrate Clusters

Introduction (120 words): Transport of metal ions across the aqueous-organic phase boundary is an essential step in a hydrometallurgical nuclear fuel reprocessing strategy. The study of transport agents for nuclear fuel elements is imperative to guide the design of ligands that boost the separation efficiency of the recovery process from fission products. However, limited studies have been made on the chemistry of these transport agents when complexing with transuranic elements in gas-phase where all surrounding factors are essentially excluded. This work investigates the reagent ligand complexations to transuranic and other metals and their dissociations in the gas phase. Comparisons are made between 4f and 5f elements and between ligands. Methods (120 words): (N,N-diisobutylcarbamoylmethyl)phenyloctylphosphine oxide (CMPO) and N,N,N',N'-tetraoctyldiglycolamide (TODGA) have been selected to complex with metal nitrates. The actinide americium and lanthanides neodymium, samarium, and europium were investigated as part of this work. The lanthanides were selected to act as size and electron configuration analogues of the minor actinides. Metal complexes with two ligands and two nitrates ([M(NO3)2(CMPO)2]+, for example) are studied in Bruker micrOTOF-Q II mass spectrometer equipped with collision-induced dissociation capability. The comparisons of the mass spectra are made in groups of homogenous ligands and mixed TODGA-CMPO ligands clusters. Comparisons are also made based on the complexed metals (Am and lanthanides). Preliminary data (300 words): Collision-induced dissociation mass spectrometry data are collected on two ligands complexed with metal nitrates where the two ligands are homogenous, with (CMPO)2 or (TODGA)2, or heterogeneous, with (TODGA)(CMPO). Several fragmentation patterns are observed among complexes with the CMPO ligand whereas the TODGA ligand commonly dissociates intact from the complex. Most of the metal complexes exhibit similar fragmentation patterns, but there are a few notable deviations in fragmentation patterns between the Am and Ln-bearing complexes. For the [M(CMPO)2(NO3)2]+ complexes, the initial loss of nitrate in the form of nitric acid is observed in all four complexes. However, [Am(CMPO)2(NO3)2]+ exhibits an additional fragmentation not found in the lanthanide complexes. Also, a significantly different ratio of the second nitric acid loss is found in the Am complex. These deviations may indicate the different interaction behaviors between actinides and lanthanides. The [M(TODGA)2(NO3)2]+ complexes exhibit the fragmentation as the loss of one TODGA ligand as an intact form and the loss of nitrate as nitric acid. The Am complex exhibits an additional fragmentation after losing the TOGDA ligand, which is not observed among the Ln complexes. The heterogeneous [M(TODGA)(CMPO)(NO3)2]+ complexes exhibit both similarities and differences between the Am and Ln complexes. For example, the heterogenous Am complex does not exhibit the loss of an intact TODGA ligand while all three Ln complexes do. This indicates that TODGA may bind more strongly to Am than Ln. Additionally, the intensity of the loss of CMPO ligand (as partially or whole) is found to be significantly larger than that of the loss of TODGA (as partially of whole) indicating that TODGA is bound to the metal significantly stronger than CMPO. Planned computational analysis will help understand the deviation in fragmentation behaviors between americium and lanthanide metal centers, or between TODGA and CMPO ligands. Novel aspect (20 words): Gas-phase actinide and lanthanide complex formation and fragmentation provide insight into the coordination environment differences of f-element metals.

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

Comparison of Gas Phase Fragmentation Behaviors of Nuclear Fuel Cycle Ligands in Lanthanide and Americium Metal Ligand Nitrate Clusters

Title (20 word): Comparison of Gas Phase Fragmentation Behaviors of Nuclear Fuel Cycle Ligands in Lanthanide and Americium Metal Ligand Nitrate Clusters Introduction (120 words): Transport of metal ions across the aqueous-organic phase boundary is an essential step in a hydrometallurgical nuclear fuel reprocessing strategy. The study of transport agents for nuclear fuel elements is imperative to guide the design of ligands that boost the separation efficiency of the recovery process from fission products. However, limited studies have been made on the chemistry of these transport agents when complexing with transuranic elements in gas-phase where all surrounding factors are essentially excluded. This work investigates the reagent ligand complexations to transuranic and other metals and their dissociations in the gas phase. Comparisons are made between 4f and 5f elements and between ligands. Methods (120 words): (N,N-diisobutylcarbamoylmethyl)phenyloctylphosphine oxide (CMPO) and N,N,N',N'-tetraoctyldiglycolamide (TODGA) have been selected to complex with metal nitrates. The actinide americium and lanthanides neodymium, samarium, and europium were investigated as part of this work. The lanthanides were selected to act as size and electron configuration analogues of the minor actinides. Metal complexes with two ligands and two nitrates ([M(NO3)2(CMPO)2]+, for example) are studied in Bruker micrOTOF-Q II mass spectrometer equipped with collision-induced dissociation capability. The comparisons of the mass spectra are made in groups of homogenous ligands and mixed TODGA-CMPO ligands clusters. Comparisons are also made based on the complexed metals (Am and lanthanides). Preliminary data (300 words): Collision-induced dissociation mass spectrometry data are collected on two ligands complexed with metal nitrates where the two ligands are homogenous, with (CMPO)2 or (TODGA)2, or heterogeneous, with (TODGA)(CMPO). Several fragmentation patterns are observed among complexes with the CMPO ligand whereas the TODGA ligand commonly dissociates intact from the complex. Most of the metal complexes exhibit similar fragmentation patterns, but there are a few notable deviations in fragmentation patterns between the Am and Ln-bearing complexes. For the [M(CMPO)2(NO3)2]+ complexes, the initial loss of nitrate in the form of nitric acid is observed in all four complexes. However, [Am(CMPO)2(NO3)2]+ exhibits an additional fragmentation not found in the lanthanide complexes. Also, a significantly different ratio of the second nitric acid loss is found in the Am complex. These deviations may indicate the different interaction behaviors between actinides and lanthanides. The [M(TODGA)2(NO3)2]+ complexes exhibit the fragmentation as the loss of one TODGA ligand as an intact form and the loss of nitrate as nitric acid. The Am complex exhibits an additional fragmentation after losing the TOGDA ligand, which is not observed among the Ln complexes. The heterogeneous [M(TODGA)(CMPO)(NO3)2]+ complexes exhibit both similarities and differences between the Am and Ln complexes. For example, the heterogenous Am complex does not exhibit the loss of an intact TODGA ligand while all three Ln complexes do. This indicates that TODGA may bind more strongly to Am than Ln. Additionally, the intensity of the loss of CMPO ligand (as partially or whole) is found to be significantly larger than that of the loss of TODGA (as partially of whole) indicating that TODGA is bound to the metal significantly stronger than CMPO. Planned computational analysis will help understand the deviation in fragmentation behaviors between americium and lanthanide metal centers, or between TODGA and CMPO ligands. Novel aspect (20 words): Gas-phase actinide and lanthanide complex formation and fragmentation provide insight into the coordination environment differences of f-element metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2011

Impact of Virtual Environments on Sensorimotor Coordination and User Safety

One critical unresolved issue related to the safe use of virtual environments (VEs) is maladaptive sensorimotor coordination following exposure to VEs. Moving visual displays used in VEs, especially in the absence of concordant vestibular signals leads to adaptive responses during VE exposure, but maladaptive responses following return to the normal environment. In the current set of investigations, we examined the effect of HMD and dome VE displays on eye-head-hand coordination, gaze holding and postural equilibrium. Subjects (61) performed a navigation and a pick and place task. Further, we compared 30 min and 60 min exposures across 3 days (each separated by 1 day). A subset of these results will be presented. In general, we found significant decrements in all three measures following exposure to the VEs. In addition, we found that these disturbances generally recovered within 1-2 hrs and decreased across days. These findings suggest the need for post-VE monitoring of sensorimotor coordination and for developing a set of recommendations for users concerning activities that are safe to engage in following use of a VE.

Harm, Deborah L.↗
NASA NTRSDate not supplied

Cognitive Engineering in Training: Monitoring and Pilot-Automation Coordination in Complex Environments

This paper reports our investigation of flight path monitoring in aviation. We interviewed experienced pilots to understand the knowledge and skills underlying effective monitoring and we developed an example learning environment to improve these skills. We explore how design of pilot training and learning, like the design of interfaces and of the underlying automation, benefits from cognitive engineering methods and perspective. In aviation, monitoring and managing flight path are critical activities. The influences on flight path are complex and come from the autoflight system, from control actions by the pilot, and from external factors, including weather and Air Traffic Control (ATC). Indeed, inadequate flight path monitoring is a current aviation concern as it has been implicated in accidents and incidents. Effective piloting depends on strategies for noticing, understanding, and anticipating these influences to monitor and manage flight path. Lack of such skills reduces pilots' ability to maintain safety margin and resilience. Although flightdeck automation is intended to aid pilot understanding and prediction, the Fight Management Systems (FMS) can mislead as well as aid the pilot's understanding and projection of what will happen. In dynamic conditions, FMS predictions may be based on old or incomplete information. Understanding such vulnerabilities is an important part of pilot-autoflight coordination. The learning environment we developed is designed to help pilots proactively monitor and manage flight path. We consider how a broad cognitive engineering approach might inform the "what" and "how" of learning in dynamic work domains.

pilot-monitoring↗
NASA NTRS2010

A Coordinated Effort to Address Space Weather and Environment Needs

The growing need for coordination of the many aspects of space environments is directly related to our increasing dependence on space assets. An obvious result is that there is a need for a coordinated effort to organize and make accessible the increasing number of space environment products that include space environment models and observations, material testing, and forecasting tools. This paper outlines a concept to establish a NASA-level Applied Spaceflight Environments (ASE) office that will provide coordination and funding for sustained multi-program support in three technical areas; (1) natural environments characterization and modeling, (2) environmental effects on materials and systems, (3) and operational and forecasting space environments modeling. Additionally the ASE office will serve as an entry point of contact for external users who wish to take advantage of data and assets associated with space environments, including space weather.

Minow, Joe↗
DOE OSTI2022

Toward Improved Charge Separation through Conformational Control in Copper Coordination Complexes

The continued development of solar energy as a renewable resource necessitates the design and study of new approaches to sustaining photodriven charge separation (CS). To this end, we present a bioinspired approach in which triggered conformational changes are used to control electron transfer (ET) events. We report, photo-induced conformational rearrangements of a ligand are translated into changes in the coordination geometry and environment about a bound metal ion. Taking advantage of the differential coordination properties of Cu I and Cu II , these dynamics facilitate intramolecular ET from Cu I to the ligand to create a CS state. The synthesis and photophysical characterization of CuCl(dpaa R ) (dpaa = dipicolylaminoacetophenone, with R = H and OMe) is presented. These ligands incorporate a fluorophore into their framework that gives rise to a twisted intramolecular charge transfer (TICT) excited state. Excited state ligand twisting provides a tetragonal coordination geometry capable of capturing Cu II in the CS state when an internal ortho-OMe binding site is present (as in dpaaOMe). We employ NMR, IR, EPR, and optical spectroscopies, X-ray diffraction, and electrochemical methods to establish the ground state properties of the Cu I and Cu II complexes. We then investigate the photophysical dynamics of these Cu I complexes via time-resolved photoluminescence (TR-PL), and optical transient absorption (OTA) spectroscopies. We show that relative to controls lacking a TICT-active ligand, the lifetime of the CS state is enhanced ~1000-fold. Further, the presence of the ortho-OMe substituent greatly enhances the lifetime of the TICT* state and biases the coordination environment toward Cu II . The presence of Cu I decreases photoinduced degradation from 14 to <2% but does not result in significant quenching via ET. Factors affecting CS in these systems are discussed, laying the groundwork for our strategy toward solar energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2016

Separation Assurance and Scheduling Coordination in the Arrival Environment

Separation assurance (SA) automation has been proposed as either a ground-based or airborne paradigm. The arrival environment is complex because aircraft are being sequenced and spaced to the arrival fix. This paper examines the effect of the allocation of the SA and scheduling functions on the performance of the system. Two coordination configurations between an SA and an arrival management system are tested using both ground and airborne implementations. All configurations have a conflict detection and resolution (CD&R) system and either an integrated or separated scheduler. Performance metrics are presented for the ground and airborne systems based on arrival traffic headed to Dallas/ Fort Worth International airport. The total delay, time-spacing conformance, and schedule conformance are used to measure efficiency. The goal of the analysis is to use the metrics to identify performance differences between the configurations that are based on different function allocations. A surveillance range limitation of 100 nmi and a time delay for sharing updated trajectory intent of 30 seconds were implemented for the airborne system. Overall, these results indicate that the surveillance range and the sharing of trajectories and aircraft schedules are important factors in determining the efficiency of an airborne arrival management system. These parameters are not relevant to the ground-based system as modeled for this study because it has instantaneous access to all aircraft trajectories and intent. Creating a schedule external to the CD&R and the scheduling conformance system was seen to reduce total delays for the airborne system, and had a minor effect on the ground-based system. The effect of an external scheduler on other metrics was mixed.

function allocation↗
NASA NTRS1999

Vision and Visual-Motor Coordination in Pitched Visual Environments

The everyday perception of one's bodily orientation is determined by two classes of sensory cues: Vision and gravity. Because these cues typically agree, as when one is standing in a lighted room, it is difficult if not impossible to determine the degree to which each contributes to spatial perception. Therefore, in order to make this judgment it is necessary to introduce a conflict between vision and gravity and note the resulting perceptual experience. One simple way to do this is to expose the observer to a visual framework that has been rolled or pitched relative to the gravitational vector. The underlying assumption is that the separate contributions of vision and gravity to the perception of bodily orientation that are measured in such a situation of intersensory conflict are the same as those that operate under normal (i.e., non-conflicting) circumstances.

Welch, Robert B.↗
NASA NTRS1989

The KALI multi-arm robot programming and control environment

The KALI distributed robot programming and control environment is described within the context of its use in the Jet Propulsion Laboratory (JPL) telerobot project. The purpose of KALI is to provide a flexible robot programming and control environment for coordinated multi-arm robots. Flexibility, both in hardware configuration and software, is desired so that it can be easily modified to test various concepts in robot programming and control, e.g., multi-arm control, force control, sensor integration, teleoperation, and shared control. In the programming environment, user programs written in the C programming language describe trajectories for multiple coordinated manipulators with the aid of KALI function libraries. A system of multiple coordinated manipulators is considered within the programming environment as one motion system. The user plans the trajectory of one controlled Cartesian frame associated with a motion system and describes the positions of the manipulators with respect to that frame. Smooth Cartesian trajectories are achieved through a blending of successive path segments. The manipulator and load dynamics are considered during trajectory generation so that given interface force limits are not exceeded.

Backes, Paul↗