The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas
Not Available
Katsenovich, Yelena P.↗
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Comparing D-optimal designs with common mixture experimental designs for logistic regression
Mixture experiments are used in applications where the proportion of mixing components affects a response variable, such as in studies involving chemical formulations. In many applications, the response is dichotomous or binary (e.g., pass or fail) and a concern for researchers is how to efficiently and informatively design such experiments. A naive approach is to use design recommendations derived from linear normal-theory models with constant variance. In this research, we investigate the potential risks of such designs by comparing them to D-optimal mixture designs for binary responses and evaluating the D-efficiency of these design alternatives for several parameter subspaces. Standard designs for normal theory models generally do not work well for binary responses due to the tendency of these designs to favor boundary points. In addition, D-optimal mixture designs for binary responses tend to locate design points in the region where the magnitude of predicted response probabilities are moderate. Lastly, we recommend that researchers pay close attention to what is known about the characteristics of the underlying process models in selecting appropriate mixture designs for binary-response applications.
D-optimality↗
A method for direct, semi-quantitative analysis of gas phase samples using gas chromatography-inductively coupled plasma-mass spectrometry
A new and complete GC–ICP-MS method is described for direct analysis of trace metals in a gas phase process stream. The proposed method is derived from standard analytical procedures developed for ICP-MS, which are regularly exercised in standard ICP-MS laboratories. In order to implement the method, a series of empirical factors were generated to calibrate detector response with respect to a known concentration of an internal standard analyte. Calibrated responses are ultimately used to determine the concentration of metal analytes in a gas stream using a semi-quantitative algorithm. The method was verified using a traditional gas injection from a GC sampling valve and a standard gas mixture containing either a 1 ppm Xe + Kr mix with helium balance or 100 ppm Xe with helium balance. Data collected for Xe and Kr gas analytes revealed that agreement of 6–20% with the actual concentration can be expected for various experimental conditions. To demonstrate the method using a relevant “unknown” gas mixture, experiments were performed for continuous 4 and 7 hour periods using a Hg-containing sample gas that was co-introduced into the GC sample loop with the xenon gas standard. System performance and detector response to the dilute concentration of the internal standard were pre-determined, which allowed semi-quantitative evaluation of the analyte. The calculated analyte concentrations varied during the course of the 4 hour experiment, particularly during the first hour of the analysis where the actual Hg concentration was under predicted by up to 72%. Calculated concentration improved to within 30–60% for data collected after the first hour of the experiment. Similar results were seen during the 7 hour test with the deviation from the actual concentration being 11–81% during the first hour and then decreasing for the remaining period. The method detection limit (MDL) was determined for the mercury by injecting the sample gas into the system following a period of equilibration. The MDL for Hg was calculated as 6.8 μg · m -3 . This work describes the first complete GC–ICP-MS method to directly analyze gas phase samples, and detailed sample calculations and comparisons to conventional ICP-MS methods are provided.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
PhD Dissertation Proposal - Introduction to Dark Mix Concept: Gamma Measurements of Capsule Mixture
Presentation slides: Intro to Inertial Confinement Fusion; Types of Mixture in ICF capsules; Previous mixture experiments; Dark Mix Concept; Measuring Dark Mix with Gamma Cherenkov Detector; Dissertation Outline.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Workflow for Developing and Operating Subsurface Hydrogen Storage Facilities in Porous Reservoirs
Long-duration (seasonal) storage of natural gas (NG), which primarily consists of methane (CH 4 ), has been practiced for more than a hundred years at underground gas storage (UGS) facilities that use depleted hydrocarbon reservoirs, saline aquifers, and salt caverns. To enable hydrogen (H 2 ) to be used as a long-duration, energy-storage medium, similar facilities are envisioned for underground H 2 storage (UHS) of either H 2 or H 2 /NG mixtures. Experience with UGS can be used to guide recommended practices for developing and operating UHS facilities in porous reservoirs. The most important factors (formation/fluid properties and engineering choices) that influence the performance of UHS reservoirs have been identified and quantified in previous studies. These factors and choices influence phenomena that determine the sweep efficiency of the stored working gas. These phenomena include viscous fingering, hysteretic capillary trapping, and gravity override of the working gas, as well as the upconing of nonproductive fluid that determine the sweep efficiency of the stored working gas. This report describes initial recommended-practices and a project-development workflow for UHS facilities that utilize porous reservoirs, based on the current state-of-knowledge about H 2 behavior in the subsurface. The workflow sequentially addresses all aspects of UHS project development, including the identification of H 2 sources and users, site ranking and down-selection, geologic and reservoir-engineering characterization, reservoir design, testing, risk management, commissioning, operations, and monitoring for a UHS facility. The goal is to enable UHS facilities to be developed in an efficient and timely manner, while carefully managing project risks. This workflow is similar to that which has been developed for UGS facilities (see Figure 1 of API, 2022), with the addition of tasks and subtasks specific to H 2 and UHS. The project-development workflow is broken down into three major stages: (1) define the H 2 use case; (2) rank, down-select, and characterize potential, candidate UHS sites; and (3) reservoir design, integrity testing, risk assessment, commissioning, operations, and monitoring for selected UHS sites. Each major stage is further broken down into tasks and subtasks, which are described at a high level. This report also provides more detailed descriptions of all tasks and subtasks that involve reservoir analysis and testing.
08 HYDROGEN↗
Chemistry of fuel deposits and sediments and their predursors
The mechanism of solid deposit formation on hot engine parts from turbine fuels is investigated. Deposit formation is associated with oxidation of the hydrocarbon fuel. Therefore, oxidation rates and soluble gum formation were measured for several jet turbine fuels and pure hydrocarbon mixtures. Experiments were performed at 130 C using thermal initiation and at 100 C using ditertiary butyl peroxide as a chemical initiator. Correlation of the data shows that the ratio of rate of oxidation to rate of gum formation for a single fuel is not much affected by experimental conditions, even though there are differences in the abilities of different hydrocarbons to initiate and continue the oxidation. This indicates a close association of gum formation with the oxidation process. Oxidations of n-dodecane, tetralin and the more unstable jet fuels are autocatalytic, while those of 2-ethylnaphthalene and a stable jet fuel are self-retarding. However, the ratio of oxidation rate to gum formation rate appear to be nearly constant for each substrate. The effect of oxygen pressure on gum and oxidation formation was also studied. Dependence of gum formation on the concentration of initiator at 100 C is discussed and problems for future study are suggested.
Mayo, F. R.↗
Coarsening in Solid-liquid Mixtures: Overview of Experiments on Shuttle and ISS
The microgravity environment on the Shuttle and the International Space Station (ISS) provides the ideal condition to perform experiments on Coarsening in Solid-Liquid Mixtures (CSLM) as deleterious effects such as particle sedimentation and buoyancy-induced convection are suppressed. For an ideal system such as Lead-Tin in which all the thermophysical properties are known, the initial condition in microgravity of randomly dispersed particles with local clustering of solid Tin in eutectic liquid Lead-Tin matrix, permitted kinetic studies of competitive particle growth for a range of volume fractions. Verification that the quenching phase of the experiment had negligible effect of the spatial distribution of particles is shown through the computational solution of the dynamical equations of motion, thus insuring quench-free effects from the coarsened microstructure measurements. The low volume fraction experiments conducted on the Shuttle showed agreement with transient Ostwald ripening theory, and the steady-state requirement of LSW theory was not achieved. More recent experiments conducted on ISS with higher volume fractions have achieved steady-state condition and show that the kinetics follows the classical diffusion limited particle coarsening prediction and the measured 3D particle size distribution becomes broader as predicted from theory.
Ostwald ripening↗
European Space Agency experiments on thermodiffusion of fluid mixtures in space
In this paper, we describe the European Space Agency (ESA) experiments devoted to study thermodiffusion of fluid mixtures in microgravity environment, where sedimentation and convection do not affect the mass flow induced by the Soret effect. First, the experiments performed on binary mixtures in the IVIDIL and GRADFLEX experiments are described. Then, further experiments on ternary mixtures and complex fluids performed in DCMIX and planned to be performed in the context of the NEUF-DIX project are presented. Finally, multi-component mixtures studied in the SCCO project are detailed.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
What can be learned from optical two-color diffusion and thermodiffusion experiments on ternary fluid mixtures?
A number of optical techniques have been developed during the recent years for the investigation of diffusion and thermodiffusion in ternary fluid mixtures, both on ground and on-board the International Space Station. All these methods are based on the simultaneous measurement of refractive index changes at two different wavelengths. Here, we discuss and compare different techniques with the emphasis on optical beam deflection (OBD), optical digital interferometry, and thermal diffusion forced Rayleigh scattering (TDFRS). We suggest to formally split the data evaluation into a phenomenological parameterization of the measured transients and a subsequent transformation from the refractive index into the concentration space. In all experiments, the transients measured at two different detection wavelengths can be described by four amplitudes and two eigenvalues of the diffusion coefficient matrix. It turns out that these six parameters are subjected to large errors and cannot be determined reliably. Five good quantities, which can be determined with a high accuracy, are the stationary amplitudes, the initial slopes as defined in TDFRS experiments and by application of a heuristic criterion for similar curves, a certain mean diffusion coefficient. These amplitudes and slopes are directly linked to the Soret and thermodiffusion coefficients after transformation with the inverse contrast factor matrix, which is frequently ill-conditioned. Since only five out of six free parameters are reliably determined, including the single mean diffusion coefficient, the determination of the four entries of the diffusion matrix is not possible. We apply our results to new OBD measurements of the symmetric (mass fractions 0.33/0.33/0.33) ternary benchmark mixture n-dodecane/isobutylbenzene/1,2,3,4-tetrahydronaphthalene and existing literature data for the same system.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Simulation experiments using hydrogen/oxygen gas mixtures in a high pressure detonation tube
Simulation of rocket plumes and reentry aerothermodynamics using oxygen/hydrogen combustion products
Hopkins, H.↗
Chevron cutting: Experiment with new runway mixtures
Chevron cutting is shown to occur in different forms depending on the type of tire and the rubber on the running surface. Hardest wear is shown by the main tires of the B-747. Four defects occurred, in the form of two rip separation and two breakouts of the running surface. Tires capped by Thompson are more affected than any of the other rubber-capping fabrics. For Thompson tires, Chevron Cutting is greatly reduced with a fiberglass-rubber mixture. For Goodyear tires, it is eliminated with spiral wrap rubbercapping; resistance to damages through cuts seems to be more positive for Goodyear tires. For Mader tires, the extent of Chevron Cutting is generally smaller than for Thompson cappings.
Tyran, K.↗
Static and dynamic properties of multi-ionic plasma mixtures
Complex plasma mixtures with three or more components are often encountered in astrophysics or in inertial confinement fusion (ICF) experiments. For mixtures containing species with large differences in atomic number Z, the modeling needs to consider at the same time the kinetic theory for low-Z elements combined with the theory of strongly coupled plasma for high-Z elements, as well as all the intermediate situations that can appear in multi-component systems. For such cases, we study the pair distribution functions, self-diffusions, mutual diffusion and viscosity for ternary mixtures at extreme conditions. These quantities can be produced from first principles using orbital free molecular dynamics at the computational expense of very intensive simulations to reach good statistics. Utilizing the first-principles results as reference data, we assess the merit of a global analytic model for transport coefficients, "Pseudo-Ions in Jellium" (PIJ), based on an iso-electronic assumption (iso-n e ). With a multi-component hypernetted-chain integral equation, we verify the quality of the iso-n e prescription for describing the static structure of the mixtures. This semi-analytical modeling compares well with the simulation results and allows one to consider plasma mixtures not accessible to simulations. Further, applications are given for the mix of materials in ICF experiments. A reduction of a multicomponent mixture to an effective binary mixture is also established in the hydrodynamic limit and compared with PIJ estimations for ICF relevant mixtures.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
The DECLIC Research Facility - a Fertile Platform for NASA/CNES Scientific Collaboration
The DECLIC (Device for the Study of Critical Liquids and Crystalization) Facility was launched to the International Space Station (ISS) on Shuttle flight 17-A (August 2009) and has been in service for a little over three years. Activity from the three originally planned investigations, the HTI (High Temperature Insert) investigation, the ALI (Alice Like Insert) investigation and the DSI (Directional Solidication Insert) investigation has led to fruitful collaborations among a team of scientists, sponsored by NASA and CNES, to extend the utility of the inserts and the breadth of science beyond its initial scope. These follow-on investigations plan to use inserts that have been returned to earth for refurbishment, two of which (i.e., HTI-R and DSI-R) simply entail changing the test sample and the third (i.e., ALI-R) entails a slight hardware modication to allow for precise changes in sample volume. The first investigation, the Supercritical Water Mixture (SCWM) experiment, uses the refurbished HTI-R, which will accommodate a dilute aqueous mixture of Na2SO4 -0.5% w. This investigation will extend earlier observations of pure water at near-critical conditions. The second experiment uses a modified insert, the DSI-R, with a different concentration of succinonitrile-camphor than the original flight sample. This will allow, among other objectives, a detailed study of dendritic sidebranch formation in extended three-dimensional arrays, with the goal of elucidating whether noise amplication and/or a deterministic limit cycle is the main cause of sidebranch formation. The final experiment, the ALI-R, uses a sample cell with variable density to allow for additional observations of thermo-physical properties on SF6 at near critical conditions. The presentation will provide a discussion of the DECLIC facility's hardware, its modied inserts, and an overview of the extended science that will be achieved through these collaborative activities.
Hicks, Michael C.↗
GC/MS Method Development for Separating Lunar Volatile Ice Simulant Headspace Gases
Various investigators propose the lunar surface contains widely distributed volatiles, especially water- like species, i.e. OH and H2O. Surface volatiles are theorized to exist as a hydrated regolith layer, concentrated in extremely cold polar permanently shadowed regions (PSR), and/or solar wind implantation reservoirs in lunar glasses. The proposed sources of lunar surface volatiles range from cometary impacts, solar wind, or a supply present during moon formation. Future Artemis missions aim to collect and return the samples containing volatiles collected near lunar polar craters or PSRs. We, as advanced curation scientists, are responsible for developing techniques and methodologies for preserving returned sample integrity as much as possible. Pristine volatile-bearing samples are invaluable to the scientific community seeking to unravel the history of the solar system. Realistically, a sample will experience alteration during collection, transportation back to earth, and storage. The Planetary Exploration and Astromaterials Research Lab (PEARL) seeks to understand temperature and pressure effects on high-fidelity volatile-containing regolith simulants, the foundation for the future of cold curation. This abstract outlines the separation, identification, and quantification of headspace gases over volatile ice feed stock material using gas chromatography/mass spectrometry (GC/MS). Preliminary objectives concentrated on sample handling, reproducibility, and understanding the elution characteristics for each analyte. Initial GC/MS method development experiments utilized diluted static headspace sample preparation. Diluted samples were used because sampling headspace gases directly from a vial containing liquid analyte resulted in overloading of the column and detector. Overloading is evident based on chromatogram peak shapes and instrument contamination, or carry over, between experiments. A mixture of three alcohols were used for a majority of the sample handling and reproducibility studies. Reproducibility was tested via multiple users, calibration curves, and check standards. Stock solutions of condensed lunar volatile analytes included methanol, ammonia in methanol, hydrogen sulfide in water, and an equal volume mixture of methanol, ethanol, and isopropanol. Current samples use room air as the headspace sample matrix, however future experiments will incorporate an inert purge gas, such as argon or nitrogen. Three mL of each analyte solution were capped in separate 20 mL crimp top GC vials. Dilutions were carried out by removing an aliquot of headspace gases with a calibrated 1 mL gastight syringe and immediately transferring to a 20 mL capped crimp top vial. The GC/MS is a Thermo Fisher Trace 1310/ISQ 7000 with a TriPlus RSH autosampler and split/splitless injector module. The experiments outlined in this abstract use the following hardware: a 2.5 mL gastight headspace syringe tool, 1 mm ID x 78.5 mm length ultra-inert straight injection liner, and a TG-BondQ 30 m × 0.32 mm × 10 μm column. Various parameters, such as hardware selection and the temperature, pressure, and split ratio set points, continue to evolve as the overall experiment is refined. Diluted headspace chromatograms were collected for the individual stock solutions. Retention times, peak shapes, and mass spectra were evaluated and added to the data processing method for each molecule of interest. Figure 1 shows the total ion chromatograms for the three major lunar volatile simulant stock solutions: methanol, 7 N ammonia in methanol, and 0.4% hydrogen sulfide in water. Tailing peak shapes for ammonia (2.98 min rt) and water (4.06 min rt) indicate the molecules are not properly eluting from the selected column with the current separation method. Additionally, hydrogen sulfide and ammonia have overlapping peak windows, which could impact quantification. Ongoing experiments aim to address the peak shape and overlapping via the separation method and hardware selection. Sample preparation reproducibility experiments used stock solution containing equal volumes of a non- interactive mixture of methanol, ethanol, and isopropanol. Mass spectrum ion traces were used to identify and quantify all three alcohols. Peaks were automatically detected, identified, and integrated through the mass spectra detection and processing parameters. Calibration response curves and check standards were used to evaluate the validity of the sample preparation procedure. Figure 2 shows the methanol chromatogram peak area versus total headspace dilution volume transferred from the alcohol mixture vial. The calibration response curves and check standards validate sample preparation procedure. Continuing data analysis efforts are working towards correlating the peak area and instrument response factor to the headspace analyte concentration and condensed phase composition. Static headspace gas chromatography theory relies on Dalton’s law, Raoult’s law, Henry’s Law, and the Kolb and Ettre equation to associate peak area to the analyte composition in a non-ideal solution. Equation 1 is a simplified expression derived from the aforementioned theories. Future experiments involve liquid injections of the individual stock solutions, liquid and headspace analysis of various stock solution combinations, and the addition of regolith simulants to the mixtures. Temperature is another variable expected to affect reaction rates and will be explored.
Cecilia L. Amick↗
Airplane Ice Detector Based on a Microwave Transmission Line
An electronic instrument that could detect the potentially dangerous buildup of ice on an airplane wing is undergoing development. The instrument is based on a microwave transmission line configured as a capacitance probe: at selected spots, the transmission-line conductors are partly exposed to allow any ice and/or liquid water present at those spots to act as predominantly capacitive electrical loads on the transmission line. These loads change the input impedance of the transmission line, as measured at a suitable excitation frequency. Thus, it should be possible to infer the presence of ice and/or liquid water from measurements of the input impedance and/or electrical parameters related to the input impedance. The sensory transmission line is of the microstrip type and thus thin enough to be placed on an airplane wing without unduly disturbing airflow in flight. The sensory spots are small areas from which the upper layer of the microstrip has been removed to allow any liquid water or ice on the surface to reach the transmission line. The sensory spots are spaced at nominal open-circuit points, which are at intervals of a half wavelength (in the transmission line, not in air) at the excitation frequency. The excitation frequency used in the experiments has been 1 GHz, for which a half wavelength in the transmission line is .4 in. (.10 cm). The figure depicts a laboratory prototype of the instrument. The impedance-related quantities chosen for use in this version of the instrument are the magnitude and phase of the scattering parameter S11 as manifested in the in-phase (I ) and quadrature (Q) outputs of the phase detector. By careful layout of the transmission line (including the half-wavelength sensor spacing), one can ensure that the amplitude and phase of the input to the phase detector keep shifting in the same direction as ice forms on one or more of the sensor areas. Although only one transmission-line sensor strip is used in the laboratory version, in a practical application, it could be desirable to install multiple strips on different areas to detect localized icing. In that case, a multiplexer should be used to connect the various strips to the phase detector for sequential measurements. Experiments have been performed with freezing and thawing of water and of water/glycol mixtures. The experiments have shown that, whether or not glycol is present, it is possible to distinguish between liquid water and ice via the I and Q outputs; in particular, the equipment can be adjusted so that when water freezes, I decreases and Q increases. With respect to the operation of this instrument, the main effect of glycol is to increase the freezing or thawing time.
Ngo, Phong↗
Ensemble Shear Strength, Stability, and Permeability of Mixed Mineralogy Fault Gouge Recovered From 3D Granular Models
We conduct numerical shear experiments on mixtures of quartz and talc gouge using a three-dimensional (3D) distinct element model. A modified slip-weakening constitutive law is applied at contacts. We perform velocity-stepping experiments on both uniform and layered mixtures of quartz and talc analogs. We separately vary the proportion of talc in the uniform mixtures and talc layer thickness in the layered mixtures. Shear displacements are cycled through velocities of 1 and 10 μm/s. We follow the resulting evolution of ensemble shear strength, slip stability, and permeability of the gouge mixture and explore the mesoscopic mechanisms. Simulation results show that talc has a strong weakening effect on shear strength—a thin shear-parallel layer of talc (three particles wide) can induce significant weakening. However, the model offsets laboratory-derived strong weakening effects of talc observed in uniform mixtures, implying the governing mechanisms may be the shear localization effect of talc, which is enhanced by its natural platy shape or preimposed layered structure. Ensemble stability (a – b ) can be enhanced by increasing talc content in uniform talc-quartz mixtures. Reactivation-induced permeability increase is amplified with increased quartz content before the maturation of shear localization. Postmaturation permeability enhances on velocity upsteps and diminishes on velocity downsteps. Talc enhances compaction at velocity downsteps, potentially reducing fault permeability. Evolution trends of stability relating to the composition and structure of the fault gouge are straightforwardly obtained from the 3D simulation. Local friction evolution indicates that talc preferentially organizes and localizes in the shear zone, dominating the shear strength and frictional stability of faults
58 GEOSCIENCES↗
SiO 2 –SiC Mixtures at High Pressures and Temperatures: Implications for Planetary Bodies Containing SiC
We present results from high–pressure and high–temperature experiments on mixtures of SiC and SiO 2 to explore the stability of SiC in the presence of oxygen–rich silicates at planetary mantle conditions. We observe no evidence of the ambient pressure predicted oxidation products, CO or SiO, resulting from oxidation reactions between SiC and SiO 2 at pressures up to ~40 GPa and temperatures up to ~2500 K. We observe the decomposition of SiC through releasing C, resulting in vacancies in the SiC lattice and consequently the contracted SiC ambient volume V0 observed in the heated regions of sample. The decomposition is further supported by the observations of diamond formation and the expanded SiO 2 V0 in the heated regions of samples indicating the incorporation of C into SiO2 stishovite. We provide a new interpretation of SiC decomposition on laboratory timescales, in which kinetics prevent the reaction from reaching equilibrium. We consider how the equilibrium decomposition reaction of SiC will influence the differentiation of a SiC–containing body on planetary timescales and find that the decomposition products may become isolated during early planetary differentiation. Here, the resulting presence of elemental Si and C within a planetary body may have important consequences for the compositions of the mantles and atmospheres of such planets.
36 MATERIALS SCIENCE↗