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At least 307 records · Page 17

Complete Initial Evaluation of Novel Complexants for Tc Holdback for Simplified Single Cycle Separations.

Management of technetium at the back end of nuclear fuel cycle is complicated by its unique physico-chemical character, but must be addressed to due to the environmental, storage and reprocessing challenges of this fission product. In a single-cycle scenario, the recovery and purification of uranium is particularly challenging due to the tendency of a pertechnetate anion to follow uranyl cation. This report summarizes initial studies directed towards finding the solution for technetium management. Two options for controlling technetium’s chemistry in solvent extraction scenarios were studied. Molecular recognition of pertechnetate by aqueous complexants based on guanidinium moieties was compared to redox manipulation of technetium using dihydrazide reagents. Solvent extraction, potentiometric and nuclear magnetic resonance spectroscopy studies were performed. The influence of guanidinium reagents on the liquid-liquid partitioning of technetium is less pronounced, relative to dihydrazides. Strong impact exerted by dihydrazides originates from the technetium-catalyzed decomposition of such compounds which reduces technetium to a tetravalent, non-extractable state. Although this route of technetium management is very effective the destruction of dihydrazides is undesirable. Guanidinium complexants show a more tempered influence on technetium. The effect on the liquid-liquid partitioning of pertechnetate is evident and likely guided by anion recognition due to ion-pair and hydrogen bond formation. Guanidiniums are stable in presence of technetium as evidenced by nuclear magnetic resonance studies. The steady state chemistry of guanidiniums identify this class of aqueous complexants as solid candidates for structure-function pertechnetate recognition studies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Integrated Direct Air Capture and H₂-Free CO₂ Valorization

This project advances fundamental understanding of a novel integrated direct air capture (DAC) and CO₂ conversion process that valorizes atmospheric CO₂ without external H₂. The research encompasses four critical components: (1) design of task-specific ionic liquids for efficient CO₂ capture under ambient conditions, (2) development of H₂-free tandem catalytic systems using ethane as a reductant, (3) advanced operando characterization to elucidate capture and conversion mechanisms, and (4) data science-driven predictive computation to accelerate material discovery. Over the project period, we developed five high-performance DAC sorbent systems—including CaO/superbase ionic liquid composites, Ni-MOF/Ionic Liquid (IL) hybrids, fluorinated covalent organic frameworks with ion-pair functional groups, defect-engineered UiO-66, and a validated kinetic model for humid-condition operation, achieving CO₂ capacities up to 1.86 mmol/g at 400 ppm with excellent cycling stability. For H₂-free conversion, we constructed atomically synergistic Zn–O–Cr binuclear catalytic sites that achieve 100% ethylene selectivity, ~9.6% ethane conversion, and 99% CO₂ utilization in equimolar co-conversion of ethane and CO₂. We further demonstrated downstream valorization pathways converting CO and C₂H₄ into polyketones and C₃ chemicals. These advances strengthen the scientific foundation for producing value-added materials from ambient CO₂.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion chambers simplify absolute intensity measurements in the vacuum ultraviolet

Single or double ion chamber technique measures absolute radiation intensities in the extreme vacuum ultraviolet region of the spectrum. The ion chambers use rare gases as the ion carrier. Photon absorbed by the gas creates one ion pair so a measure of these is a measure of the number of incident photons.

Sampson, J. A. R.↗

Four pi-recoil proportional counter used as neutron spectrometer

Study considers problems encountered in using 4 pi-recoil counters for neutron spectra measurement. Emphasis is placed on calibration, shape discrimination, variation of W, the average energy loss per ion pair, and the effects of differentiation on the intrinsic counter resolution.

Bennett, E. F.↗

Degradation and recovery mechanisms in lithium-doped solar cells

Several groups of lithium-doped solar cells have been evaluated under 1-MeV electron irradiation. Many of these groups indicated superior electrical output after irradiation and recovery as compared to similarly irradiated n/p solar cells. The superior cells are those with lithium concentrations of 2 to 5 x 10 to the 14th power atoms per cu cm at the junction. An irradiation of lithium-doped cells with 28-MeV electrons indicated a tenfold advantage of lithium-doped cells over n/p cells. Studies of the changes in the lithium concentration during recovery have shown the amounts of lithium reacting is highly nonlinear in regard to the electron fluence and varies greatly with distance from the junction. The results indicate that precipitation of lithium on radiation defects may be the cause of recovery rather than ion pairing.

Downing, R. G.↗

Electron deposition in water vapor, with atmospheric applications.

Examination of the consequences of electron impact on water vapor in terms of the microscopic details of excitation, dissociation, ionization, and combinations of these processes. Basic electron-impact cross-section data are assembled in many forms and are incorporated into semianalytic functions suitable for analysis with digital computers. Energy deposition in water vapor is discussed, and the energy loss function is presented, along with the 'electron volts per ion pair' and the efficiencies of energy loss in various processes. Several applications of electron and water-vapor interactions in the atmospheric sciences are considered, in particular, H2O comets, aurora and airglow, and lightning.

Olivero, J. J.↗

Electron energy deposition in CO2.

Semiempirical cross sections of Strickland and Green (1969) are compared with and supplemented by more recent data. The composite set is used in the energy degradation calculation of electrons with emphasis on energies below 100 ev. Good agreements are obtained with accepted values of the loss function and the average electron volts per ion pair at high energies. Efficiencies associated with various loss channels are obtained. The relationship with the recent Mariner UV data is discussed.

Sawada, T.↗

Ionization sources of the ionospheric D and E regions.

Solar radiation in the extreme ultraviolet, lambda less than 1216 A, and X-ray regions of the spectrum is deposited between 60 and 200 km producing free electrons and ions. Below 60 km cosmic radiation creates ion pairs. Energetic electron precipitation, as during auroral events, creates additional ionization as do protons originating from solar flares, which also enhance solar X-ray and extreme ultraviolet emission. At night scattered solar Lyman alpha (1216 A) and Lyman beta (1026 A) as well as He I (584 A) and He II (304 A) are present. These and other lesser known sources, for example cosmic X-ray and extreme ultraviolet radiation, contribute to the formation of the nocturnal D and E regions.

Aikin, A. C.↗

Design, performance, and calculated error of a Faraday cup for absolute beam current measurements of 600-MeV protons

A mobile self-contained Faraday cup system for beam current measurments of nominal 600 MeV protons was designed, constructed, and used at the NASA Space Radiation Effects Laboratory. The cup is of reentrant design with a length of 106.7 cm and an outside diameter of 20.32 cm. The inner diameter is 15.24 cm and the base thickness is 30.48 cm. The primary absorber is commercially available lead hermetically sealed in a 0.32-cm-thick copper jacket. Several possible systematic errors in using the cup are evaluated. The largest source of error arises from high-energy electrons which are ejected from the entrance window and enter the cup. A total systematic error of -0.83 percent is calculated to be the decrease from the true current value. From data obtained in calibrating helium-filled ion chambers with the Faraday cup, the mean energy required to produce one ion pair in helium is found to be 30.76 + or - 0.95 eV for nominal 600 MeV protons. This value agrees well, within experimental error, with reported values of 29.9 eV and 30.2 eV.

Beck, S. M.↗

Chemical analysis of LARC-160 polyimide

As part of a detailed NASA-sponsored study of chemical composition/property sensitivity of the LARC-160 polymerization of monomeric reactants (PMR) polyimide system, a number of liquid chromatographic techniques have been employed. The ester monomers in this system are characterized by a reverse-phase ion-suppression method. Mono, di, and triesters of the 3,3',4,4'-benzophenonetetracarboxylic acid ingredient are identified and their isomeric forms resolved. The 5-norbornene-2,3-dicarboxylic acid ester (nadic ester) endcapper is detected by low wavelength ultraviolet sensing. A second method, reverse-phase ion-pair chromatography, is employed for determining unreacted amines. The extent of resin B-staging is monitored through analysis of the ester/amine oligomers.

Dynes, P. J.↗

A Method for Characterizing PMR-15 Resin

Quantitative analysis technique based on reverse-phase, highperformance liquid chromatography (HPLC) and paired-ion chromatography (PIC) developed for PMR-15 resins. In reverse-phase HPLC experiment, polar solvent containing material to be analyzed passed through column packed with nonpolar substrate. Composition of PMR-15 Resin of 50 weight percent changes as resin ages at room temperature. Verification of proper resin formulation and analysis of changes in resin composition during storage important to manufacturers of PMR-15 polymer matrix composite parts. Technique especially suitable for commercial use by manufacturers of high-performance composite components.

Roberts, G. D.↗

Solar flare ionization in the mesosphere observed by coherent-scatter radar

The coherent-scatter technique, as used with the Urbana radar, is able to measure relative changes in electron density at one altitude during the progress of a solar flare when that altitude contains a statistically steady turbulent layer. This work describes the analysis of Urbana coherent-scatter data from the times of 13 solar flares in the period from 1978 to 1983. Previous methods of measuring electron density changes in the D-region are summarized. Models of X-ray spectra, photoionization rates, and ion-recombination reaction schemes are reviewed. The coherent-scatter technique is briefly described, and a model is developed which relates changes in scattered power to changes in electron density. An analysis technique is developed using X-ray flux data from geostationary satellites and coherent scatter data from the Urbana radar which empirically distinguishes between proposed D-region ion-chemical schemes, and estimates the nonflare ion-pair production rate.

Parker, J. W.↗

Non-enzymatic synthesis of the coenzymes, uridine diphosphate glucose and cytidine diphosphate choline, and other phosphorylated metabolic intermediates

Using urea and cyanamide, the two condensing agents considered to have been present on the primitive earth, uridine diphosphate glucose (UDPG), cytidine diphosphate choline (CDP-choline), glucose-1-phosphate (G1P), and glucose-6-phosphate (G6P) were synthesized under simulated prebiotic conditions. The reaction products were separated and identified using paper chromatography, thin layer chromatography, enzymatic analyses, and ion-pair reverse-phase high performance liquid chromatography. The possibility of nonenzymatic synthesis of metabolic intermediates on the primitive earth from simple precursors was thus demonstrated.

Mar, A.↗

Effect of solar proton events in 1978 and 1979 on the odd nitrogen abundance in the middle atmosphere

Daily average solar proton flux data for 1978 and 1979 are used in a proton energy degradation scheme to derive ion pair production rates and atomic nitrogen production rates. The latter are computed in a form suitable for inclusion in an atmopheric, two-dimensional, time-dependent photochemical model. Odd nitrogen distributions are computed from the model, including atomic nitrogen production from solar protons, and are compared with baseline distributions. The comparisons show that the average effect of the solar protons in 1978 and 1979 was to cause changes in odd nitrogen only above 10 mbar and at latitudes only above about 50 deg in both hemispheres. The influence of the solar proton-produced odd nitrogen on the local abundance of odd nitrogen depends primarily on the background odd nitrogen abundance as well as the altitude and season.

Jackman, Charles H.↗

Development of liquid xenon detectors for gamma ray astronomy

The application of liquid xenon in high-resolution detectors for gamma-ray astronomy is being investigated. Initial results from a pulse-shape analysis of ionization signals in a liquid-xenon gridded chamber indicate that it is possible to achieve the necessary liquid purity for the transport of free electrons with simple techniques. The energy resolution has been measured as a function of applied electric field, using electrons and gamma-rays from a 207Bi source. At a field of 12 kV/cm the noise-substracted energy resolution of the dominant 569-keV gamma-ray line is 34 keV FWHM (full width at half maximum). This value is mostly determined by recombination of electron-ion pairs on delta-electron tracks.

Aprile, Elena↗

Effect of solar proton events on the middle atmosphere during the past two solar cycles as computed using a two-dimensional model

This paper investigates the effects of solar proton events (SPEs) on the middle atmosphere during the past two solar cycles (1963-1984), by examining changes in the production of odd nitrogen, NO(y), and ozone and using a proton energy degradation scheme to derive ion pair production rates. These calculations show that NO(y) is not substantially changed over a solar cycle by SPEs; significant SPEs last only 1-5 days, tend to occur near solar maximum, and are typically months to years apart, preventing a build up of SPE-produced NO(y). Fractional ozone changes are even smaller than the fractional NO(y) changes and are significant only for the August 1972 SPE. Ozone, like NO(y), returns to its ambient levels on time scales of several months to a year.

Jackman, Charles H.↗

Auroral modeling of the 3371 A emission rate - Dependence on characteristic electron energy

An efficient two-stream auroral electron model is used to study the deposition of auroral energy and the dependence of auroral emission rates on characteristic energy. This model incorporates the concept of average energy loss to reduce the computation time. This simple two-stream model produces integrated emission rates that are in excellent agreement with the much more complex multistream model of Strickland et al. (1983) but disagrees with a recent study by Rees and Lummerzheim (1989) that indicates that the N2 second positive emission rate is a strongly decreasing function of the characteristic energy of the precipitating flux. These calculations reveal that a 10 keV electron will undergo approximately 160 ionizing collisions, with an average energy loss per collision of 62 eV before thermalizing. The secondary electrons are created with an average energy of 42 eV. When all processes including the backscattered escape fluxes are taken into account, the average energy loss per electron-ion pair is 35 eV in good agreement with laboratory results.

Richards, P. G.↗