Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ion pairing”

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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Recovery of precious metals from space

The overall objective is to develop efficient and economical separation and recovery methods for the platinum group and other precious metals. The separation of Pd(II) from Pt(II), Ir(III), and Rh(III) with trioctylphosphine oxide (TOPO) in heptane using centrifugal partition chromatography (CPC) was investigated. Activities to achieve this objective focussed on selection and evaluation of extraction systems for the PGM and modification of selected systems for multistage operation with a view to scaling up to desired macro levels. On the basis of preliminary evaluation of a series of simple metal complexing agents and chelating agents, the TOPO in heptane was selected as a likely system for isolating of Pd(II) and Pt(II) from the other PGM. A multistage apparatus capable of configuration as a simple rugged device, a centrifugal partition chromatograph (CPC), was shown to be effective. The extraction of Pd(II) was studied by CPC and batch solvent extraction. The distribution ratios for Pd(II) determined by both methods agree well. In low HCl concentrations (less than 0.1 M), the extracted species was PdCl2.(TOPO)2, irrespective of the chloride concentration, while at acid concentrations above 0.1 M, the Pd was extracted as the ion pair, 2(TOPO.H+).(PdCl4)2-. Base line separation of Pd(II) and Pt(II) in CPC was obtained under a variety of chloride and HCl concentration. It was demonstrated that the efficiency of CPC for metal separation was limited by chemical kinetic factors rather than instrumental factors, strongly suggesting that dramatic improvements can be achieved by studying reaction kinetics of formation and dissociation of the extractable metal complex.

Freiser, Henry↗
NASA NTRS1992

Inclusive inelastic scattering of heavy ions in the independent particle model

We consider the inclusive inelastic scattering of heavy ions using the Glauber (1959) model and the independent particle approximation. Inclusive inelastic distributions for projectile excitation of the target and total inelastic scattering, where all projectile and target excited states are summed, are discussed using closure. The total inelastic distribution, when integrated, is shown to be equivalent to the absorption cross section, found from applying the optical theorem to the elastic scattering amplitude in the coherent approximation. Calculations are presented for several heavy-ion pairs, using realistic nuclear densities in a large mass number approximation.

Cucinotta, Francis A.↗
NASA NTRS1992

Formation of negative ions by electron impact on SiF4 and CF4

First measurements of cross sections for the formation of negative ions by electron attachment to SiF4 and CF4 are reported for an electron impact energy range of 0 to 50 eV. The energies at which the various ions appear and the positions at which the ionization efficiency curves peak have been obtained and compared with previous measurements. Thermochemical data have been used to predict and identify the various channels of dissociation. Cross sections for the production of ion pairs through the process of polar dissociation have also been measured.

Iga, I.↗
NASA NTRS1994

Energy deposition and middle atmosphere electrodynamic response to a highly relativistic electron precipitation event

Rocket data have been used to evaluate the characteristics of precipitating relativistic electrons and their effects on the electrodynamic structure of the middle atmosphere. These data were obtained at Poker Flat, Alaska, on May 13 and 14, 1990, during a midday, highly relativistic electron (HRE) precipitation event. Solid state detectors were used to measure the electron fluxes and their energy spectra. An X ray scintillator was included on each flight to measure bremsstrahlung X rays produced by energetic electrons impacting on the upper atmosphere. However, these were found the be of negligible importance for this particular event. The energy deposition by the electrons has been determined from the flux measurements and compared with in situ measurements of the atmospheric electrical response. The electrodynamic measurements were obtained by the same rockets and additionally on May 13, with an accompanying rocket. The impact flux was highly irregular, containing short-lived bursts of relativistic electrons, mainly with energies below 0.5 MeV and with fluxes most enhanced between pitch angles of 0 deg - 20 deg. Although the geostationary counterpart of this measured event was considered to be of relatively low intensity and hardness, energy deposition peaked near 75 km with fluxes approaching an ion pair production rate in excess of 100/cu cm s. This exceeds peak fluxes in relativistic electron precipitation (REP) events as observed by us in numerous rocket soundings since 1976. Conductivity measurements from a blunt probe showed that negative electrical conductivities exceeded positive conductivities down to 50 km or lower, consistent with steady ionization by precipitating electrons above 1 MeV. These findings imply that the electrons from the outer radiation zone can modulate the electrical properties of the middle atmosphere to altitudes below 50 km. During the decline and activity minimum of the current solar cycle, we anticipate the occurence of similar events but with fluxes 1-2 orders of magnitude above that reported here, based on studies of earlier solar cycles (e.g., Baker et al., 1993).

Goldberg, R. A.↗
NASA NTRS1994

Electron energy deposition in carbon monoxide gas

A comprehensive set of electron impact cross sections for carbon monoxide molecules is presented on the basis of the most recent experimental measurements and theoretical calculations. The processes by which energetic electrons lose energy in CO gas are analyzed with these input cross sections. The efficiencies are computed of vibrational and electronic excitation, dissociation, ionization, and heating for CO gas with fractional ionization ranging from 0% to 10%. The calculated mean energy per ion pair for neutral CO gas is 32.3 eV, which is in excellent agreement with the experimental value of 32.2 eV. It increases to 35.6 eV at a fractional ionization of 1%, typical of supernovae ejecta.

Liu, Weihong↗
NASA NTRS1999

Mesospheric Odd Nitrogen Enhancements During Relativistic Electron Precipitation Events

The behavior of mesospheric odd nitrogen species during and following relativistic and diffuse auroral precipitation events is simulated, Below 75 km nitric oxide is enhanced in proportion to the ion pair production function associated with the electron precipitation and the length of the event. Nitrogen dioxide and nitric acid are also enhanced. At 65 km the percentage of odd nitrogen for N is 0.1%, HNO3 is 1.6%, NO2 is 15%, and NO is 83.3%. Between 75 and 85 km NO is depleted during particle events due to the faster destruction of NO by N relative to the production of NO by N reacting with O2. Recovery of NO depends on transport from the lower thermosphere, where NO is produced in abundant amounts during particle events.

Aikin, A. C.↗
NASA NTRS2001

Total Electron-Impact Ionization Cross-Sections of CFx and NFx (x = 1 - 3)

The discrepancy between experimental and theoretical total electron-impact ionization cross sections for a group of fluorides, CFx, and NFx, (x = 1 - 3), is attributed to the inadequacies in previous theoretical models. Cross-sections calculated using a recently developed siBED (simulation Binary-Encounter-Dipole) model that takes into account the shielding of the long-range dipole potential between the scattering electron and target are in agreement with experimentation. The present study also carefully reanalyzed the previously reported experimental data to account for the possibility of incomplete collection of fragment ions and the presence of ion-pair formation channels. For NF3, our experimental and theoretical cross-sections compare well with the total ionization cross-sections recently reported by Haaland et al. in the region below dication formation.

Huo, Winifred M.↗
NASA NTRS2011

NASA's Lunar Atmosphere and Dust Environment Explorer (LADEE)

Nearly 40 years have passed since the last Apollo missions investigated the mysteries of the lunar atmosphere and the question of levitated lunar dust. The most important questions remain: what is the composition, structure and variability of the tenuous lunar exosphere? What are its origins, transport mechanisms, and loss processes? Is lofted lunar dust the cause of the horizon glow observed by the Surveyor missions and Apollo astronauts? How does such levitated dust arise and move, what is its density, and what is its ultimate fate? The US National Academy of Sciences/National Research Council decadal surveys and the recent "Scientific Context for Exploration of the Moon" (SCEM) reports have identified studies of the pristine state of the lunar atmosphere and dust environment as among the leading priorities for future lunar science missions. These measurements have become particularly important since recent observations by the Lunar Crater Observation and Sensing Satellite (LCROSS) mission point to significant amounts of water and other volatiles sequestered within polar lunar cold traps. Moreover Chandrayaan/M3, EPOXI and Cassini/VIMS have identified molecular water and hydroxyl on lunar surface regolith grains. Variability in concentration suggests these species are likely to be present in the exosphere, and thus constitute a source for the cold traps. NASA s Lunar Atmosphere and Dust Environment Explorer (LADEE) is currently under development to address these goals. LADEE will determine the composition of the lunar atmosphere and investigate the processes that control its distribution and variability, including sources, sinks, and surface interactions. LADEE will also determine whether dust is present in the lunar exosphere, and reveal its sources and variability. LADEE s results are relevant to surface boundary exospheres and dust processes throughout the solar system, will address questions regarding the origin and evolution of lunar volatiles, and will have implications for future exploration activities. LADEE will be the first mission based on the Ames Common Bus design. LADEE employs a high heritage instrument payload: a Neutral Mass Spectrometer (NMS), an Ultraviolet/Visible Spectrometer (UVS), and the Lunar Dust Experiment (LDEX). It will also carry a space terminal as part of the Lunar Laser Communication Demonstration (LLCD), which is a technology demonstration. LLCD will also supply a ground terminal. LLCD is funded by the Space Operations Mission Directorate (SOMD), managed by GSFC, and built by MIT Lincoln Lab. NMS was directed to the Goddard Space Flight Center (GSFC) and UVS to Ames Research Center (ARC). LDEX was selected through the Stand Alone Missions of Opportunity Notice (SALMON) Acquisition Process, and is provided by the University of Colorado at Boulder. The LADEE NMS covers a m/z range of 2-150 and draws its design from mass spectrometers developed at GSFC for the MSL/SAM, Cassini Orbiter, CONTOUR, and MAVEN missions. The UVS instrument is a next-generation, high-reliability version of the LCROSS UV-Vis spectrometer, spanning 250-800 nm wavelength, with high (<1 nm) spectral resolution. UVS will also perform dust occultation measurements via a solar viewer optic. LDEX senses dust impacts in situ, at LADEE orbital altitudes of 50 km and below, with a particle size range of between 100 nm and 5 micron. Dust particle impacts on a large hemispherical target create electron and ion pairs. The latter are focused and accelerated in an electric field and detected at a microchannel plate. LADEE is an important part of NASA s portfolio of near-term lunar missions; launch is planned for May, 2013. The lunar atmosphere is the most accessible example of a surface boundary exosphere, and may reveal the sources and cycling of volatiles. Dynamic dust activity must be accounted for in the design and operation of lunar surface operations.

Elphic, Richard↗
NASA NTRS2020

An Experimental Validation of a Revised Paschen's Law Relating to the ESD of Aerospace Vehicle Surfaces

This work seeks to experimentally validate a modified Paschen law which takes into account the effects of electron-ion pair removal between two electrodes within a dynamic gas medium. A test facility has been designed and fabricated in order to create supersonic flow conditions within the test section. Custom designed electrodes are mounted into the test section at desired gap distances. A power supply is utilized to charge the electrodes until discharge occurs. The discharge voltage of the electrode is recorded over a range of pressures within the test section. An operational pressure range is calculated using isentropic flow and normal shock relations at the desired Mach numbers. These values are plotted against the modified Paschen curve as a function of Mach number, electrode gap distance, and pressure as a means of validation.

ESD↗
DOE OSTI2023

Polyoxometalate derivatized metal oxide electrodes

A porous transparent electrode is formed where a film comprising of semiconducting nanoparticles is decorated with polyoxometalates (POMs) bonded to their surfaces. The semiconducting nanoparticles are transparent metal oxide. The semiconducting nanoparticles include tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), or titanium dioxide (TiO 2 ). In an embodiment, the POM is [SiW 12 O 40 ]L 4− ; [α-P 2 W 18 O 62 ] 6− ; or [α 2 -P 2 W 17 O 61 ] 10− . The semiconducting nanoparticles bond to the POM through a combination of electrostatic interactions and hydrogen bonds. The porous transparent electrode can be placed in a protonated form or ion-paired with alkali metal cations or tetraalkylammonium cations.

Dares, Christopher J.↗
DOE OSTI2023

Tutorial for Non-Orthogonal Configuration Interaction Fragment Studies Using GronOR

A brief tutorial is presented for the GronOR non-orthogonal configuration interaction application illustrating the download and build process, setting up calculations with OpenMolcas and GronOR, and a description of the file structure and input options. An overview of the computational workflow includes the generation of fragment wave functions and integrals with an adapted version of OpenMolcas, running GronOR calculations, and accounting for dynamic correlation corrections. Three end-to-end use cases are provided, representing a molecular dimer, an ion pair, and overlapping molecular fragments.

Straatsma, T.P.↗
DOE OSTI2024

EF-Hand Battle Royale: Hetero-ion Complexation in Lanmodulin

The lanmodulin (LanM) protein has emerged as an effective means for rare earth element (REE) extraction and separation from complex feedstocks without the use of organic solvents. Whereas the binding of LanM to individual REEs has been well characterized, little is known about the thermodynamics of mixed metal binding complexes (i.e., heterogeneous ion complexes), which limits the ability to accurately predict separation performance for a given metal ion mixture. In this paper, we employ the law of mass action to establish a theory of perfect cooperativity for LanM-REE complexation at the two highest-affinity binding sites. The theory is then used to derive an equation that explains the nonintuitive REE binding behavior of LanM, where separation factors for binary pairs of ions vary widely based on the ratio of ions in the aqueous phase, a phenomenon that is distinct from single-ion-binding chemical chelators. We then experimentally validate this theory and perform the first quantitative characterization of LanM complexation with heterogeneous ion pairs using resin-immobilized LanM. Importantly, the resulting homogeneous and heterogeneous constants enable accurate prediction of the equilibrium state of LanM in the presence of mixtures of up to 10 REEs, confirming that the perfect cooperativity model is an accurate mechanistic description of REE complexation by LanM. We further employ the model to simulate separation performance over a range of homogeneous and heterogeneous binding constants, revealing important insights into how mixed binding differentially impacts REE separations based on the relative positioning of the ion pairs within the lanthanide series. In addition to informing REE separation process optimization, these results provide mathematical and experimental insight into competition dynamics in other ubiquitous and medically relevant, cooperative binding proteins, such as calmodulin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Revisiting the π → π* transition of the nitrite ion at the air/water interface: A combined experimental and theoretical study

Broadband deep ultraviolet electronic sum frequency generation spectroscopy allows measurement of electronic |χ (2) | 2 -spectra at aqueous interfaces, providing considerable improvement over deep ultraviolet electronic second harmonic generation spectroscopy that yields error-prone, pointwise spectra. Reexamination of the π → π* transition of nitrite at the air/water interface reveals that the interfacial |χ (2) | 2 -spectrum is strikingly similar to the bulk absorption spectrum. Molecular dynamics simulations and SOS-CIS(D 0 ) electronic structure calculations provide no evidence for the previously reported contact ion pair-induced red-shift of the π → π* transition at the air/water interface. Finally, our results thus revise the previous description for nitrite interfacial adsorption as a contact ion pair.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Cross section for production of low-energy electron-positron pairs by relativistic heavy ions

Starting with the lowest-order unscreened QED matrix element for electron-positron pair production by heavy charged particles, the paper calculates the cross section for this process differential in all independent variables and valid for all pair energies small compared to the incident particle energy. Integration over the possible emission angles of one of the pair members gives an expression that is valid for low-energy pairs that can be compared with previous work based on the Weizsaecker-Williams method. Integration over the possible angles of the other pair member then yields an expression identical to one derived by Racah. The high energy-transfer limit of the expression for the cross section integrated over electron and positron angles is found to be identical to that of Kelner in the unscreened case.

Eby, P. B.↗
DOE OSTI2024

Heavy ion induced e + e − pair production: Theoretical and preliminary experimental efforts

The production of real e + e − pairs is an important quantum electrodynamics phenomenon, that could have significant implications on low energy heavy ion dynamics. Here, we employ an established Schwingerinspired theory to study this effect in nuclear disintegrations. We extend the current framework with a Monte Carlo approach to include non-perturbative contributions. Simultaneously, we supplement our study with a preliminary experimental procedure, via the use of the Global Spectrometer for Positron and Electron Characterization developed at the Texas Petawatt Laser facility of the University of Texas at Austin. Theory and experiment agree within one order of magnitude, which signals promise for further investigations.

Depastas, T.↗
DOE OSTI2024

Colloidal Stability of PFSA-Ionomer Dispersions. Part I. Single-Ion Electrostatic Interaction Potential Energies

Charged colloidal particles neutralized by a single counterion are increasingly important for many emerging technologies. Attention here is paid specifically to hydrogen fuel cells and water electrolyzers whose catalyst layers are manufactured from a perfluorinated sulfonic acid polymer (PFSA) suspended in aqueous/alcohol solutions. Partially dissolved PFSA aggregates, known collectively as ionomers, are stabilized by the electrostatic repulsion of overlapping diffuse double layers consisting of only protons dissociated from the suspended polymer. We denote such double layers containing no added electrolyte as "single ion". Size-distribution predictions build upon interparticle interaction potential energies from the Derjaguin-Landau-Verwey-Overbeek (DLVO) formalism. However, when only a single counterion is present in solution, classical DLVO electrostatic potential energies no longer apply. Accordingly, here a new formulation is proposed to describe how single-counterion diffuse double layers interact in colloidal suspensions. Part II (Srivastav, H.; Weber, A. Z.; Radke, C. J. Langmuir 2024 DOI: 10.1021/acs.langmuir.3c03904) of this contribution uses the new single-ion interaction energies to predict aggregated size distributions and the resulting solution pH of PFSA in mixtures of n-propanol and water. A single-counterion diffuse layer cannot reach an electrically neutral concentration far from a charged particle. Consequently, nowhere in the dispersion is the solvent neutral, and the diffuse layer emanating from one particle always experiences the presence of other particles (or walls). Thus, in addition to an intervening interparticle repulsive force, a backside osmotic force is always present. With this new construction, we establish that single-ion repulsive pair interaction energies are much larger than those of classical DLVO electrostatic potentials. The proposed single-ion electrostatic pair potential governs dramatic new dispersion behavior, including dispersions that are stable at a low volume fraction but unstable at a high volume fraction and finite volume-fraction dispersions that are unstable with fine particles but stable with coarse particles. Finally, the proposed single-counterion electrostatic pair potential provides a general expression for predicting colloidal behavior for any charged particle dispersion in ionizing solvents with no added electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Improved calculation of total cross section for pair production by relativistic heavy ions

A calculation of the total cross section for direct electron-positron pair production by heavy ions is described. It combines the use of the Weizsaecker-Williams method for low-energy transfers and existing calculations for high-energy transfers. Higher-order corrections to the total cross section are calculated based on the Weizsaecher-Williams method and existing results for pair production by photons.

Eby, P. B.↗