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NASA NTRS2014

Method of Minimizing Size of Heat Rejection Systems for Thermoelectric Coolers to Cool Detectors in Space

A thermal design concept of attaching the thermoelectric cooler (TEC) hot side directly to the radiator and maximizing the number of TECs to cool multiple detectors in space is presented. It minimizes the temperature drop between the TECs and radiator. An ethane constant conductance heat pipe transfers heat from the detectors to a TEC cold plate which the cold side of the TECs is attached to. This thermal design concept minimizes the size of TEC heat rejection systems. Hence it reduces the problem of accommodating the radiator within a required envelope. It also reduces the mass of the TEC heat rejection system. Thermal testing of a demonstration unit in vacuum verified the thermal performance of the thermal design concept.

thermoelectric coolers↗
NASA NTRS2015

Phase 1 Final Report: Titan Submarine

The conceptual design of a submarine for Saturn's moon Titan was a funded NASA Innovative Advanced Concepts (NIAC) Phase 1 for 2014. The proposal stated the desire to investigate what science a submarine for Titan's liquid hydrocarbon seas might accomplish and what that submarine might look like. Focusing on a flagship class science system (100 kg), it was found that a submersible platform can accomplish extensive science both above and below the surface of the Kraken Mare. Submerged science includes mapping using side-looking sonar, imaging and spectroscopy of the lake, as well as sampling of the lake's bottom and shallow shoreline. While surfaced, the submarine will not only sense weather conditions (including the interaction between the liquid and atmosphere) but also image the shoreline, as much as 2 km inland. This imaging requirement pushed the landing date to Titan's next summer period (2047) to allow for lighted conditions, as well as direct-to-Earth communication, avoiding the need for a separate relay orbiter spacecraft. Submerged and surfaced investigation are key to understanding both the hydrological cycle of Titan as well as gather hints to how life may have begun on Earth using liquid, sediment, and chemical interactions. An estimated 25 Mb of data per day would be generated by the various science packages. Most of the science packages (electronics at least) can be safely kept inside the submarine pressure vessel and warmed by the isotope power system.The baseline 90-day mission would be to sail submerged and surfaced around and through Kraken Mare investigating the shoreline and inlets to evaluate the sedimentary interaction both on the surface and then below. Depths of Kraken have yet to be sensed (Ligeia to the north is thought to be 200 m (656 ft) deep), but a maximum depth of 1,000 m (3,281 ft) for Kraken Mare was assumed for the design). The sub would spend 20 d at the interface between Kraken Mare and Ligeia Mare for clues to the drainage of liquid methane into the currently predicted predominantly ethane Kraken Mare. During an extended ninety-day mission, it would transit the throat of Kraken (now Seldon Fretum) and perform similar explorations in other areas of Kraken Mare. Once this half year of exploration is completed the submarine could be tasked to revisit points of interest and perhaps do a complete sonar mapping of the seas. All in all, the submarine could explore over 3,000 km (1,864 mi) in its primary mission at an average speed of 0.3 meters per second.

Titan↗
NASA NTRS2016

Generalized Fluid System Simulation Program, Version 6.0

The Generalized Fluid System Simulation Program (GFSSP) is a general purpose computer program for analyzing steady state and time-dependent flow rates, pressures, temperatures, and concentrations in a complex flow network. The program is capable of modeling real fluids with phase changes, compressibility, mixture thermodynamics, conjugate heat transfer between solid and fluid, fluid transients, pumps, compressors, and external body forces such as gravity and centrifugal. The thermofluid system to be analyzed is discretized into nodes, branches, and conductors. The scalar properties such as pressure, temperature, and concentrations are calculated at nodes. Mass flow rates and heat transfer rates are computed in branches and conductors. The graphical user interface allows users to build their models using the 'point, drag, and click' method; the users can also run their models and post-process the results in the same environment. Two thermodynamic property programs (GASP/WASP and GASPAK) provide required thermodynamic and thermophysical properties for 36 fluids: helium, methane, neon, nitrogen, carbon monoxide, oxygen, argon, carbon dioxide, fluorine, hydrogen, parahydrogen, water, kerosene (RP-1), isobutene, butane, deuterium, ethane, ethylene, hydrogen sulfide, krypton, propane, xenon, R-11, R-12, R-22, R-32, R-123, R-124, R-125, R-134A, R-152A, nitrogen trifluoride, ammonia, hydrogen peroxide, and air. The program also provides the options of using any incompressible fluid with constant density and viscosity or ideal gas. The users can also supply property tables for fluids that are not in the library. Twenty-four different resistance/source options are provided for modeling momentum sources or sinks in the branches. These options include pipe flow, flow through a restriction, noncircular duct, pipe flow with entrance and/or exit losses, thin sharp orifice, thick orifice, square edge reduction, square edge expansion, rotating annular duct, rotating radial duct, labyrinth seal, parallel plates, common fittings and valves, pump characteristics, pump power, valve with a given loss coefficient, Joule-Thompson device, control valve, heat exchanger core, parallel tube, and compressible orifice. The program has the provision of including additional resistance options through User Subroutines. GFSSP employs a finite volume formulation of mass, momentum, and energy conservation equations in conjunction with the thermodynamic equations of state for real fluids as well as energy conservation equations for the solid. The system of equations describing the fluid network is solved by a hybrid numerical method that is a combination of the Newton-Raphson and successive substitution methods. The application and verification of the code has been demonstrated through 30 example problems.

Majumdar, A. K.↗
NASA NTRS2014

Miniature Cryogenic Valves for a Titan Lake Sampling System

The Cassini mission has revealed Titan to be one of the most Earthlike worlds in the Solar System complete with many of the same surface features including lakes, river channels, basins, and dunes. But unlike Earth, the materials and fluids on Titan are composed of cryogenic organic compounds with lakes of liquid methane and ethane. One of the potential mission concepts to explore Titan is to land a floating platform on one of the Titan Lakes and determine the local lake chemistry. In order to accomplish this within the expected mass volume and power budgets there is a need to pursue the development for a low power lightweight cryogenic valves which can be used along with vacuum lines to sample lake liquid and to distribute to various instruments aboard the Lander. To meet this need we have initiated the development of low power cryogenic valves and actuators based on a single crystal piezoelectric flextensional stacks produced by TRS Ceramics Inc. Since the origin of such high electromechanical properties of Relaxor-PT single crystals is due to the polarization rotation effect, (i.e., intrinsic contributions), the strain per volt decrease at cryogenic temperatures is much lower than in standard Lead Zirconate Titanate (PZT) ceramics. This makes them promising candidates for cryogenic actuators with regards to the stroke for a given voltage. This paper will present our Titan Lake Sampling and Sample Handling system design and the development of small cryogenic piezoelectric valves developed to meet the system specifications.

Piezoelectric Devices↗
NASA NTRS2012

The Origin and Evolution of Saturn's 2011-2012 Stratospheric Vortex

The planet-encircling springtime storm in Saturn's troposphere (December 2010-July 2011, Fletcher, L.N. et al. [2011]. Science 332, 1413-1414; Sánchez-Lavega, A. et al. [2011]. Nature 475, 71-74; Fischer, G. et al. [2011]. Nature 475, 75-77) produced dramatic perturbations to stratospheric temperatures, winds and composition at mbar pressures that persisted long after the tropospheric disturbance had abated. Thermal infrared (IR) spectroscopy from the Cassini Composite Infrared Spectrometer (CIRS), supported by ground-based IR imaging from the VISIR instrument on the Very Large Telescope and the MIRSI instrument on NASA's IRTF, is used to track the evolution of a large, hot stratospheric anticyclone between January 2011 and March 2012. The evolutionary sequence can be divided into three phases: (I) the formation and intensification of two distinct warm airmasses near 0.5 mbar between 25 and 35degN (B1 and B2) between January-April 2011, moving westward with different zonal velocities, B1 residing directly above the convective tropospheric storm head; (II) the merging of the warm airmasses to form the large single 'stratospheric beacon' near 40degN (B0) between April and June 2011, disassociated from the storm head and at a higher pressure (2 mbar) than the original beacons, a downward shift of 1.4 scale heights (approximately 85 km) post-merger; and (III) the mature phase characterised by slow cooling (0.11 +/- 0.01 K/day) and longitudinal shrinkage of the anticyclone since July 2011. Peak temperatures of 221.6 +/- 1.4 K at 2 mbar were measured on May 5th 2011 immediately after the merger, some 80 K warmer than the quiescent surroundings. From July 2011 to the time of writing, B0 remained as a long-lived stable stratospheric phenomenon at 2 mbar, moving west with a near-constant velocity of 2.70 +/- 0.04 deg/day (24.5 +/- 0.4 m/s at 40degN relative to System III longitudes). No perturbations to visible clouds and hazes were detected during this period. With no direct tracers of motion in the stratosphere, we use thermal windshear calculations to estimate clockwise peripheral velocities of 200-400 m/s at 2 mbar around B0. The peripheral velocities of the two original airmasses were smaller (70-140 m/s). In August 2011, the size of the vortex as defined by the peripheral collar was 65deg longitude (50,000 km in diameter) and 25deg latitude. Stratospheric acetylene (C2H2) was uniformly enhanced by a factor of three within the vortex, whereas ethane (C2H6) remained unaffected. The passage of B0 generated a new band of warm stratospheric emission at 0.5 mbar at its northern edge, and there are hints of warm stratospheric structures associated with the beacons at higher altitudes (p < 0.1 mbar) than can be reliably observed by CIRS nadir spectroscopy. Analysis of the zonal windshear suggests that Rossby wave perturbations from the convective storm could have propagated vertically into the stratosphere at this point in Saturn's seasonal cycle, one possible source of energy for the formation of these stratospheric anticyclones.

evolution↗
NASA NTRS2015

The Quick Fire Emissions Dataset (QFED): Documentation of Versions 2.1, 2.2 and 2.4: Technical Report Series on Global Modeling and Data Assimilation - Volume 38

Biomass burning is an important source of particulates and trace gases and a major element of the terrestrial carbon cycle. Well constrained emissions from vegetation fires are needed to model direct and indirect effects of biomass burning aerosols, to model homogeneous and heterogeneous chemistry in the atmosphere, and to perform credible Earth system analysis, and climate and air pollution studies. To improve the performance of NASA Goddard Earth Observing System Model (GEOS) in the areas of atmospheric constituent modeling with a focus on biomass burning we developed the Quick Fire Emissions Dataset (QFED). The QFED emissions are based on the fire radiative power (top-down) approach and draw on the cloud correction method developed in the Global Fire Assimilation System (GFAS). Location and fire radiative power of fires are obtained from the Moderate Resolution Imaging Spectroradiometer (MODIS) Level 2 fire products (MOD14 and MYD14) and the MODIS Geolocation products (MOD03 and MYD03). QFED strengths are high spatial and temporal resolutions and near-real time availability. Daily mean emissions are available at 0.3125 times 0.25 degrees and in recent versions also at 0.1 times 0.1 degrees. QFED provides emissions of black carbon, organic carbon, sulfur dioxide, carbon monoxide, carbon dioxide, PM2.5, ammonia, nitrogen oxides, methyl ethyl ketone, propylene, ethane, propane, n- and i-butane, acetaldehyde, formaldehyde, acetone and methane. Two QFED product systems are maintained by the NASA Global Modeling and Assimilation Office (GMAO): one that produces near real-time daily emissions used operationally in the GEOS-5 Data Assimilation System, and one that produces an extended historical dataset with daily emissions from March 2000 to the present. The historical dataset also provides monthly mean and monthly climatological emissions.

Koster, Randal D.↗
NASA NTRS2013

Compositions of the Surfaces of Pluto and its Satellites

The information we have on the chemical compositions of the surfaces of Pluto and Charon has been obtained from Earth-based near-infrared spectroscopy. These bodies are seen in diffusely scattered sunlight upon which absorption bands diagnostic of specific ices are superimposed. Identified so far on Pluto are molecular nitrogen (N2), methane (CH4), carbon monoxide (CO), and ethane (C2H6), all in the frozen state. Charon has the clear spectral signature of H2O ice in the crystalline phase, plus an absorption band near 2.2 microns identified as a hydrated form of NH3. No diagnostic spectra of Pluto's other satellites are currently available. A fraction of Pluto's CH4 is dissolved in solid N2, which is in the hexagonal beta-phase. When a small concentration of CH4 exists in a N2 crystalline matrix, its absorption bands are shifted in wavelength by a small but detectable amount. Indeed the shifting of the CH4 bands is diagnostic of a host matrix. In the case of Pluto, the N2 band (2.148 microns) itself is detected, but for other trans-Neptunian objects where the N2 band cannot be seen, the shifted CH4 bands demonstrate the presence of N2 or (less likely) some other spectrally neutral and transparent matrix material (e.g., Ar). The absence of detectable CO2 and H2O ices on Pluto, while they are clearly present on the otherwise very similar Triton, is noteworthy. The ices of Pluto distributed non-uniformly across its surface, and the distribution shows long-term (decadal) changes. Both seasonal and secular changes may be occurring through transport across the surface as a result of changing temperature, and by seasonal changes in the vapor pressure equilibrium of the ice with the tenuous and variable atmosphere. Models of the photochemistry of the surface ices and the atmosphere of Pluto predict the presence of several materials not yet detected; the most abundant photoproducts are expected to be C2H2, C4H2, HCN, C2H6; HCN has been detected on Triton. Both Pluto and Charon have surface components in addition to the detected ices. These materials of presently unknown composition serve to reduce the albedos of both bodies below that expected for pure ices, and in the case of Pluto impart a yellow-brown coloration; the color of Charon is more nearly neutral. It is generally thought that the non-ice components are more refractory than the ices and that they may be complex carbonaceous materials derived from the ultraviolet and charged particle processing of the surface ices. Minerals are also plausible candidates for the non-ice fraction. The refractory colored components may constitute bedrock upon which variable amounts of the ices are alternately deposited and evaporated as the seasons change. Water ice is expected to be a component of the bedrock, although it has not yet been reliably identified.

Pluto↗
NASA NTRS2019

A Laser Heterodyne Radiometer for Sampling Plumes of Icy Moons

We propose to develop an instrument capable of passively sampling plumes in icy moon environments for the components needed for life and habitability. The compact, low-mass and power, orbital instrument would be an occultation-viewing laser heterodyne radiometer (LHR) that collects sunlight passing through the plumes of icy moons to measure abundancies of key trace gases such as water vapor, methane, ethane, carbon dioxide, and their isotopes. Laser heterodyne radiometers are based on radio receiver technology and have been applied to measurements of trace gases in Earth and planetary atmospheres since the 1960s. Our team has recently adapted this technology into a 4U (20cm x 20cm x 10cm) CubeSat instrument to measure carbon dioxide, methane and water vapor in the Earth's atmosphere (launching on Virgin Orbit in 2019) and have the experience to develop this into a compact science payload to monitor gases emerging from icy moons of Saturn and Jupiter.

laser heterodyne radiometer (LHR)↗
NASA NTRS2021

Intercomparison of the representations of the atmospheric chemistry of pre-industrial methane and ozone in earth system and other global chemistry-transport models

An intercomparison has been set up to study the representation of the atmospheric chemistry of the pre-industrial troposphere in earth system and other global tropospheric chemistry-transport models. The intercomparison employed a constrained box model and utilised tropospheric trace gas composition data for the pre-industrial times at ninety mid-latitude surface locations. Incremental additions of four organic compounds: methane, ethane, acetone and propane, were used to perturb the constrained box model and generate responses in hydroxyl radicals and tropospheric ozone at each location and with each chemical mechanism. Although the responses agreed well across the chemical mechanisms from the selected earth system and other global tropospheric chemistry-transport models, there were differences in the detailed responses between the chemical mechanisms that could be tracked down by sensitivity analysis to differences in the representation of C1–C3 chemistry. Inter-mechanism ranges in NOx compensation points were about 0.17 ± 0.12 when expressed relative to the inter-mechanism average. Monte Carlo uncertainty analysis carried out with a single chemical mechanism put the intra-mechanism range a factor of three higher at 0.50 ± 0.12. Similar differences between inter-mechanism and intra-mechanism ranges were found for hydroxyl radical depletion but were up to a factor of six wider for ozone formation from incremental additions of organic compounds. The cause of the discrepancies between the inter- and intra-mechanism ranges was found to be the large uncertainties that are present in the laboratory determinations of the rate coefficients and product channel branching ratios of some key chemical reactions involving organic peroxy radicals and hydroperoxides. Whilst these large uncertainties are present in the laboratory determinations, there will be irreducible uncertainties in the predictions from the earth system and other chemistry-transport models of methane and tropospheric ozone trends since pre-industrial times and hence their contributions to the radiative forcing of climate change. Further definitive laboratory studies of the reaction rates and product yields of the reactions of the simple organic peroxy radicals and hydroperoxides are required to resolve and reduce current uncertainties in earth system and chemistry-transport model predictions.

atmospheric chemistry↗
NASA NTRS2020

The Global Methane Budget 2000–2017

Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. Atmospheric emissions and concentrations of CH4 continue to increase, making CH4 the second most important human-influenced greenhouse gas in terms of climate forcing, after carbon dioxide (CO2). The relative importance of CH4 compared to CO2 depends on its shorter atmospheric lifetime, stronger warming potential, and variations in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in reducing uncertainties in the atmospheric growth rate arise from the variety of geographically overlapping CH4 sources and from the destruction of CH4 by short-lived hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate new research aimed at improving and regularly updating the global methane budget. Following Saunois et al. (2016), we present here the second version of the living review paper dedicated to the decadal methane budget, integrating results of top-down studies (atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up estimates (including process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). For the 2008–2017 decade, global methane emissions are estimated by atmospheric inversions (a top-down approach) to be 576 Tg CH4/yr (range 550–594, corresponding to the minimum and maximum estimates of the model ensemble). Of this total, 359 Tg CH4/yr or ∼ 60 % is attributed to anthropogenic sources, that is emissions caused by direct human activity (i.e. anthropogenic emissions; range 336–376 Tg CH4/yr or 50 %–65 %). The mean annual total emission for the new decade (2008–2017) is 29 Tg CH4/yr larger than our estimate for the previous decade (2000–2009), and 24 Tg CH4/yr larger than the one reported in the previous budget for 2003–2012 (Saunois et al., 2016). Since 2012, global CH4 emissions have been tracking the warmest scenarios assessed by the Intergovernmental Panel on Climate Change. Bottom-up methods suggest almost 30 % larger global emissions (737 Tg CH4/yr, range 594–881) than top-down inversion methods. Indeed, bottom-up estimates for natural sources such as natural wetlands, other inland water systems, and geological sources are higher than top-down estimates. The atmospheric constraints on the top-down budget suggest that at least some of these bottom-up emissions are overestimated. The latitudinal distribution of atmospheric observation-based emissions indicates a predominance of tropical emissions (∼ 65 % of the global budget, < 30° N) compared to mid-latitudes (∼ 30 %, 30–60° N) and high northern latitudes (∼ 4 %, 60–90° N). The most important source of uncertainty in the methane budget is attributable to natural emissions, especially those from wetlands and other inland waters. Some of our global source estimates are smaller than those in previously published budgets (Saunois et al., 2016; Kirschke et al., 2013). In particular wetland emissions are about 35 Tg CH4/yr lower due to improved partition wetlands and other inland waters. Emissions from geological sources and wild animals are also found to be smaller by 7 Tg CH4/yr by 8 Tg CH4/yr, respectively. However, the overall discrepancy between bottom-up and top-down estimates has been reduced by only 5 % compared to Saunois et al. (2016), due to a higher estimate of emissions from inland waters, highlighting the need for more detailed research on emissions factors. Priorities for improving the methane budget include (i) a global, high-resolution map of water-saturated soils and inundated areas emitting methane based on a robust classification of different types of emitting habitats; (ii) further development of process-based models for inland-water emissions; (iii) intensification of methane observations at local scales (e.g., FLUXNET-CH4 measurements) and urban-scale monitoring to constrain bottom-up land surface models, and at regional scales (surface networks and satellites) to constrain atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) development of a 3D variational inversion system using isotopic and/or co-emitted species such as ethane to improve source partitioning.

methane budget↗
NASA NTRSDate not supplied

Thermal Performance Comparison and Lessons Learned for the Thermal Infrared Sensor Instruments 1 & 2

The Thermal Infrared Sensor (TIRS-1) is one of two instruments on the Landsat-8 Mission, which launched in February of 2013 and remains operational. The TIRS-2 instrument was developed for the Landsat-9 Mission, which is scheduled to launch in September of 2021. The TIRS-2 instrument design was adjusted to account for requirements changes and to include key lessons learned from its predecessor. The overall thermal subsystem design of the TIRS Sensor Unit remained comparable from mission to mission, but there were some areas that needed modifications. The general design is comprised of five thermal zones which range in temperature from less than 43 Kelvin to 320 Kelvin. Most zones are proportional heater controlled. A two-stage cryocooler provided by Ball Aerospace is used to cool the cryogenic subsystem, and excess power dissipation is rejected via ammonia transport heat pipes to a dedicated cryocooler radiator with embedded ammonia heat pipes. The cryogenic subsystem includes a series of shells used to radiatively and conductively isolate the cold stage from the warmer surroundings. The Optical System (telescope) is passively cooled to 180-195 Kelvin using a dedicated radiator with embedded dual-bore ethane heat pipes. The warmer end of the instrument includes a Scene Select Mechanism, an on-board Black Body Calibrator with a dedicated radiator, and a Focal Plane Electronics Box, all of which are attached to the Sensor Unit primary structure. The TIRS-1 thermal subsystem design was successfully verified during an extended testing campaign and during more than 8years of on-orbit operations. The TIRS-2 thermal subsystem design was successfully verified during months of ground testing prior to delivery in August of 2019and at the Observatory level in the Spring of 2021. A detailed comparison of the thermal performance of the two instruments has been made with a focus on key lessons learned during each instrument development, and with the benefit of on-orbit data acquired for the TIRS-1 instrument.

Veronica Otero↗
NASA NTRSDate not supplied

Proposal for a Sample Return from Titan

We propose to explore a Titan sample return mission using in-situ volatile propellants available on its surface. Titan is unique in the outer solar system in that it is the only moon with a thick atmosphere, andthe only body in the solar system outside the Earth with liquid seas on its surface. The Titanian oceans, however, are seas of liquid hydrocarbons, and the rocks on the surface are solid water ice. Many studies of space development emphasize use of the in-situ resources to eliminate the requirement to launch propellants from Earth. With water, liquid methane,and ethane easily available, Titan is a rocket scientist’s dream for propellants.

Titan↗
NASA NTRSDate not supplied

Tangerine Dream: Observations of Titan from the Earth

From its discovery in 1655 by the Dutch astronomer Christiaan Huygens, Titan perplexed and confounded Earth-based astronomers for three centuries with its stubborn refusal to yield virtually any clues about its nature. Until the Voyager 1 1980, even fundamentals such as its true diameter, surface pressure, and major atmospheric gas were uncertain [1]. Most of the information we now know about Titan has been wrestled at great expense of time and effort by three spacecraft visitors: Voyager 1, Cassini and Huygens. So why then continue to bother with Earth-based telescopic observations? In this review talk I will describe how significant clues about Titan’s atmospheric composition began to emerge from ground-based observations in the 1940s through 1970s, in the run-up to the revolutionary Voyager 1 flyby. These included the discovery of methane [2], and other significant hydrocarbons including ethane and acetylene in Titan’s stratosphere [3, 4]. Further ground and space-based telescopic work in the 1980s and 1990s revealed the presence of the fourth most abundance gas, carbon monoxide [5], spotted for the first time the bright continent on Titan’s leading hemisphere now known as Xanadu [6], and the comings and goings of bright tropospheric clouds [7]. The Cassini-Huygens mission of 2004-2017 [8, 9] greatly expanded our knowledge of Titan, including the first in situ measurements of the atmosphere and detailed imaging of the surface. However in the two-decades long gap before the next mission, Dragonfly, reaches Titan we are finding new ways to further our knowledge of Titan using the current generation of telescopes and instruments. With high-resolution spectroscopy at infrared and sub-millimeter wavelengths we are finding new chemical constituents in the atmosphere, and even measuring wind fields at middle altitudes. I will conclude by discussing how the next generation of Earth and space-based telescopes and instruments promises yet more breakthroughs via astronomy, including with large aperture 30 and 40 meter class telescopes that will become available in the late 2020s, and spectroscopy with airborne

Titan↗
NASA NTRS2022

On the Stability and Phase Behavior of Titan's Subsurface Liquid Columns

On Titan, liquid hydrocarbon may stay in the subsurface porous permeable crust known as the alkanofer, analogous to water in Earth’s aquifer. In addition to pressure gradient, the subsurface liquid in alkanofers is subject to vertical compositional grading due to the gravity and temperature gradient. The common wisdom is that the liquid would normally stay underground in a stability established by the pressure that increases with depth as observed in aquifers on Earth. However, Titan’s liquids consist of nitrogen and hydrocarbons, mainly methane and ethane, the behavior of which is very sensitive to temperature and pressure. Consequently, the liquid density does not always increase with depth, thus may introduce a reverse density profile that leads to vertical convective instability of the liquid column. If reverse density profiles are present, capillary pressures arising from liquid trapped within small pores in the crust can help with the column stability. The liquid held in the capillaries can seal the space below it thus helping with the stability, unless the overpressure built from underneath becomes larger than the capillary pressure, which causes leakage to allow the liquids to seep upward from the deep. This situation is analogous to hydrocarbon seeps on Earth, where oil and natural gas escape the reservoir and flow slowly through network of cracks to the surface. An algorithm based on an extended Gibbs equation commonly used in petroleum reservoir engineering is employed in this work to produce pressure, density, and compositional profiles for evaluating the stability and phase behavior of Titan’s subsurface fluids.

Sugata Tan↗
NASA NTRS2022

Radiation-induced D/H Exchange Rate Constants in Aliphatics Embedded in Water Ice

Gas-phase and solid-state chemistry in low-temperature interstellar clouds and cores leads to a D/H enhancement in interstellar ices, which is eventually inherited by comets, meteorites, and even planetary satellites. Hence, the D/H ratio has been widely used as a tracer for the origins of extraterrestrial chemistry. However, the D/H ratio can also be influenced by cosmic rays, which are ubiquitous and can penetrate even dense interstellar molecular cores. The effects of such high-energy radiation on deuterium fractionation have not been studied in a quantitative manner. In this study, we present rate constants for radiation-induced D-to-H exchange for fully deuterated small (1–2 C) hydrocarbons embedded in H2O ice at 20 K and H-to-D exchange for the protiated forms of these molecules in D2O ice at 20 K. We observed larger rate constants for H-to-D exchange in the D2O ice versus D-to-H exchange in H2O ice, which we have attributed to the greater bond strength of C–D versus C–H. We find that the H-to-D exchange rate constants are smaller for protiated methane than ethane, in agreement with bond energies from the literature. We are unable to obtain rate constants for the unsaturated and reactive hydrocarbons ethylene and acetylene. Interpretation of the rate constants suggest that D/H exchange products are formed in abundance alongside radiolysis products. We discuss how our quantitative and qualitative data can be used to interpret the D/H ratios of aliphatic compounds observed throughout space.

Ice destruction↗
NASA NTRSDate not supplied

Evaluation of Low-Energy Hydrogen Separation Method Using Metal-Organic Frameworks (MOFs) for Closed-Loop ECLSS Air Revitalization (CLEAR)

The State-of-the-Art (SOA) air revitalization architecture onboard the International Space Station (ISS) recovered approximately 50% of the oxygen (O 2 ) from metabolic carbon dioxide (CO 2 ) via the Sabatier process from 2011 to 2017. O 2 recovery is currently constrained by the limited availability of reactant hydrogen (H 2 ) preventing complete conversion of CO 2 to H 2 O. Increasing O 2 recovery within Closed-Loop ECLSS is essential to reducing resupply mass for long-duration manned missions; specifically focusing on water (H 2 O) which supplies H 2 for Sabatier via water electrolysis. Past ground test endeavors at Marshall Space Flight Center (MSFC) have attempted to recover H 2 from Sabatier-produced CH 4 using technologies such as carbon vapor deposition (CVD) and plasma pyrolysis. The byproducts of these technologies can act as a catalyst poison or reactor deadload to the Sabatier reactor. Hydrogen separation techniques must be utilized to maintain the Sabatier catalyst during gas recycling and must be scalable, non-energy intensive, and safe to operate in a habitation setting. Research indicated that metal-organic frameworks (MOFs) could meet these criteria and were tested for their capability to capture the various carbon-based gaseous products of CVD and plasma pyrolysis such as acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 H 6 ), and carbon monoxide (CO) which would purify the hydrogen gas stream passing through the MOF. A sub-scale adsorption column was developed by Marshall Space Flight Center to test three MOF candidates against a synthetic gas mixture comprised of process-relevant carbonous gases and hydrogen to evaluate the separation capability of the MOFs. The results of the hydrogen separation capability, isothermal desorption capability, and demonstrated cyclic reuse of the MOF are presented in this paper.

Kagen Crawford↗
DOE OSTI2018

Electrolytes for supercapacitors

A supercapacitor and a related electrolyte composition suitable for use in a supercapacitor are provided. An electrolyte composition can include a conductive sodium salt component comprising NaTFSI and a non-aqueous solvent component comprising dimethoxy ethane (DME). The conductive sodium salt component and the non-aqueous solvent component can be present at a molar ratio of NaTFSI:DME of 1:1 to 1:3, inclusive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Understanding coking on Platinum catalysts by in situ TEM

Light alkenes are widely use as building blocks for the production of rubber, plastics, and other polymers, and are currently produced by steam cracking of alkanes or naphtha at high temperatures. However, these processes exhibit low alkene selectivity and produce significant amounts of methane and coke. Catalytic dehydrogenation of C2-C5 alkanes offers an attractive alternative because it utilizes low-cost reactants and can be carried out with high selectivity(1). Platinum is known to be the most effective transition metal for dehydrogenation of light alkanes. However, in the absence of a promoting element such as Sn, platinum catalysts deactivate rapidly due to coke formation, making it difficult to measure the true initial activity in comparison with bimetallic PtSn catalysts(2). Furthermore, it is difficult to assess composition and nanoparticle size effects with catalysts synthesized by traditional impregnation methods. We have developed a colloidal synthesis in which we form the metal particles ex-situ, enabling stricter control over the nucleation and growth of nanoparticles(3). Following immobilization and reduction, model catalysts of fixed composition and size are used in this study. This talk will present the effects of composition (PtxSny) and size (2-8 nm) on ethane dehydrogenation at low residence-time, a novel method that we show to significantly reduce coke formation and measure the true activity of these catalysts. Catalysts composition and size are characterized by XRD, TEM, and EDX. The results show that the addition of Sn favors higher ethene production and selectivity, even in the absence of coke formation. Furthermore, the reaction is more favored on large particles that can be explained by poisoning of corner sites on small particles. In conjunction with these studies, we have examined coke formation on Pt particles in-situ using a Titan 80-300 ETEM to better understand the location of carbon nucleation along with the formation of multiple graphene layers. If these issues are resolved, design of future catalysts to limit deactivation can be achieved(4). However, imaging challenges to avoid beam effects exist and obtaining an optimal imaging strategy to observe carbon formation on Pt will be discussed.

Wu, J↗