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IDAES-PSE 2.4.0 Release

The Institute for the Design of Advanced Energy Systems (IDAES) Integrated Platform is a versatile computational environment offering extensive process systems engineering (PSE) capabilities for optimizing the design and operation of complex, interacting technologies and systems. IDAES enables users to efficiently search vast, complex design spaces to discover the lowest cost, most environmentally sustainable solutions while supporting the full process modeling lifecycle, from conceptual design to dynamic optimization and control. The extensible, open platform empowers users to create models of novel processes and rapidly develop custom analyses, workflows, and end-user applications.. Deprecations • Convergence Analysis tool (idaes/core/util/convergence): deprecated in favor of new Parameter Sweep tools. To be removed in v3.0.0. New Beta Capabilities • Parameter Sweep Tool (idaes.core.util.parameter_sweep) o A new API for defining and performing parameter sweep studies on IDAES models has been developed • Diagnostics Tools (idaes.core.util.model_diagnostics) o New methods for identifying duplicate variables and constraints have been added to the diagnostics toolbox o New tools for detecting ill conditioning in Jacobians have been developed and are available in the model_diagnostics module. These provide alternatives to the existing DegeneracyHunter toolbox, and will eventually be merged with this capability, but initial working versions have been provided as beta capabilities for interested users o IpoptConvergenceAnalysis (replaces deprecated Convergence Analysis tool):  A new tool for performing convergence analysis studies that leverages the new Parameter Sweep tools has been developed. This tool allows users to define the input parameters to their model and sampling methods for these (leveraging Pysmo's sampling tools) and to then solve their model across the sampled domains and return a summary of the solver performance (IPOPT only) Improved Models • Thickener model (idaes.models.unit_models.solid_liquid.thickener) o Improved model to include predictive correlations for unit sizing based on settling velocity measurements (steady-state only) • Modular Property Packages o Added general support for calculating critical properties of mixtures using defined Equation of State modules. New API defined for Equation of State modules in order to define the necessary constraints for calculating critical properties (most EoS modules DO NOT support calculation of critical properties (yet)) o Added new methods to Cubic Equation of State module to support calculation of critical properties

DiagnosticsToolbox↗

Properties of the highly ionized disk and halo gas toward two distant high-latitude stars

Goddard High Resolution Spectrograph (GHRS) intermediate -resolution observations of S III, Si III, Al III, Si IV, C IV, and N V absorption along the sight lines to HD 18100 (l = 217.9 deg, b = -62.7, d = 3.1 kpc, z = -2.8 kpc) and HD 100340 (l = 258.9 deg, b = +61.2 deg, d = 5.3 kpc, z = 4.6 kpc) are presented. These small science aperture spectra have resolutions ranging from 11 to 20 km/s full width at half maximum (FWHM) and S/N from 30 to 65 per diode substep. Strong absorption by moderately and highly ionized gas is seen in each direction. The absorption in the direction of the south Galactic polar region (HD 18100) is kinematically simple, while the absorption in the direction of north Galactic polar region (HD 100304) is kinematically complex. In each case the absorption by the highly ionized gas lies within the velocity range of absorption by neutral and weakly ionized gas. Along each sight line, the velocity dispersion determined from the unsaturated absorption lines increases with the energy required to create each ion. The logarithmic column densities for Al III, Si IV, C IV, and N V are log N(atoms/sq cm = 12.71, 13.10, 13.58, and 12.75 toward HD 18100 and log N = 12.88, 13.31, 13.83, and 13.04 toward HD 100340. Average ionic ratios among these species are very similar along the two sight lines. Differences in profile shape between the absorption for AL II, Si IV, C IV, and N V provide additional support for the claim of Savage, Sembach, & Cardelli (1994) that there exists two types of highly ionized gas in the interstellar medium. One type of highly ionized gas is responsible for the structured Si IV absorption and part of the C IV absorption. In this gas N(C IV)/N(Si IV) approximately 3.0 and N(C IV)/N(N V) greater than 6. The absorption by this gas seems to be associated with some type of self-regulating interface or mixing layer between the warm and hot interstellar medium. The other type of highly ionized gas is responsible for most of the N V absorption, part of the C IV absorption, and has very little associated Si IV absorption. In this gas N(C IV)/N(N V) is approximately 1 to 3. This gas is hot (T greater than 2 x 10(exp 5) K) and may be tracing the cooling gas of supernova (SN) bubbles or a Galactic fountain. The relative mixture of these two types of highly ionized gas varies from one sight line to the next. The two sight lines in this study sample halo gas in the solar neighborhood and have a smaller percentage of the more highly ionized gas than inner Galaxy sight lines.

Savage, Blair D.↗

Development of a Testbed for Pipeline Flushing - 20425

Pipelines which carry high-level waste within the DOE complex should be properly flushed in the cases where stationary or moving beds of solid sediment occur, or lines are prone to hydrogen gas buildup. Present guidelines establish a minimum for the amount of water (flush volume) and flush velocity values used for post-transfer flushing operations to achieve satisfactory cleaning of pipelines. However, further studies are needed to find optimal operating velocity modes/values in order to minimizing the flush volume and consequent downstream waste. These efforts are significantly helpful to DOE waste remediation sites by preserving tank storage, preventing additional waste processing, and minimizing dilution and changes in waste chemistry. An experimental test loop was recently developed for study of non-Newtonian slurry flushing at the Florida International University (FIU). This loop was designed to create sediment beds of various materials and bed heights and investigate parameters that effect the efficiency of flushing operations. The objective is to find flush velocity values/modes which lead to satisfactory cleaning of transport lines with a minimum amount of water usage. A 165 ft experimental test loop made of 3-inch carbon steel pipes was constructed and used in initial testing campaigns. This pipe loop was equipped with real-time monitoring instruments to record variation of pressure, density, mass flow rate, and temperature during testing. Post-flush in-situ no-flow evaluations were performed using ultrasonic, endoscopy, and visual inspection. Additional post-flush evaluations were conducted using filtration and density monitoring of residuals within a designated circulations loop. These provisions enable comparison of pipeline cleanness before the start and after termination of flushing operations for efficiency evaluation. This paper presents efforts associated with flushing of kaolin-water mixtures at different concentrations and with various flush volume and flush velocity values/modes. In initial testing, efforts focused on creating repeatable sediment beds inside the pipeline in both fully-flooded (no pre-flush drainage) and gravity-drained (pre-flush drained) systems. Bed characterization (i.e., measurement of sediment height and solids concentration) was conducted to ensure about consistency of initial conditions between tests. Preliminary results for flushing study of 10% vol. kaolin-water mixtures starting from a fully-flooded initial condition showed that flushing with 1-line volume (65 gallons) could remove up to 72 percent of solids from the pipeline. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Rhenium-Sulfido and -Dithiolato Corroles: Reflections on Chalcophilicity

The high-temperature (~180 °C) reaction between free-base meso-triarylcorroles and Re 2 (CO) 10 , followed by exposure to PCl 3 and thiols (or elemental sulfur), affords rhenium-sulfido (ReS) corroles in 67-76% yields. The use of shorter reaction times, lower temperatures (~130 °C), and a dithiol (e.g., ethane-1,2-dithiol) also allows the isolation of rhenium-dithiolato corroles, presumptive intermediates on the path to ReS corroles. The ReS corroles exhibit high thermal stability and two reversible oxidations and reductions in their cyclic voltammograms, with redox potentials nearly identical to those observed for analogous ReO corroles. The electrochemical HOMO-LUMO gaps of the complexes, at 2.2 eV, are consistent with ligand-centered oxidation and reduction. The UV-vis spectra of ReS corroles, on the other hand, differ significantly from those of their ReO counterparts. Scalar-relativistic DFT calculations suggest that this difference reflects low-energy LUMO+2 and LUMO+3 levels, consisting of Re-S π-antibonding interactions; the ReO corroles, in contrast, exhibit a larger LUMO+1/LUMO+2 gap, as expected for a relatively classical Gouterman-type metalloporphyrin analogue. The high stability of ReS corroles is consistent with geochemists' view of rhenium as a moderately chalcophilic element (i.e., one that partitions into sulfide melts) as well as with a recent quantitative analysis of thiophilicity, which indicates that rhenium's oxophilicity and thiophilicity are essentially evenly balanced.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of Hydrodynamic (Landau) Instability in Liquid-Propellant Combustion at Normal and Reduced Gravity

The burning of liquid propellants is a fundamental combustion problem that is applicable to various types of propulsion and energetic systems. The deflagration process is often rather complex, with vaporization and pyrolysis occurring at the liquid/gas interface and distributed combustion occurring either in the gas phase or in a spray. Nonetheless, there are realistic limiting cases in which combustion may be approximated by an overall reaction at the liquid/gas interface. In one such limit, the gas flame occurs under near-breakaway conditions, exerting little thermal or hydrodynamic influence on the burning propellant. In another such limit, distributed combustion occurs in an intrusive regime, the reaction zone lying closer to the liquid/gas interface than the length scale of any disturbance of interest. Finally, the liquid propellant may simply undergo exothermic decomposition at the surface without any significant distributed combustion, such as appears to occur in some types of HydroxylAmmonium Nitrate (HAN)-based liquid propellants at low pressures. Such limiting models have recently been formulated,thereby significantly generalizing earlier classical models that were originally introduced to study the hydrodynamic stability of a reactive liquid/gas interface. In all of these investigations, gravity appears explicitly and plays a significant role, along with surface tension, viscosity, and, in the more recent models, certain reaction-rate parameters associated with the pressure and temperature sensitivities of the reaction itself. In particular, these parameters determine the stability of the deflagration with respect to not only classical hydrodynamic disturbances, but also with respect to reactive/diffusive influences as well. Indeed, the inverse Froude number, representing the ratio of buoyant to inertial forces, appears explicitly in all of these models, and consequently, in the dispersion relation that determines the neutral stability boundaries beyond which steady, planar burning is unstable to nonsteady, and/or nonplanar (cellular) modes of burning. These instabilities thus lead to a number of interesting phenomena, such as the sloshing type of waves that have been observed in mixtures of HAN and TriEthanolAmmonium Nitrate (TEAN) with water. Although the Froude number was treated as an O(1) quantity in these studies, the limit of small inverse Froude number corresponding to the microgravity regime is increasingly of interest and can be treated explicitly, leading to various limiting forms of the models, the neutral stability boundaries, and, ultimately, the evolution equations that govern the nonlinear dynamics of the propagating reaction front. In the present work, we formally exploit this limiting parameter regime to compare some of the features of hydrodynamic instability of liquid-propellant combustion at reduced gravity with the same phenomenon at normal gravity.

Margolis, Stephen B.↗

Premixed Atmosphere and Convection Influences on Flame Inhibition and Combustion (Pacific)

Flame spread over flat solid fuel beds is a useful paradigm for studying the behavior of more complex two-phase nonpremixed flames. For practical applications, two of the most important elements of flame spreading are the effects of (1) the ambient atmosphere (e.g. pressure and composition) and (2) the flow environment on the spread rate and extinction conditions. Concerning (1), studies of flame spread in vitiated air and non-standard atmospheres such as those found in undersea vessels and spacecraft are particularly important for the assessment of fire hazards in these environments as well as determination of the effectiveness of fire suppressants. Concerning (2), the flow environment may vary widely even when no forced flow is present because of buoyancy effects. Consequently, the goal of this work is to employ microgravity (micro g) experiments to extend previous studies of the effects of ambient atmosphere and the flow environment on flame spread through the use of microgravity (micro g) experiments. Because of the considerable differences between upward (concurrent-flow) and downward (opposed-flow) flame spread at 1g (Williams, 1976, Fernandez-Pello, 1984), in this work both upward and downward 1g spread are tested. Two types of changes to the oxidizing atmosphere are considered in this work. One is the addition of sub-flammability-limit concentrations of a gaseous fuel ('partially premixed' atmospheres). This is of interest because in fires in enclosures, combustion may occur under poorly ventilated conditions, so that oxygen is partially depleted from the air and is replaced by combustible gases such as fuel vapors, H2 or CO. Subsequent fire spread over the solid fuel could occur under conditions of varying oxygen and gaseous fuel content. The potential significance of flame spread under vitiated or partially premixed conditions has been noted previously (Beyler, 1984). The second change is the diluent type, which affects the radiative properties of the mixture as well as the Lewis number (Le) of the reactants in the atmosphere, which for oxygen is defined as the thermal diffusivity of the bulk mixture divided by the mass diffusivity of oxygen into the bulk mixture. Understanding the effect of diluent type is desirable because in some undersea and spaceborne habitations, it is desirable to use diluent gases other than nitrogen. Prior experiments have shown that both radiation (Bhattacharjee and Altenkirch, 1993) and Lewis number (Zhang et al, 1992) effects are important in flame spreading problems.

Honda, Linton K.↗

Learning for Autonomous Navigation

Robotic ground vehicles for outdoor applications have achieved some remarkable successes, notably in autonomous highway following (Dickmanns, 1987), planetary exploration (1), and off-road navigation on Earth (1). Nevertheless, major challenges remain to enable reliable, high-speed, autonomous navigation in a wide variety of complex, off-road terrain. 3-D perception of terrain geometry with imaging range sensors is the mainstay of off-road driving systems. However, the stopping distance at high speed exceeds the effective lookahead distance of existing range sensors. Prospects for extending the range of 3-D sensors is strongly limited by sensor physics, eye safety of lasers, and related issues. Range sensor limitations also allow vehicles to enter large cul-de-sacs even at low speed, leading to long detours. Moreover, sensing only terrain geometry fails to reveal mechanical properties of terrain that are critical to assessing its traversability, such as potential for slippage, sinkage, and the degree of compliance of potential obstacles. Rovers in the Mars Exploration Rover (MER) mission have got stuck in sand dunes and experienced significant downhill slippage in the vicinity of large rock hazards. Earth-based off-road robots today have very limited ability to discriminate traversable vegetation from non-traversable vegetation or rough ground. It is impossible today to preprogram a system with knowledge of these properties for all types of terrain and weather conditions that might be encountered.

mixture of Gaussians↗

Soot Aerosol In The Atmosphere: Pole-to-Pole Distribution And Contributions by Aircraft

Interest in the distribution of black carbon (soot) aerosol (BCA) in the atmosphere is warranted for the following reasons: (1) BCA has the highest absorption cross section of any compound known, thus it can absorb solar radiation to cause atmospheric warming; (2) BCA is a strong adsorber of gases, thus it can catalyze heterogeneous chemical reactions to modify the chemical composition of the atmosphere; (3) If aircraft emission is the major source of atmospheric BCA, it can serve as an atmospheric tracer of aircraft exhaust. We collect BCA particles greater than or equal to 0.02 micrometer diameter by wires mounted on both the DC-8 and ER-2 aircraft. After return to the laboratory, the wires are examined with a field emission scanning electron microscope to identify BCA particles by their characteristic morphology. Typically, BCA exists in the atmosphere as small particles of complex morphology. The particle sizes at the source are measured in tens of Angstrom units; after a short residence time in the atmosphere, individual particles coalesce to loosely packed agglomerates of typical dimensions 0.01 to 0.1 micrometer. We approximate the size of each BCA aggregate by that of a sphere of equivalent volume. This is done by computing the volume of a sphere whose diameter is the mean between averaged minimum and maximum dimensions of the BCA particle. While this procedure probably underestimates the actual surface area, it permits us to compare BCA size distributions among themselves and with other types of aerosols. When statistically justified, we fit lognormal distributions to the data points to determine number concentrations, geometric mean radii, standard deviations, BCA surface areas and volumes. Results to date permit the following conclusions: (1) BCA concentration in the northern stratosphere averages 0.6 ng per cubic meters. This amount is one part in 10(exp 4) after a volcanic eruption (e.g., Pinatubo) increasing to about one percent during volcanic quiescence. In the northern troposphere, BCA concentration averages 3.2 ng per cubic meters, or 0.3 percent of the background aerosol. (2) Applying an BCA emission index EI(BCA)=5 x 10(exp -5), measured in the exhaust wake of a Concorde supersonic jet aircraft, to realistic estimates of fuel burnt by the current and projected fleets permits us to conclude that: (i) Most BCA in the northern stratosphere results from aircraft emissions; (ii) Most BCA in the northern troposphere results from other sources than aircraft; (iii) A projected supersonic fleet will increase the northern stratospheric BCA concentration by one order of magnitude, unless the emission index is substantially reduced. (3) A strong gradient between the northern and southern hemispheres indicates that mixing across the equator is greatly inhibited in relation to atmospheric residence times of BCA. (4) The single scatter albedo of BCA/"background" aerosol mixtures suggests a cooling effect for most of the globe; an exemption is the Arctic because of the high surface albedo of the snow/ice covered earth's surface.

Pueschel, R. F.↗

Turbulent Jet Flames Into a Vitiated Coflow

Examined is the vitiated coflow flame, an experimental condition that decouples the combustion processes of flows found in practical combustors from the associated recirculating fluid mechanics. The configuration consists of a 4.57 mm diameter fuel jet into a coaxial flow of hot combustion products from a lean premixed flame. The 210 mm diameter coflow isolates the jet flame from the cool ambient, providing a hot environment similar to the operating conditions of advanced combustors; this important high temperature element is lacking in the traditional laboratory experiments of jet flames into cool (room) air. A family of flows of increasing complexity is presented: 1) nonreacting flow, 2) all hydrogen flame (fuel jet and premixed coflow), and 3) set of methane flames. This sequence of experiments provides a convenient ordering of validation data for combustion models. Laser Raman-Rayleigh-LIF diagnostics at the Turbulent Diffusion Flame laboratory of Sandia National Laboratories produced instantaneous multiscalar point measurements. These results attest to the attractive features of the vitiated coflow burner and the well-defined boundary conditions provided by the coflow. The coflow is uniform and steady, isolating the jet flame from the laboratory air for a downstream distance ranging from z/d = 50-70. The statistical results show that differential diffusion effects in this highly turbulent flow are negligible. Complementing the comprehensive set of multiscalar measurements is a parametric study of lifted methane flames that was conducted to analyze flame sensitivity to jet and coflow velocity, as well as coflow temperature. The linear relationship found between the lift-off height and the jet velocity is consistent with previous experiments. New linear sensitivities were found correlating the lift-off height to coflow velocity and temperature. A blow-off study revealed that the methane flame blows off at a common coflow temperature (1260 K), regardless of coflow or jet velocity. An explanation for this phenomenon is that entrainment of ambient air at the high lift-off heights prevents autoignition. Analysis of the results suggests that flame stabilization occurs through a combination of flame propagation, autoignition, and localized extinction processes. Proposed is an expanded view of distributed reaction combustion based on analysis of the distributions of probe volume conditions at the stabilization region of the lifted hydrogen and methane flames. Turbulent eddies the size of the flame thickness mix fuel and hot coflow across the flame front, thereby enhancing the reaction zone with autoignition of reactants at elevated temperatures; this is the reverse effect of turbulent flames in ambient air, where intense turbulence in cool mixtures result in localized extinction. Each of the three processes (i.e., flame propagation, autoignition and localized extinction) contributes to flame stabilization in varying degrees, depending on flow conditions.

Holdeman, James D.↗

A Strategy to Assess Aerosol Direct Radiative Forcing of Climate Using Satellite Radiation Measurements

Atmospheric aerosols have a complex internal chemical composition and optical properties. Therefore it is difficult to model their impact on redistribution and absorption of solar radiation, and the consequent impact on atmospheric dynamics and climate. The use in climate models of isolated aerosol parameters retrieved from satellite data (e.g. optical thickness) may result in inconsistent calculations, if the model assumptions differ from these of the satellite retrieval schemes. Here we suggest a strategy to assess the direct impact of aerosol on the radiation budget at the top and bottom of the atmosphere using satellite and ground based measurements of the spectral solar radiation scattered by the aerosol. This method ensures consistent use of the satellite data and increases its accuracy. For Kaufman and Tanre: Strategy for aerosol direct forcing anthropogenic aerosol in the fine mode (e.g. biomass burning smoke and urban pollution) consistent use of satellite derived optical thickness can yield the aerosol impact on the spectral solar flux with accuracy an order of magnitude better than the optical thickness itself. For example, a simulated monthly average smoke optical thickness of 0.5 at 0.55 microns (forcing of 40-50 W/sq m) derived with an error of 20%, while the forcing can be measured directly with an error of only 0-2 W/sq m. Another example, the effect of large dust particles on reflection of solar flux can be derived three times better than retrievals of optical thickness. Since aerosol impacts not only the top of the atmosphere but also the surface irradiation, a combination of satellite and ground based measurements of the spectral flux, can be the most direct mechanism to evaluate the aerosol effect on climate and assimilate it in climate models. The strategy is applied to measurements from SCAR-B and the Tarfox experiments. In SCAR-B aircraft spectral data are used to derive the 24 hour radiative forcing of smoke at the top of the atmosphere of (Delta)F(sub 24hr)/(Delta)tau = - 25 +/- 5 W/sq m. Ground based data give forcing at the surface of (Delta)F(sub 24hr)/(Delta)taur = -80 +/- 5 W/sq m. In TARFOX a mixture of maritime and regional pollution aerosol resulted in a varied forcing at the top of the atmosphere, (Delta)F(sub 24hr)/(Delta)tau, between -26 W/sq 2 and -50 W/sq m depending on mixture of coarse and accumulation modes, for Angstrom exponents of 1.0 and 0.2 respectively.

Kaufman, Yoram J.↗

Quantification of Residual Water in Spent Fuel Dry Storage Canisters Using Mass Spectrometry

The purpose of this report is to document updates on the apparatus to simulate commercial vacuum drying procedures at the Nuclear Energy Work Complex at Sandia National Laboratories. Validation of the extent of water removal in a dry spent nuclear fuel storage system based on drying procedures used at nuclear power plants is needed to close existing technical gaps. Operational conditions leading to incomplete drying may have potential impacts on the fuel, cladding, and other components in the system during subsequent storage and disposal, such as fuel degradation; cladding corrosion, embrittlement, or breaching; and the creation of a flammable environment via radiolysis of water. A general lack of data suitable for model validation of commercial nuclear canister drying processes necessitates well-designed investigations of drying process efficacy and water retention. Scaled tests that incorporate relevant physics and well-controlled boundary conditions are essential to provide insight and guidance to the simulation of prototypic systems undergoing drying processes. This report documents details on the quantification of residual water in the Advanced Drying Cycle Simulator (ADCS), an apparatus built to simulate commercial drying procedures and quantify the amount of residual water remaining in a pressurized water reactor (PWR) fuel assembly after drying. The ADCS was constructed with a prototypic 17×17 PWR fuel skeleton and waterproof heater rods to simulate decay heat. The ADCS is outfitted with thermocouples to measure the thermal response of the ADCS to simulated decay heats and internal helium fill pressures relevant to commercial drying procedures. The ADCS is also instrumented with pressure transducers to measure the pressures and vacuum levels observed during simulated commercial drying. The most unique instrumentation used for quantifying residual water in the ADCS is a Hiden Analytical HPR-30 mass spectrometer (MS), which measures gas compositions of the ADCS internal free volume, based on partial pressures calculated from relative proportions of gas molecules detected by the MS. This report details the methodology used to implement MS measurements in quantifying residual water in the ADCS. This methodology includes the calibration of the HPR-30 MS to a Buck Research Instruments CR-4 chilled mirror hygrometer, which itself is calibrated to a NIST-traceable standard. Data collected by both the MS and the chilled mirror hygrometer from water/helium mixtures ranging from 150 to 500,000 ppmv water in helium were used to generate calibration curves, establishing a source of verification of MS measured water contents. Details regarding water content measurement uncertainties are included in this report, defining the accuracy and verifiability of the HPR-30 MS in measuring residual water content in simulated dry storage canister environments.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Standoff Detection of Chemical Plumes Using Swept-ECQCL Remote Detection Technology: Results from EMRTC Complex Terrain Dual Tracer Experiment

As part of the Complex Terrain Dual Tracer Experiments performed in support of the LYNM program, a swept-wavelength external cavity quantum cascade laser (swept-ECQCL) remote detection system was deployed to measure chemical plume propagation with high temporal resolution. The swept-ECQCL remote detection technology was initially developed at PNNL, and is now under further development at Opticslah, LLC under SBIR funding from DOE (DOE SBIR Phase I Project DE-SC0019855, Remote Detection Technologies, Program Manager Chris Ramos). The swept-ECQCL technology provides a single-frequency infrared laser source which is rapidly scanned over a large wavelength range to measure the infrared absorption of gases, liquids, or solids. Analysis of the measured infrared absorption spectrum is used to detect, identify, and quantify the chemical species which are present. While most previous laser-based techniques used small wavelength tuning ranges to measure only a few isolated spectral lines of a few species, the swept-ECQCL provides the large tuning range needed to measure multiple species simultaneously, and to detect broad absorption features from large molecules or condensed phase materials. In addition, the swept-ECQCL systems have high enough spectral resolution and sensitivity to measure narrow lines of small molecules and determine isotope ratios. The remote detection system for gas plumes is based on the swept-ECQCL technology, and consists of a swept-ECQCL source, infrared detector, control electronics, and beam transmitting and alignment optics. The remote detection system directs the infrared output of the swept-ECQCL to a target retro reflector typically located at ~10-10,000 m distance. The swept-ECQCL wavelength is varied continuously over a large wavelength range (>1000 nm) at rates up to 1000 Hz. The swept ECQCL light reflected from the remote target is collected and focused onto an infrared photodetector. By measuring the detector signal continuously as the swept-ECQCL wavelength is varied, a time-series of absorption spectra are measured for the gases along the beam line of-sight. Based on analysis and fitting of the measured absorption spectra, the time-dependent chemical concentrations of species are determined. Multiple species and mixtures can be detected simultaneously, for all species with absorption features above the sensor noise floor. The sensor output is thus a continuous, high-speed record of identified chemicals along with their concentrations and isotope ratios of interest. The high-speed operation enables low-noise operation in conditions of atmospheric turbulence and allows tracking of fluctuating concentrations in transient chemical plumes as needed for reliable remote detection applications. All components operate with minimal cooling requirements and no cryogens are needed. In addition, the output infrared light is invisible with an intensity below the maximum permissible exposure (MPE) threshold of 100 mW/cm2 for these infrared wavelengths and thus eye safe. The measurement concept for plume detection using the swept-ECQCL remote detection system is as follows. The ECQCL beam is directed toward a remote retro-reflector, which reflects the beam back to the ECQCL system where it is focused onto an infrared photodetector. The line-of-sight from the ECQCL system to the retro-reflector defines the measurement path. The detected infrared signal is recorded continuously and detects the absorption of molecular species along the measurement path. Before a plume release, the system measures absorption from atmospheric constituents, which in this LWIR band consist primarily of lines from H 2 O and CO 2 , with additional weaker absorption from N 2 O, NH 3 , and O 3 possibly contributing. The system then measures any changes in absorption due to the tracer compounds when they enter the measurement path. The shape of absorption features is used to distinguish and identify the different tracer compounds, and the strength of the absorption is used to determine the path-integrated concentration – also called the column density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-resolution rovibrational spectroscopy of trans -formic acid in the v 1 OH stretching fundamental: Dark state coupling and evidence for charge delocalization dynamics

High-resolution infrared (IR) reduced-Doppler absorption spectra of jet-cooled gas phase trans-formic acid in the v 1 OH stretching fundamental region are reported for the first time, obtained by supersonically expanding trans- formic acid/Ar mixtures through a slit jet nozzle source and rotationally cooling to T rot ≈ 10.9(5) K, with ab- sorption signals recorded by high-resolution difference-frequency IR absorption spectroscopy. Two a/b-type rovibrational bands of comparable intensity, one ~10-fold weaker b-type band, and one ~6-fold weaker a-type band are observed, with vibrational band origins at 3570.493(5), 3566.793(5), 3560.032(9), and 3534.6869(2) cm –1 , respectively. Based on previous Raman jet spectroscopic work by Nejad and Sibert [A. Nejad, E.L. Sibert III, The Raman jet spectrum of trans-formic acid and its deuterated isotopologs: Combining theory and experi- ment to extend the vibrational database, J. Chem. Phys. 154(6) (2021) 064301.], these four rovibrational bands have been assigned to v 1 , (v 2 + v 7 ), (v 6 + 2v 7 + 2v 9 ), and 2v 3 , respectively. Specifically, two of the three upper dark states (2 1 7 1 (a') and 6 1 7 2 9 2 (a')) are close enough to the “bright” 1 1 (a') state to facilitate strong anharmonic resonance interactions, which results in intensity mixing into the two zero-order bands that would otherwise be “dark”. Furthermore, our high-resolution spectral analysis reveals that there are local rotational crossings be- tween these zero-order 1 1 and 2 1 7 1 states resulting in extra lines (i.e., some upper levels in the nominally v 1 band have majority zero-order 2 1 7 1 state character). This motivates development of a 3 coupled state (1 1 , 2 1 7 1 , and 6 1 7 2 9 2 ) picture to aid in the spectral analysis, which is able to match all 3 observed band origins and relative band intensities, as well as indicate the necessity of multistate (> 2) coupling. Though limited by range of J and Ka levels (J’ ≤ 9 and K a ’ ≤ 3) populated at supersonic jet temperatures, this work offers first precision spec- troscopic analysis of trans-formic acid in the v 1 OH stretch region, which should aid in assignment of the more complete yet highly congested room temperature FTIR spectra. Lastly, and in sharp contrast to the spectral complexity in the three predominantly b-type bands, the lone a-type 2v 3 rovibrational band at 3534.6869(2) cm –1 is well described by a simple, rigid asymmetric top Hamiltonian.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of Hf 6 Ta 2 O 17 superstructure via spark plasma sintering for improved oxidation resistance of multi-component ultra-high temperature ceramics

Ultra-high temperature ceramics (UHTCs) have shown aspiration to overcome challenges in the thermal protection system (TPS) by designing new materials referred to as multi-component UHTCs (MC-UHTCs) in the compositional space. MC-UHTCs have shown remarkable improvement in oxidation resistance due to the formation of the Hf6Ta2O17 superstructure during plasma exposure. Herein, the Hf 6 Ta 2 O 17 superstructure is synthesized via a solid-state reaction between HfO 2 and Ta 2 O 5 powder mixtures during spark plasma sintering (SPS). The compositions chosen are 50 vol% of HfO 2 -50 vol% of Ta 2 O 5 (50HO-50TO) and 70 vol% of HfO 2 -30 vol% of Ta 2 O 5 (70HO-30TO). The phase quantification via Rietveld analysis showed Hf 6 Ta 2 O 17 as a principal phase with some residual Ta 2 O 5 phase in both the samples. The high-temperature thermal stability of the samples was evaluated using high-velocity plasma jet exposure for up to 3 min. 50HO-50TO was able to withstand the intense plasma condition, which is attributed to the higher content of the Hf 6 Ta 2 O 17 phase (~84%) and lower strain in the Ta 2 O 5 phase. The augmentation in the Hf 6 Ta 2 O 17 phase to 94.7% (in 50HO-50TO) post plasma exposure has been attributed to the invariant transformation from a liquid state to Hf 6 Ta 2 O 17 at temperatures >2500 °C during testing. The mechanical integrity is elucidated from the insignificant change in the hardness ~13.3 GPa before and 11.2 GPa after plasma exposure of the 50HO-50TO sample. As a result, the Hf 6 Ta 2 O 17 superstructure's thermo-mechanical stability suggests developing novel oxidation-resistant MC-UHTCs in compositional space for reusable space vehicle applications.

36 MATERIALS SCIENCE↗

Effects of Heating Configuration and Operating Parameters on Heat Transfer and Interfacial Physics of Microgravity Flow Boiling With Subcooled Inlet Conditions –Experiments Onboard the International Space Station

This study is part of the Flow Boiling and Condensation Experiment (FBCE), a collaborative effort between the Purdue University Boiling and Two-Phase Flow Laboratory (PU-BTPFL) and the NASA Glenn Research Center. The FBCE fitted with the Flow Boiling Module (FBM) was launched to the International Space Station (ISS) in August 2021 and experiments were successfully performed from February to July 2022 to amass a large microgravity-flow-boiling database. This study is focused on heat transfer and flow visualization of microgravity flow boiling of n-Perfluorohexane in a rectangular channel of 5.0 mm height, 2.5 mm width (heated), and 114.6 mm length, with subcooled inlet conditions. High-speed-video photography is utilized to present flow patterns and temporal interfacial behavior. Heat transfer results are presented in the form of flow boiling curves and both parametric curves and streamwise profiles of wall temperature and heat transfer coefficient. Firstly, the parametric effects of mass velocity (199.4 – 3200.0 kg/m 2 s), inlet subcooling (0.2 – 46.0°C), and inlet pressure (124.2 – 176.7 kPa), on the aforementioned aspects are assessed for double-sided heating to establish them for a microgravity environment. Of these three parameters, mass velocity and inlet subcooling mostly determine the microgravity flow boiling behavior, while inlet pressure plays an insignificant role. Flow patterns for double-sided heating are more complex than those for single-sided heating due to interaction between the two vapor layers. Vapor interaction is minimized at high subcoolings and high mass velocities due to strong condensation offered by the subcooled bulk liquid layer separating them. Despite the different flow patterns, both single- and double-sided heating generally result in similar parametric trends and local heat transfer coefficients for similar operating conditions. Flow instabilities manifest as temporal flow anomalies and temperature oscillations, and their severity increases with increasing boiling number. Secondly, the effects of heating configuration are analyzed by comparing and contrasting several aspects of single- and double-sided heating data. The heat fluxes at which onset of nucleate boiling degradation (ONBD) and critical heat flux (CHF) occur are distinctly different for single- and double-sided heating. There exists a threshold inlet subcooling demarcating the dominance of flow acceleration and condensation effects in vapor removal from the near-wall region and replenishment of fresh liquid for boiling. Above the threshold, condensation from the near-wall region is dominant and single-sided heating yields higher heat fluxes, and below it, acceleration is dominant and double-sided yields higher heat fluxes. At mass velocity in the range of 200 – 2400 kg/m 2 s, the threshold inlet subcooling lies in the approximate range of 20 – 30°C (corresponding inlet quality of roughly -0.40 – -0.20).

Microgravity↗

Investigation of Magmatic Activities on Early Mars Using Igneous Mineral Chemistry in Gale Crater, Mars

One objective of rover missions is exploring the geological context of the surroundings. Over the years, igneous petrology and sedimentology have been disconnected, the first investigating magmatic processes and volcanic activities, and the second seeking environmental conditions in the past and assessing the habitability of the planet. Although different, one is related to the other: igneous rocks are altered and broken down, leading to the formation of sedimentary rocks, which can in turn be used to back out the nature of their magmatic source. The Curiosity rover that landed in the 3.7 Gyr old impact crater Gale is traveling through sedimentary rocks. About fifty float rocks have been observed, and several of them with ambiguous texture and composition have been classified as igneous or sedimentary depending on studies such as Jake_M. The composition of several unambiguous igneous rocks has been analyzed [4- 6] but their heterogeneity at a larger instrumental (measurement size < 2 cm) scale prevents the measurement of a bulk composition as performed on Earth. An original approach avoiding these two last issues is to consider igneous mineral chemistry analyzed within igneous and sedimentary rocks to assess magmatic processes that could have formed them. Most Curiosity data are used to explore ancient environmental conditions, and a significant number of compositional analyses are under-explored for constraining magmatic activities. We will present how we can make use of sedimentary data for investigating igneous processes in the vicinity of Gale crater. Geological Context: We focus on the first 750 martian days, corresponding to measurements in a coherent lacustrine sedimentary unit called Bradbury, because all sedimentary rocks were sourced from the same watershed and appear to have a consistent source with minimal alteration [2-3]. Igneous detrital minerals including feldspar and pyroxene, are observed in sedimentary rocks. Monte Carlo models showed that minimal cation loss is observed based on the composition of all Bradbury rocks, implying negligible weathering [3]. Although clay minerals are detected in few rocks [7], chemical compositions of rocks can be explained by a mixture of primary igneous minerals [3]. Variation of composition within Bradbury rocks can be explained by mineral sorting and one distinct source component. While a common magmatic source is suggested, Bradbury sediments likely come from several volcanic eruptions from a single magmatic chamber [9- 10]. The occurrence of alkali minerals like sanidine and K-rich rocks throughout Bradbury supports the presence of a potassic component, likely trachytic, while plagioclase and a mafic composition suggest a basaltic component [8-9]. Instruments: Mineral chemistry can be estimated by three instruments onboard Curiosity. The CheMin instrument enables detection of mineral assemblages using X-ray diffraction (XRD). Using Rietveld refinement, each mineral is identified according to their 1D XRD pattern [11]. Note that distinction between pyroxene minerals is challenging with the CheMin instrument due to overlapping peaks on XRD patterns and low angular resolution of the instrument [12]. Then, using least square regression and optimization algorithms based on unit-cell parameters, mineral chemistry has been estimated by [11]. Plagioclase composition has been estimated using the NaAlSi3O8- CaAl2Si2O8 system and alkali feldspar is based on the NaAlSi3O8-KAlSi3O8 system (stars in Fig.1). Two mudstone samples (John Klein and Cumberland) and one sandstone sample (Windjana) were analyzed by CheMin at Yellowknife Bay and Kimberley, respectively. Figure 1. Ternary diagrams of feldspars (top) and pyroxene (bottom) quadrilateral. Stars correspond to CheMin composition and the gray patches to ChemCam composition. The colored dots are the composition of feldspar and pyroxene that crystallized during fractional crystallization at FMQ+1 of a melt extracted at distinct melting degree during the adiabatic ascent of a primitive mantle composition, without any water (left panels) and with 0.5 wt.% of water (right panels) at distinct pressure. The ChemCam instrument enables the analysis of the chemical compositions of rocks at hundreds of micrometer scale (350-550 μm) using laser induced breakdown spectroscopy (LIBS), which may provide the composition of minerals when they are larger than the beam spot (>550 μm) [13]. Within >5000 LIBS points, we performed a typical stoichiometric filtering allowing us to distinguish 56 feldspar and 10 pyroxene mineral compositions (grey patches in Fig. 1). Finally, the Alpha Particle X-ray Spectrometer (APXS) analyzes the composition of rocks with a 1.6 cm diameter spot size. Monte Carlo mass balance modeling allowed [3] to decipher a feldspar range varying between An30 and An40 (Fig. 1). Discussion: Although there could be a more complex history and other ways to form the whole compositional range of igneous minerals analyzed within the Bradbury formation, we are presenting here simple magmatic pathways commonly occurring on Earth using the thermodynamical softwares pMELTS and rhyoliteMELTS [14]. The objective is to find reasonable igneous processes that produce minerals that parallel the compositions of feldspar and pyroxene analyzed by the Curiosity rover. As commonly observed for mid-ocean ridge basalts, the adiabatic ascent of a primitive mantle composition [15] partially melting at 2 GPa has been modeled, followed by the extraction of a liquid at distinct degrees of partial melting, which undergoes fractional crystallization at an oxygen fugacity +1 log unit above the fayalite-magnetite-quartz (FMQ) buffer within the crust (0.02-0.4 GPa) with H2O = 0- 0.5 wt. %. These latter conditions correspond to those recorded within igneous clasts from the Noachian martian breccia NWA 7034 and paired and within Gale igneous rocks (colored dots in Fig. 1) [16-17]. To check the reliability of these 2-step models, we also tested fractional crystallization at similar conditions (FMQ+1; P=0.02-0.4 GPa; H2O = 0-0.5 wt. %) of starting compositions corresponding to that of magmas with distinct melting degrees obtained from isobaric experiments at 2 GPa [18]. Mineral compositions obtained from both models are similar. As shown on Fig. 1, the whole range of observed feldspar compositions cannot be reproduced by fractionation of one magma only. Indeed, while alkali feldspar and Na-plagioclase likely crystallized from fractional crystallization of a low-degree melt (here <15%), plagioclase and pyroxene can only be formed by fractional crystallization of a higher degree melt (here >19%). The corresponding liquid descent lines are broadly in agreement with compositions estimated by ChemCam corresponding to float igneous rocks (Fig. 2) [4-6]. Figure 2. Silica versus alkali content. Lines show the liquid lines of descent from magmas with distinct degrees of melting. Gray patches represents the composition of Gale igneous rocks [4-6]. Trachytic to rhyolitic magmas crystallize alkali feldspar, and andesite to dacite magmas likely form plagioclase. Therefore, at least two starting magmas at distinct melting degrees, which could easily come from a single mantle source, are necessary to explain the whole compositional range of feldspar and pyroxene analyzed within Bradbury rocks. Conclusion: Because rocks from the Bradbury formation are likely originating from the same magmatic source with minimal weathering as supported by several studies using different approaches, igneous mineral chemistry analyzed by CheMin and ChemCam allows us to back out reasonable magmatic pathways that could have crystallized them. Fractional crystallization of at least two starting magmas originating from distinct melting degrees of a single mantle source can explain the whole range of feldspar and pyroxene composition. Both alkaline and sub-alkaline liquids can be produced, with compositions corresponding to those of the igneous rocks analyzed by ChemCam within the Bradbury formation, highlighting the complexity of Mars magmatism.

Payre, V.↗

Temperature-Sensitive Coating Sensor Based on Hematite

A temperature-sensitive coating, based on hematite (iron III oxide), has been developed to measure surface temperature using spectral techniques. The hematite powder is added to a binder that allows the mixture to be painted on the surface of a test specimen. The coating dynamically changes its relative spectral makeup or color with changes in temperature. The color changes from a reddish-brown appearance at room temperature (25 C) to a black-gray appearance at temperatures around 600 C. The color change is reversible and repeatable with temperature cycling from low to high and back to low temperatures. Detection of the spectral changes can be recorded by different sensors, including spectrometers, photodiodes, and cameras. Using a-priori information obtained through calibration experiments in known thermal environments, the color change can then be calibrated to yield accurate quantitative temperature information. Temperature information can be obtained at a point, or over an entire surface, depending on the type of equipment used for data acquisition. Because this innovation uses spectrophotometry principles of operation, rather than the current methods, which use photoluminescence principles, white light can be used for illumination rather than high-intensity short wavelength excitation. The generation of high-intensity white (or potentially filtered long wavelength light) is much easier, and is used more prevalently for photography and video technologies. In outdoor tests, the Sun can be used for short durations as an illumination source as long as the amplitude remains relatively constant. The reflected light is also much higher in intensity than the emitted light from the inefficient current methods. Having a much brighter surface allows a wider array of detection schemes and devices. Because color change is the principle of operation, the development of high-quality, lower-cost digital cameras can be used for detection, as opposed to the high-cost imagers needed for intensity measurements with the current methods. Alternative methods of detection are possible to increase the measurement sensitivity. For example, a monochrome camera can be used with an appropriate filter and a radiometric measurement of normalized intensity change that is proportional to the change coating temperature. Using different spectral regions yields different sensitivities and calibration curves for converting intensity change to temperature units. Alternatively, using a color camera, a ratio of the standard red, green, and blue outputs can be used as a self-referenced change. The blue region (less than 500 nm) does not change nearly as much as the red region (greater than 575 nm), so a ratio of color intensities will yield a calibrated temperature image. The new temperature sensor coating is easy to apply, is inexpensive, can contour complex shape surfaces, and can be a global surface measurement system based on spectrophotometry. The color change, or relative intensity change, at different colors makes the optical detection under white light illumination, and associated interpretation, much easier to measure and interpret than in the detection systems of the current methods.

Bencic, Timothy J.↗

The Curious Case of [AnH(NR 2 ) 3 ] (An = Th, U; R = SiMe 3 ): Two Monomeric Actinide Hydrides Revisited

The reaction of AnCl 4 (DME) x (An = Th, x = 2; An = U, x = 0) with 4 equiv of NaNR 2 (R = SiMe 3 ) in THF at 65 °C results in the formation of [An{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] (An = U, 1; An = Th, 2), and not the reported monomeric actinide hydrides, [AnH(NR 2 ) 3 ], as expected. Furthermore, both complexes 1 and 2 were characterized by X-ray crystallography. Surprisingly, their unit cell parameters are remarkably close to those reported for [AnH(NR 2 ) 3 ], suggesting that the original crystals of [AnH(NR 2 ) 3 ] were, in fact, [An{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ], but were misidentified. Reduction of 1 with 1.1 equiv of KC 8 in THF, in the presence of 1 equiv of 2.2.2-cryptand, results in the formation of [K(2.2.2-cryptand)][U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] (3) in good yield. Likewise, the reaction of 1 with 1 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) results in the formation of the BAC adduct, [(BAC)U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] (4), in moderate yield. Finally, the addition of H 2 (10 bar) to 2 in C 6 D 6 at room temperature results in the formation of the targeted monomeric hydride, [ThH(NR 2 ) 3 ], in 32% yield, according to integrations against an internal standard. However, removal of the H 2 atmosphere results in rapid reformation of 2. In contrast, the addition of H 2 (10 bar) to 1 in C 6 D 6 at room temperature results in no apparent reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗