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DOE OSTI2022

Zeolitic Imidazolate Framework Membranes: Novel Synthesis Methods and Progress Toward Industrial Use

In the last decade, zeolitic imidazolate frameworks (ZIFs) have been studied extensively for their potential as selective separation membranes. In this review, we highlight unique structural properties of ZIFs that allow them to achieve certain important separations, like that of propylene from propane, and summarize the state of the art in ZIF thin-film deposition on porous substrates and their modification by postsynthesis treatments. We also review the reported membrane performance for representative membrane synthesis approaches and attempt to rank the synthesis methods with respect to potential for scalability. To compare the dependence of membrane performance on membrane synthesis methods and operating conditions, we map out fluxes and separation factors of selected ZIF-8 membranes for propylene/propane separation. Finally, we provide future directions considering the importance of further improvements in scalability, cost effectiveness, and stable performance under industrially relevant conditions.

Chemistry↗

NASA NTRS2004

Glow Discharge Plasma Demonstrated for Separation Control in the Low-Pressure Turbine

Flow separation in the low-pressure turbine (LPT) is a major barrier that limits further improvements of aerodynamic designs of turbine airfoils. The separation is responsible for performance degradation, and it prevents the design of highly loaded airfoils. The separation can be delayed, reduced, or eliminated completely if flow control techniques are used. Successful flow control technology will enable breakthrough improvements in gas turbine performance and design. The focus of this research project was the development and experimental demonstration of active separation control using glow discharge plasma (GDP) actuators in flow conditions simulating the LPT. The separation delay was shown to be successful, laying the foundation for further development of the technologies to practical application in the LPT. In a fluid mechanics context, the term "flow control" means a technology by which a very small input results in a very large effect on the flow. In this project, the interest is to eliminate or delay flow separation on LPT airfoils by using an active flow control approach, in which disturbances are dynamically inserted into the flow, they interact with the flow, and they delay separation. The disturbances can be inserted using a localized, externally powered, actuating device, examples are acoustic, pneumatic, or mechanical devices that generate vibrations, flow oscillations, or pulses. A variety of flow control devices have been demonstrated in recent years in the context of the external aerodynamics of aircraft wings and airframes, where the incoming flow is quiescent or of a very low turbulence level. However, the flow conditions in the LPT are significantly different because there are high levels of disturbances in the incoming flow that are characterized by high free-stream turbulence intensity. In addition, the Reynolds number, which characterizes the viscous forces in the flow and is related to the flow speed, is very low in the LPT passages.

Ashpis, David e.↗

NASA NTRS1977

Coherence between internal and external noise generated by gas turbine combustors

Experiments and analysis on a gas turbine combustor unit are reported with a view in mind to separate propagated acoustic power from non-propagating 'pseudo-sound'. Analytically, it is suggested that a transition frequency will exist below which the interior pressure fluctuations are non-propagating, whereas above this frequency, of the order of 100 Hz, the noise is dominated by propagating acoustic waves. Coherence measurements are reported which show this concept to be borne out experimentally. Coherence between interior and exterior microphones is measured over a wide range of experimental conditions for a gas turbine combustor exhausting directly to the atmosphere. The purpose is to show that below a certain frequency, measurements of interior noise are not indicative of combustion noise ultimately propagating from an engine.

Strahle, W. C.↗

NASA NTRS1994

Acoustic instability driven by cosmic-ray streaming

We study the linear stability of compressional waves in a medium through which cosmic rays stream at the Alfven speed due to strong coupling with Alfven waves. Acoustic waves can be driven unstable by the cosmic-ray drift, provided that the streaming speed is sufficiently large compared to the thermal sound speed. Two effects can cause instability: (1) the heating of the thermal gas due to the damping of Alfven waves driven unstable by cosmic-ray streaming; and (2) phase shifts in the cosmic-ray pressure perturbation caused by the combination of cosmic-ray streaming and diffusion. The instability does not depend on the magnitude of the background cosmic-ray pressure gradient, and occurs whether or not cosmic-ray diffusion is important relative to streaming. When the cosmic-ray pressure is small compared to the gas pressure, or cosmic-ray diffusion is strong, the instability manifests itself as a weak overstability of slow magnetosonic waves. Larger cosmic-ray pressure gives rise to new hybrid modes, which can be strongly unstable in the limits of both weak and strong cosmic-ray diffusion and in the presence of thermal conduction. Parts of our analysis parallel earlier work by McKenzie & Webb (which were brought to our attention after this paper was accepted for publication), but our treatment of diffusive effects, thermal conduction, and nonlinearities represent significant extensions. Although the linear growth rate of instability is independent of the background cosmic-ray pressure gradient, the onset of nonlinear eff ects does depend on absolute value of DEL (vector differential operator) P(sub c). At the onset of nonlinearity the fractional amplitude of cosmic-ray pressure perturbations is delta P(sub C)/P(sub C) approximately (kL) (exp -1) much less than 1, where k is the wavenumber and L is the pressure scale height of the unperturbed cosmic rays. We speculate that the instability may lead to a mode of cosmic-ray transport in which plateaus of uniform cosmic-ray pressure are separated by either laminar or turbulent jumps in which the thermal gas is subject to intense heating.

Begelman, Mitchell C.↗

NASA NTRS2012

SOFIA Observations of S106: Dynamics of the Warm Gas

Context The H II region/PDR/molecular cloud complex S106 is excited by a single O-star. The full extent of the warm and dense gas close to the star has not been mapped in spectrally resolved high-J CO or [C II] lines, so the kinematics of the warm. partially ionized gas, are unknown. Whether the prominent dark lane bisecting the hourglass-shaped nebula is due solely to the shadow cast by a small disk around the exciting star or also to extinction in high column foreground gas was an open question until now. Aims. To disentangle the morphology and kinematics of warm neutral and ionized gas close to the star, study their relation to the bulk of the molecular gas. and to investigate the nature of the dark lane. Methods. We use the heterodyne receiver GREAT on board SOFIA to observe velocity resolved spectral lines of [C II] and CO 11 yields 10 in comparison with so far unpublished submm continuum data at 350 micron (8HARC-Il) and complementary molecular line data. Results. The high angular and spectral resolution observations show a very complex morphology and kinematics of the inner S106 region, with many different components at different excitation conditions contributing to the observed emission. The [C II] lines are found to be bright and very broad. tracing high velocity gas close to the interface of molecular cloud and H II region. CO 11 yields 10 emission is more confined.. both spatially and in velocity, to the immediate surroundings of S 106 IR showing the presence of warm, high density (clumpy) gas. Our high angular resolution submm continuum observations rule out the scenario where the dark lane separating the two lobes is due solely to the shadow cast by a small disk close to the star. The lane is clearly seen also as warm, high column density gas at the boundary of the molecular cloud and H II region.

Simon, R.↗

DOE OSTI2020

Nemchinov-Dyson Solutions of the Two-Dimensional Axisymmetric Inviscid Compressible Flow Equations [Review]

We investigate the two-dimensional (2D) inviscid compressible flow equations in axisymmetric coordinates, constrained by an ideal gas equation of state (EOS). Beginning with the assumption that the 2D velocity field is space-time separable and linearly variable in each corresponding spatial coordinate, we proceed to derive an in nite family of elliptic or hyperbolic, uniformly expanding or contracting \gas cloud" solutions. Construction of specific example solutions belonging to this family is dependent on the solution of a system of nonlinear, coupled, second-order ordinary differential equations, and the prescription of an additional physical process of interest (e.g., uniform temperature or uniform entropy flow). The physical and computational implications of these solutions as pertaining to quantitative code verification or model qualification studies are discussed in some detail.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS1974

Investigation of a catalytic gas generator for the Space Shuttle APU

An investigation was conducted to establish the capability of a monopropellant hydrazine catalytic gas generator to meet the requirements specified for the Space Shuttle APU. Detailed analytical and experimental studies were conducted on potential problem areas including long-term nitriding effects on materials, design variables affecting catalyst life, vehicle vibration effects, and catalyst oxidation/contamination. A full-scale gas generator, designed to operate at a chamber pressure of 750 psia and a flow rate of 0.36 lbm/sec, was fabricated and subjected to three separate life test series. The objective of the first test series was to demonstrate the capability of the gas generator to successfully complete 20 simulated Space Shuttle missions in steady-state operation. The gas generator was then refurbished and subjected to a second series of tests to demonstrate the pulse-mode capability of the gas generator during 20 simulated missions. The third series of tests was conducted with a refurbished reactor to further demonstrate pulse-mode capability with a modified catalyst bed.

Emmons, D. L.↗

DOE OSTI2026

Off-gas capture: a promising strategy for removal and recovery of toxic bioproducts in aerobic fermentation

In many bioprocesses, maximum achievable titers are limited below economically viable levels by toxic accumulation of the primary end-product. To combat end-product inhibition, a variety of in situ product removal technologies have been developed to selectively remove or partition toxic bioproducts, thereby prolonging fermentation and improving overall process efficiency. Use of an in situ organic overlay to partition toxic hydrophobic products is a commonly employed approach, but this technique occupies valuable space in the fermentor, imposes replacement costs for unrecovered solvent, and increases downstream separation due to formation of stable emulsions. In addition, for many volatile hydrophobic products produced under aerobic conditions—including medium-chain alcohols, esters, monoterpenes, and other aviation fuel precursors—a significant fraction of the product is volatilized to the fermentor off-gas and must be recovered separately to maximize product yield. To address these challenges, we explore the viability of leveraging existing aeration energy to fully strip and recover volatile products from the fermentor off-gas. We compare two strategies of in situ product removal—liquid–liquid extraction and direct recovery from fermentation off-gas—for the production and recovery of intermediates used to generate isoprene and DMCO (1,4-dimethylcyclooctane), a high-performance jet fuel. We evaluate product toxicity, solvent toxicity, solvent partitioning, and the impact of aeration and internal overlay configurations on product volatilization rates. We then optimize product recovery from fermentor off-gas via condensation in chilled solvent, achieving 84% capture efficiency. In addition to greatly simplifying downstream processing, relying on aeration for product volatilization in the absence of an internal overlay enables continuous removal of toxic fermentation products up to maximum isoprenol titers of 20.4 g/L, the highest reported to date.

isoprene↗

NASA NTRS2008

Investigation of Condensing Ice Heat Exchangers for MTSA Technology Development

Metabolic heat regenerated Temperature Swing Adsorption (MTSA) technology is being developed for thermal, carbon dioxide (CO2) and humidity control for a Portable Life Support Subsystem (PLSS). Metabolically-produced CO2 present in the ventilation gas of a PLSS is collected using a CO2selective adsorbent via temperature swing adsorption. The temperature swing is initiated through cooling to well below metabolic temperatures. Cooling is achieved with a sublimation heat exchanger using water or liquid carbon dioxide (LCO2) expanded below sublimation temperature when exposed to low pressure or vacuum. Subsequent super heated vapor, as well as additional coolant, is used to further cool the astronaut. The temperature swing on the adsorbent is then completed by warming the adsorbent with a separate condensing ice heat exchanger (CIHX) using metabolic heat from moist ventilation gas. The condensed humidity in the ventilation gas is recycled at the habitat. The water condensation from the ventilation gas is a significant heat transfer mechanism for the warming of the adsorbent bed because it represents as much as half of the energy potential in the moist ventilation gas. Designing a heat exchanger to efficiently transfer this energy to the adsorbent bed and allow the collection of the water is a challenge since the CIHX will operate in a temperature range from 210K to 280K. The ventilation gas moisture will first freeze and then thaw, sometimes existing in three phases simultaneously. A NASA Small Business Innovative Research (SBIR) Phase 1 contract was performed to investigate condensing and icing as applied to MTSA to enable higher fidelity modeling and assess the impact of geometry variables on CIHX performance for future CIHX design optimization. Specifically, a design tool was created using analytical relations to explore the complex, interdependent design space of a condensing ice heat exchanger. Numerous variables were identified as having nontrivial contributions to performance such as hydraulic diameter, heat exchanger effectiveness, ventilation gas mass flow rate and surface roughness. Using this tool, four test articles were designed and manufactured to map to a full MTSA subassembly (the adsorbent bed, the sublimation heat exchanger for cooling and the condensing ice heat exchanger for warming). The design mapping considered impacts due to CIHX geometry as well as subassembly impacts such as thermal mass and thermal resistance through the adsorbent bed. The test articles were tested at simulated PLSS ventilation loop temperature, moisture content and subambient pressure. Ice accumulation and melting were observed. Data and test observations were analyzed to identify drivers of the condensing ice heat exchanger performance. This paper will discuss the analytical models, the test article designs, and testing procedures. Testing issues will be discussed to better describe data and share lessons learned. Data analysis and subsequent conclusions will be presented.

Padilla, Sebastian↗

NASA NTRS1972

Hydrophobic liquid/gas separator for heat pipes

Perforated nonwetting plug of material such as polytetrafluoroethylene is mounted in gas reservoir feed tube, preferably at end which extends into heat pipe condenser section, to prevent liquid from entering gas reservoir of passively controlled heat pipe.

Marcus, B. D.↗

NASA NTRS2009

Investigation of Condensing Ice Heat Exchangers for MTSA Technology Development

Padilla, Sebastian↗

DOE OSTI2021

Molecular bridge-mediated ultralow-power gas sensing

Abstract We report the electrical detection of captured gases through measurement of the quantum tunneling characteristics of gas-mediated molecular junctions formed across nanogaps. The gas-sensing nanogap device consists of a pair of vertically stacked gold electrodes separated by an insulating 6 nm spacer (~1.5 nm of sputtered α-Si and ~4.5 nm ALD SiO 2 ), which is notched ~10 nm into the stack between the gold electrodes. The exposed gold surface is functionalized with a self-assembled monolayer (SAM) of conjugated thiol linker molecules. When the device is exposed to a target gas (1,5-diaminopentane), the SAM layer electrostatically captures the target gas molecules, forming a molecular bridge across the nanogap. The gas capture lowers the barrier potential for electron tunneling across the notched edge region, from ~5 eV to ~0.9 eV and establishes additional conducting paths for charge transport between the gold electrodes, leading to a substantial decrease in junction resistance. We demonstrated an output resistance change of >10 8 times upon exposure to 80 ppm diamine target gas as well as ultralow standby power consumption of <15 pW, confirming electron tunneling through molecular bridges for ultralow-power gas sensing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS1973

Argon in Apollo 15 green glass spherules /15426/ - Ar-40-Ar-39 age and trapped argon

The results of thermal-release argon analyses of neutron-irradiated green glass spherules separated from the lunar sample 15426 are discussed. It is shown that the gas-retention age determined by the Ar-40-Ar-39 method is similar to that of local mare basalts, and differs from the ages of Appenine Front samples recovered from the same region as 15426. Trapped argon is present in near-surface regions of the spherules, and can be resolved into at least two components requiring separate origins: a shallow (0.1 micron) component with Ar-40/Ar-39 not less than 30, and a deeper (2.0 micron) component with an Ar-40/Ar-39 ratio of 2.9. The ratio of trapped Ar-40 to Ar-36 is higher than in any lunar soil samples, and suggests that the trapped gas was implanted early in the spherules history.

Podosek, F. A.↗

NASA NTRS1996

A Computational Fluid Dynamic and Heat Transfer Model for Gaseous Core and Gas Cooled Space Power and Propulsion Reactors

A computational model based on the axisymmetric, thin-layer Navier-Stokes equations is developed to predict the convective, radiation and conductive heat transfer in high temperature space nuclear reactors. An implicit-explicit, finite volume, MacCormack method in conjunction with the Gauss-Seidel line iteration procedure is utilized to solve the thermal and fluid governing equations. Simulation of coolant and propellant flows in these reactors involves the subsonic and supersonic flows of hydrogen, helium and uranium tetrafluoride under variable boundary conditions. An enthalpy-rebalancing scheme is developed and implemented to enhance and accelerate the rate of convergence when a wall heat flux boundary condition is used. The model also incorporated the Baldwin and Lomax two-layer algebraic turbulence scheme for the calculation of the turbulent kinetic energy and eddy diffusivity of energy. The Rosseland diffusion approximation is used to simulate the radiative energy transfer in the optically thick environment of gas core reactors. The computational model is benchmarked with experimental data on flow separation angle and drag force acting on a suspended sphere in a cylindrical tube. The heat transfer is validated by comparing the computed results with the standard heat transfer correlations predictions. The model is used to simulate flow and heat transfer under a variety of design conditions. The effect of internal heat generation on the heat transfer in the gas core reactors is examined for a variety of power densities, 100 W/cc, 500 W/cc and 1000 W/cc. The maximum temperature, corresponding with the heat generation rates, are 2150 K, 2750 K and 3550 K, respectively. This analysis shows that the maximum temperature is strongly dependent on the value of heat generation rate. It also indicates that a heat generation rate higher than 1000 W/cc is necessary to maintain the gas temperature at about 3500 K, which is typical design temperature required to achieve high efficiency in the gas core reactors. The model is also used to predict the convective and radiation heat fluxes for the gas core reactors. The maximum value of heat flux occurs at the exit of the reactor core. Radiation heat flux increases with higher wall temperature. This behavior is due to the fact that the radiative heat flux is strongly dependent on wall temperature. This study also found that at temperature close to 3500 K the radiative heat flux is comparable with the convective heat flux in a uranium fluoride failed gas core reactor.

Anghaie, S.↗

DOE OSTI2022

Thermoacoustic Soret separation

In a fluid mixture in a channel with an axial time-averaged temperature gradient, high-amplitude oscillating flow can greatly increase the axial flux of thermal diffusion (Soret) separation of the components of the mixture. The enhancement occurs when the oscillating lateral temperature gradient greatly exceeds the axial gradient, causing a large oscillating concentration that can be favorably time-phased with the oscillating flow. This process can occur even with a negligible pressure oscillation or with a negligible temperature response to pressure, as is the case in most liquid solutions. The thermal boundary condition imposed by realistic solids on thermoacoustic liquids is imperfect, adding mathematical complications that are absent for typical gases, for which the solid surface is temporally isothermal. Compared with gas mixtures, the high Lewis number in typical liquid solutions reduces the separation flux associated with the time-averaged temperature gradient, but it also reduces the remixing associated with the time-averaged mole-fraction gradient. For large enough channels, the second-law separation efficiency is only slightly reduced from that of steady liquid Soret separation.

36 MATERIALS SCIENCE↗

NASA NTRS1989

Plasma ion heating of an SO2 atmosphere on Io

The Jovian plasma-ion heating of any atmospheric gas over Io is shown to be important for determining the temperature structure and the location of the exobase and for limiting diffusive separation in Io's atmosphere. This is used, along with the plasma supply rate, to estimate an average column of gas over the trailing hemisphere of about 3 x 10 to the 16th SO2/sq cm with exobase at about 1.4 Io radii.

Johnson, R. E.↗

DOE OSTI2022

Modeling Integrated Electricity and Natural Gas Systems Using Co-Simulation

One approach for modeling natural gas and electricity networks as integrated systems is co-simulation, which involves separating a single model into subproblems that are solved iteratively, with coupling information passed between then. Although a fully integrated problem might be more direct, co-simulation offers advantages in that it can sometimes be more computationally tractable, and can also leverage existing simulation tools to represent the subproblems. Here we present a framework for co-simulation of natural gas and electricity networks using the HELICS tool. We provide validation of the co-simulation approach by comparing results with a fully integrated approach that uses the same simulation tool, finding that the two approaches provide identical results for a range of test cases. We then present results from natural gas and electricity network co-simulation case study of the Colorado Front Range, with an evaluation of the present-day system and also a future system with higher shares of renewable power. The presentation will close with a discussion on future avenues of work for co-simulation of gas and power networks.

co-simulation↗

NASA NTRS1993

Isotopic composition and concentration of sulfur in carbonaceous chondrites

New sulfur isotopic ratio measurements are reported for seven carbonaceous chondrites. Newly developed procedures permit measurement of delta S-33, delta S-34, and delta S-36 at precisions significantly greater than previously reported. A search for S-36 nucleosynthetic anomalies coproduced with anomalies in, for example, Ti-50 and Ca-48 was negative. The high endemic sulfur concentration probably dilutes any S-36 anomaly, and separation of individual sulfur phases may be needed to identify S-36 carrier phases. Large internal isotopic variations are observed, deriving from parent body and possibly nebular processes. Chondrule separates from Allende demonstrate isotopic compositions which vary as a function of diameter. High-temperature gas-solid exchange and a two-component mixing model may account for the observations. High-resolution isotopic data and structural information are reported for organic sulfur compounds separated by chemical extractions. The insoluble organics appear to be of either aliphatic or alicyclic structure and are dominant phases.

Gao, Xia↗