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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

An experimental, theoretical and kinetic modeling study of the N 2 O-H 2 system: Implications for N 2 O + H

The reaction of N 2 O with His the key step in consumption of nitrous oxide in thermal processes. The major product channel is N 2 + OH, while NH + NO constitute minor products. In addition, a pathway involving HNNO, initiated by N 2 O + H (+M)$\rightleftarrows$HNNO (+M) (R3, R4), has been inferred from experiment and theory by Burke and coworkers. At longer reaction times, the reaction may reach partial equilibration, and in addition to k 3 and k 4 the importance of this channel depends on the thermodynamic properties of HNNO and its consumption reactions, mainly HNNO + H. In the present work, we re-examined the thermochemistry of HNNO and calculated rate constants and branching fractions for the HNNO + H reaction. Experiments on the N 2 O-H 2 system were conducted in a high-pressure flow reactor at 100 atm as a function of temperature (600-925 K) and stoichiometry and explained in terms of an updated chemical kinetic model. The results support the importance of the HNNO pathway, which results in inhibition of N 2 O consumption and formation of NH 3 . In addition, selected literature results on the N 2 O-H 2 system are re-examined and the implications for the other product channels of N 2 O + H, in particular NH + NO, are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1976

A model study of diurnal behavior of the ionosphere and the protonosphere coupling

A new method to study dynamic behavior of the ionosphere-protonosphere coupling within the plasmasphere is developed and used to calculate ion distributions above 500 km using observed electron densities at 500 km. The method is based on the relation between the total magnetic flux tube content of H(+) above some reference height (e.g., 3000 km) and the H(+) flux at that height, which is uniquely determined by the coupled momentum and continuity equations for the quasi-steady state. The O(+) profile is perturbed from diffusive equilibrium only by ion drag with H(+). The time dependency is taken into account by applying self-consistent boundary conditions which are obtained from the solution of the time-dependent equation for the tube content of H(+). Calculations are carried out for two models. The first model deals with the ion dynamics in a tube of force which rotates with the earth. In the second model, effects of the cross-L plasma drifts are considered. Both models produce diurnal variations of H(+) and O(+) densities near 1000 km similar to observational results.

Marubashi, K.↗
NASA NTRS1991

Heterogeneous processes: Laboratory, field, and modeling studies

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Poole, Lamont R.↗
NASA NTRS1998

Trifluoroacetic Acid from Degradation of HCFCs and HFCs: A Three-dimensional Modeling Study

Trifluoroacetic acid (TFA; CF3 COOH) is produced by the degradation of the halocarbon replacements HFC-134a, HCFC-124, and HCFC-123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF3COX (X = F or CI), followed by in-cloud hydrolysis of CF3COX to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long-term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC-134a, HCFC-124, and HCFC-123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 microg/L if washout were the only removal mechanism for TFA. We present 3-D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS/Harvard/ UCI) but coarse-resolution (8 deg latitude by 10 deg longitude) chemical transport model was used. The anually averaged rainwater concentration of 0.12 gg/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger, 0.15-0.20 microg/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3-0.45 microg/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF3CHFO is produced in the degradation of HFC-134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.

Kotamarthi, V. R.↗
NASA NTRS1998

Trifluoroacetic Acid from Degradation of HCFCs and HFCs: A Three-Dimensional Modeling Study

Trifluoroacetic acid (TFA; CF3COOH) is produced by the degradation of the halocarbon replacements HFC-134a, HCFC-124, and HCFC-123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF3COX (X = F or CI), followed by in-cloud hydrolysis of CF3COX to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long-term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC-134a, HCFC-124, and HCFC-123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 micro g/L if washout were the only removal mechanism for TFA. We present 3-D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS/Harvard/ UCI) but coarse-resolution (8 deg latitude by 10 deg longitude) chemical transport model was used. The annually averaged rainwater concentration of 0.12 micro g/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger, 0.15-0.20 micro g/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3-0.45 micro g/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF3CHFO is produced in the degradation of HFC-134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.

Kotamarthi, V. R.↗
NASA NTRS1998

Trifluoroacetic Acid from Degradation of HCFCs and HFCs: A Three-Dimensional Modeling Study

Trifluoroacetic acid (TFA; CF3 COOH) is produced by the degradation of the halocarbon replacements HFC-134a, HCFC-124, and HCFC-123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF3COX (X = F or CI), followed by in-cloud hydrolysis of CF to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long-term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC-134a, HCFC-124, and HCFC-123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 micro g/L if washout were the only removal mechanism for TFA. We present 3-D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS[Harvard/ UCI) but coarse-resolution (8 deg latitude by 10 deg longitude) chemical transport model was used. The annually averaged rainwater concentration of 0.12 micro g/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger. 0.15-0.20 micro g/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3 - 0.45 micro g/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF3CHFO is produced in the degradation of HFC-134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.

Kotamarthi, V. R.↗
DOE OSTI2021

Oxidation of an iso-paraffinic alcohol-to-jet fuel and n-heptane mixture: an experimental and modelling study

Oxidation of ATJ/n-heptane blends was studied over a wide range of test conditions, using single pulse shock tubes. Test conditions were designed to study the effect of pressure (4 and 50 bar), and fuel loading (~100-1400 ppm) on the oxidation of the blends across a wide range of temperatures (800-1300 K). These effects were observed by measuring concentrations of intermediate species formed using in-line Gas Chromatography (GC) and GCxGC TOF-MS. Results showed that increasing the initial fuel load does not have a significant impact on the results. However, increasing the pressure shifts the mixture reactivity to a lower temperature by about 150 K and causes the fuel to be oxidized instead of decomposing pyrolytically as at lower pressures. Additional experiments for pure ATJ and pure n-heptane were performed at conditions matching the ATJ/n-heptane 50 bar experiments to analyze the differences between the pure and mixed fuels. Speciation measurements were compared against predictions from a detailed kinetic model. The ability of the kinetic model to capture the effects of varying experimental test conditions on the evolution of intermediate species is discussed and kinetic analyses have been conducted to identify the important reaction pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

An experimental and modeling study of the application of membrane contactor reactors to methanol synthesis using pure CO 2 feeds

We describe here a post-combustion CO 2 capture and utilization (CCU) technology that converts the CO 2 into methanol (MeOH), a valuable chemical, thus providing a way to monetize the carbon captured to offset process costs. Methanol synthesis (MeS) has been discussed recently for application to CCU, but thermodynamic limitations make it difficult to convert in a single pass a large CO 2 fraction. Conventional catalysts show slow kinetics in converting CO 2 -rich syngas (or pure CO 2 ) into MeOH. Our Group developed a novel MeS process, employing a membrane contactor reactor (MCR) system that attains carbon conversions significantly higher than equilibrium. Our focus here is to process pure CO 2 streams by combining the MCR with a separate reactor, which converts the CO 2 into a syngas via the reverse water gas shift (RWGS) reaction. In this preliminary effort, the RWGS reactor (RWGSR) is assumed to reach equilibrium. Additional MeS kinetic rate data are generated validating experimentally the ability of the MeS-MCR to process as a feed the RWGSR exit stream. The performance of the combined (RWGSR/MeS-MCR) system is then simulated using a recently developed MeS-MCR model. In conclusion, the findings are encouraging, and research is currently ongoing to experimentally validate the RWGSR/MeS-MCR system performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2013

Erosion, Transportation, and Deposition on Outer Solar System Satellites: Landform Evolution Modeling Studies

Mass movement and landform degradation reduces topographic relief by moving surface materials to a lower gravitational potential. In addition to the obvious role of gravity, abrasive mechanical erosion plays a role, often in combination with the lowering of cohesion, which allows disaggregation of the relief-forming material. The identification of specific landform types associated with mass movement and landform degradation provides information about local sediment particle size and abundance and transportation processes. Generally, mass movements can be classified in terms of the particle sizes of the transported material and the speed the material moved during transport. Most degradation on outer planet satellites appears consistent with sliding or slumping, impact erosion, and regolith evolution. Some satellites, such as Callisto and perhaps Hyperion and Iapetus, have an appearance that implies that some additional process is at work, most likely sublimation-driven landform modification and mass wasting. A variant on this process is thermally driven frost segregation as seen on all three icy Galilean satellites and perhaps elsewhere. Titan is unique among outer planet satellites in that Aeolian and fluvial processes also operate to erode, transport, and deposit material. We will evaluate the sequence and extent of various landform-modifying erosional and volatile redistribution processes that have shaped these icy satellites using a 3-D model that simulates the following surface and subsurface processes: 1) sublimation and re-condensation of volatiles; 2) development of refractory lag deposits; 3) disaggregation and downward sloughing of surficial material; 4) radiative heating/cooling of the surface (including reflection, emission, and shadowing by other surface elements); 5) thermal diffusion; and 6) vapor diffusion. The model will provide explicit simulations of landform development and thusly predicts the topographic and volatile evolution of the surface and final landscape form as constrained by DEMs. We have also simulated fluvial and lacustrine modification of icy satellites landscapes to evaluate the degree to which fluvial erosion of representative initial landscapes can replicate the present Titan landscape.

erosion↗
NASA NTRS2002

Are Solar Activity Variations Amplified by the QBO: A Modeling Study

Solar cycle activity effects (SCAE) in the lower and middle atmosphere, reported in several studies, are difficult to explain on the basis of the small changes in solar radiation that accompany the 11-year cycle. It is therefore natural to speculate that dynamical processes may come into play to produce a leverage. Such a leverage may be provided by the Quasi-Biennial Oscillation (QBO) in the zonal circulation of the stratosphere, which has been linked to solar activity variations. Driven primarily by wave mean flow interaction, the QBO period and its amplitude are variable but are also strongly influenced by the seasonal cycle in the solar radiation. This influence extends to low altitudes and is referred to as 'downward control'. Small changes in the solar radiative forcing may produce small changes in the period and phase of the QBO, but these in turn may produce measurable differences in the wind field. Thus, the QBO may be an amplifier of solar activity variations and a natural conduit of these variations to lower altitudes. To test this hypothesis, we conducted experiments with a 2D version of our Numerical Spectral Model that incorporates Hines' Doppler Spread Parameterization for small-scale gravity waves (GW). Solar cycle radiance variations (SCRV) are accounted for by changing the radiative heating rate on a logarithmic scale from 0.1% at the surface to 1% at 50 km to 10% at 100 km. With and without SCRV, but with the same GW flux, we then conduct numerical experiments to evaluate the magnitude of the SCAE in the zonal circulation. The numerical results indicate that, under certain conditions, the SCAE is significant and can extend to lower altitudes where the SCRV is small. For a modeled QBO period of 30 months, we find that the seasonal cycle in the solar forcing acts as a strong pacemaker to lock up the phase and period of the QBO. The SCAE then shows up primarily as a distinct but relatively weak amplitude modulation. But with a different QBO period between 30 and 34 (or less than 30, presumably) months, the seasonal phase lock is weak. Solar flux variations in the seasonal cycle then cause variations in the QBO period and phase. These amplify the SCAE to produce relatively large variations in the wind field. The SCAE in this case extends to mid-latitudes.

Mengel, J. G.↗
NASA NTRS2001

Solar Cycle Variations and Equatorial Oscillations: Modeling Study

Solar cycle activity effects (SCAE) in the lower and middle atmosphere, reported in several studies, are difficult to explain on the basis of the small changes in solar radiation that accompany the 11-year cycle, It is therefore natural to speculate that dynamical processes may come into play to produce a leverage. Such a leverage may be provided by the Quasi-Biennial Oscillation (QBO) in the zonal circulation of the stratosphere, which has been linked to solar activity variations. Driven primarily by wave mean flow interaction, the QBO period and its amplitude are variable but are also strongly influenced by the seasonal cycle in the solar radiation. This influence extends to low altitudes referred to as "downward control". Relatively small changes in solar radiative forcing can produce small changes in the period and phase of the QBO, but this in turn can produce measurable differences in the wind field. Thus, the QBO may be an amplifier of solar activity variations and a natural conduit of these variations to lower altitudes. To test this hypothesis, we conducted experiments with a 2D (two-dimensional) version of our Numerical Spectral Model that incorporates Hines' Doppler Spread Parameterization for small-scale gravity waves (GW). Solar cycle radiance variations (SCRV) are accounted for by changing the radiative heating rate on a logarithmic scale from 0.1 % at the surface to 1 % at 50 km to 10% at 100 km. With and without SCRV, but with the same GW flux, we then conduct numerical experiments to evaluate the magnitude of the SCAE in the zonal circulation. The numerical results indicate that, under certain conditions, the SCAE is significant and can extend to lower altitudes where the SCRV is inconsequential. At 20-km the differences in the modeled wind velocities are as large as 5 m/s. For a modeled QBO period of 30 months, we find that the seasonal cycle in the solar forcing (through the Semi-annual Oscillation (SAO)) acts as a strong pacemaker to lockup the phase and period of the QBO. The SCAE then shows up primarily as a distinct but relatively weak amplitude modulation. But with the QBO period between 30 and 34 (or less than 30, presumably) months, the seasonal phase lock is weak. Solar flux radiance variations in the seasonal cycle then cause variations in the QBO period and phase that amplify the SCAE to produce relatively large variations in the wind field. These variations also extend to mid latitudes.

Mayr, H. G.↗
NASA NTRS2023

Combined Experimental and Modeling Study of the Interactions of Acid Gas with Common Spacecraft Surfaces for Fire Safety Applications

A fire in a spacecraft poses detrimental consequences and risks mission success in addition to crew safety. This is compounded during long-duration missions when the crew has limited options to recover from a fire. A common spacecraft fire concern is the smoldering of wire insulation, typically made from Polyvinyl chloride (PVC) or Polytetrafluoroethylene (PTFE). This creates acid gases such as Hydrogen Chloride (HCl), Hydrogen Fluoride (HF) and Hydrogen Cyanide (HCN). These poisonous gases are hazardous to the crew. They also interact with common surfaces within the spacecraft more than dominant combustion products such as CO2 and H2O. This makes them more difficult to track for potential fire detection techniques, or for postfire clean-up. It is imperative to be able to understand and predict the fate of these poisonous species in a microgravity environment in order to design a safe vehicle. HCl interacts with a number of materials inside a spacecraft. Primary among these materials is aluminum, which is abundantly used due to its strong and light weight nature. Aluminum has a natural oxide layer that protects it from corrosion but is typically treated to enhance this oxide layer. Among these treatments is a chromate conversion coating (CCC), which provides a thin enough protective oxide layer to still conduct electricity, and a traditional anodized material that has a thicker oxide layer that does not conduct electricity. Nomex is another common material found inside a spacecraft. It is a flame-resistant woven polymer that is related to nylon. This commercially available material is used for cargo storage bags and as a fire barrier. Physics-based models were developed to predict the uptake of HCl by these materials. The ultimate objective of these models is to predict the fate of HCl within the spacecraft so that sensors can be placed in meaningful locations in future missions based on the model predictions. To support these modeling efforts, experiments were performed in a cast acrylic test cell that measured the difference between the inlet and outlet concentration of HCl after inserting a sample rod of the test material. Different uptake capacities were realized for each type of sample tested. A computational fluid dynamics model (CFD) model of the reactor was then constructed that used a one-step global reaction rate with calibratable reaction (or kinetic) constants. These constants were calibrated to match the HCl uptake on the CCC aluminum samples, and the same kinetic constants were then tested for the stock and anodized aluminum samples. Model predictions matched the experimental data for the stock aluminum, and to a much lesser extent, the anodized aluminum. The model was additionally validated at different flow rates, sample surface areas, and inlet concentrations, and showed good agreement for all stock and CCC samples. The model did not accurately predict the HCl uptake in the anodized samples compared to the other two types of aluminum. Adjusting the kinetic constants and transport properties did little to improve the prediction. X-Ray Photoelectron Spectroscopy (XPS) was used to determine that the oxide layer thickness of anodized aluminum is approximately 5,000 nm, compared to 250 nm for CCC and 50 nm for stock. XPS also revealed presence of chlorine further down in the aluminum oxide layer in anodized samples than CCC and stock samples after the samples were saturated with HCl, indicating that accounting for diffusion of HCl into the oxide layer is important for accurate prediction of HCl uptake onto anodized aluminum. Consequently, a multi-scale model was developed and tested. First, a single pore inside the anodized aluminum oxide layer was modeled and is referred to as the pore-scale model. In this model, HCl diffused through the pore and reacted with the aluminum oxide pore wall to create aluminum chloride. The sample was then saturated when the mass transfer resistance through the growing aluminum chloride layer became too large for the HCl to reach the aluminum oxide wall and continue the reaction. This pore-scale model was coupled to the reactor-scale model using a concentration-dependent diffusion coefficient, resulting in much more accurate predictions (approximately half the sum square error of the aforementioned reactor-scale model that produced good agreement for stock and CCC) for a variety of operating conditions. The amount of water vapor or relative humidity (RH) in the flow during a reactor experiment was determined to influence HCl uptake. Experiments were performed to understand the interaction of gaseous HCl with aluminum surfaces in the presence of water vapor. The results show that increasing levels of RH increased the capacity of aluminum to adsorb HCl but decreased the capacity of Nomex to uptake HCl. A series of tests were performed on individual aluminum samples after they had been saturated with a fixed concentration of HCl in dry air conditions with the goal of determining how their HCl uptake capacity changes after various treatments with water relative to the original saturation tests. HCl-saturated aluminum samples subjected to a second dry air flow at the same HCl concentration as the original test had an uptake of 23.5% of the original sample with no treatment in between. Saturated aluminum samples subjected to an air flow with a RH of 90% in between tests had an uptake of 35.6% of the original. Saturated aluminum samples submerged in distilled water for 12 hours in between tests had an uptake of 82.2% of the original sample. Previously saturated aluminum tested with HCl and a 50% RH air flow resulted in similar uptake characteristics in multiple repeated tests. The experiments show the profound effect water vapor has on HCl uptake onto aluminum surfaces. In the samples subjected to water vapor or liquid water, capillary condensation and capillary diffusion alters the transport of HCl significantly. A model was proposed that developed a relationship between RH and the coefficient of HCl diffusion in aluminum chloride. This produced an “S-shaped” curve with diffusion coefficient as a function of RH, with 45% RH represented as the point where the diffusion coefficient is halfway between no water saturation and 100% water saturation in the aluminum chloride product layer. No difference in uptake characteristics for the experiment or model were realized between 50% and 62% RH. The results from the large-scale microgravity experiment, Saffire, are discussed as they pertain to the fate of HCl throughout a spacecraft. HCl was released, both as a standalone event, and in concurrence with the burning of a structured cloth. These events only produced a small response in the far field HCl sensor, while a PMMA burn that did not produce HCl had a significantly greater response. A ground-based large-scale facility was constructed to flow acid gas at the scale and configuration realized in the Saffire experiments. A CFD model of this duct was constructed to test kinetic parameters developed in this work at a larger scale and different geometric configuration and to predict the results of the large-scale facility. The models developed in this work were used to interpret the results of the microgravity tests and lead the discussion on what further experiments and models are needed in order to predict the fate of acid gas in a spacecraft environment. To summarize, the major contributions of this work are as follows: the capacity to uptake HCl, with and without the presence of water vapor, was measured for a variety of real spacecraft surfaces. Several different models (single reactor-scale, multiscale, spacecraft-scale) were developed and with the aid of modeling, the rate of uptake for those surfaces was also predicted and validated. The kinetic parameters determined from the small-scale reactor experiments and models were used to predict large-scale and microgravity tests. Conclusions from this research will be used in the design of spacecraft vehicles and large-scale microgravity fire safety experiments. The models built by this work will aid designers in sensor placement and could be used to predict acid gas transport from fires in partial gravity, as would be seen in Lunar and Martian habitats.

fire safety↗
NASA NTRS2003

Magnetic Microspheres and Tissue Model Studies for Therapeutical Applications

Hyperthermia is a well known cancer therapy and consists of heating a tumor region to the elevated temperatures in the range of 40-45 C for an extended period of time (2-8 hours). This leads to thermal inactivation of cell regulatory and growth processes with resulting widespread necrosis, carbonization and coagulation. Moreover, heat boosts the tumor response to other treatments such as radiation, chemotherapy or immunotherapy. Of particular importance is careful control of generated heat in the treated region and keeping it localized. Higher heating, to about 56 C can lead to tissue thermo-ablation. With accurate temperature control, hyperthermia has the advantage of having minimal side effects. Several heating techniques are utilized for this purpose, such as whole body hyperthermia, radio-frequency (RF) hyperthermia, ultrasound technique, inductive microwave antenna hyperthermia, inductive needles (thermoseeds), and magnetic fluid hyperthermia (MFH).MFH offers many advantages as targeting capability by applying magnets. However, this technology still suffers significant inefficiencies due to lack of thermal control. This paper will provide a review of the topic and outline the ongoing work in this area. The main emphasis is in devising ways to overcome the technical difficulty in hyperthermia breast therapy of achieving a uniform therapeutic temperature over the required region of the body and holding it steady for an extended period (2-3 hours). The basic shortcomings of the presently utilized heating methods stem from the non-uniform thermal properties of the tissue and the point heating characteristics of the techniques without any thermal control. Our approach is to develop a novel class of magnetic fluids, which have inherent thermoregulating properties. We have identified a few magnetic alloys which can serve as suitable nano to micron-size particle material. The objective is to synthesize, characterize and evaluate the efficacy of Thermo Regulating Magnetic Fluids (TRMF) for hyperthermia therapy. The development of a tissue model and testing the fluid dynamics of particle motion, settling, distribution in the tissue matrix and heat generation will be discussed.

Ramachandran, N.↗
DOE OSTI2022

An experimental and modeling study on auto-ignition kinetics of ammonia/methanol mixtures at intermediate temperature and high pressure

A rapid compression machine (RCM) has been applied to measure the ignition delay times of NH 3 /CH 3 OH mixtures covering pressures of 20 and 40 bar, equivalence ratios of 0.5, 1.0 and 2.0, and temperatures between 845 and 1100 K. Here the measurements show that the NH 3 /CH 3 OH mixtures become more reactive with increasing methanol addition. Addition of merely 1% (molar basis) of CH 3 OH to NH 3 lowers the ignition temperature around 100 K at 40 bar in comparison to pure NH 3 . The ignition delay is a complex function of fuel mixture and stoichiometry. For the 1% CH 3 OH mixture, the leaner mixtures are more reactive, while the reverse trend is found for mixtures with 5%, 20% and pure CH 3 OH. Analysis of the pressure profiles shows three distinct ignition modes for NH 3/ CH 3 OH mixtures, facilitated by the pre-ignition heat release from NH 3 consumption. A detailed mechanism for ignition of NH 3 /CH 3 OH fuel blends has been developed, capable of reproducing the ignition behavior of mixtures with reasonable accuracy. A subset for amine / methanol interactions was established, with rate constants for the key reaction between NH 2 and CH 3 OH calculated from ab initio theory. A sensitivity analysis indicates that the critical reactions during the auto-ignition process vary with the CH 3 OH mole fraction in the fuel. The ammonia chemistry, namely NH 2 + NO, NH2 + NO 2 and NH 2 + HO 2 , is dominant for the mixture with 1% CH 3 OH, while the reactions related to CH 3 OH and H 2 O 2 are more important for the 20% CH 3 OH mixture. The interaction between ammonia and methanol shows a more prominent effect on auto-ignition for mixtures with 5% CH 3 OH in fuel as compared to those with 1% and 20% CH 3 OH. According to the modeling results, methanol addition is found to enrich the O/H radical pool, consuming ammonia and promoting auto-ignition through different reaction pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

ZAM Modeling Study to Support the Tank Closure Cesium Removal (TCCR) 1A Unit

Currently at the Savannah River Site (SRS), the Tank Closure Cesium Removal (TCCR) is an “at-tank” process designed to remove cesium from aqueous tank waste. Cesium will be removed by ion exchange using the engineered IONSIV® R9120 form of Crystalline Silicotitanate (CST) media. The current TCCR design has two columns online in a lead-lag configuration to optimize media usage and achieve the target decontamination. Once the lead column is saturated with cesium, it will be removed from service, the lag column will rotate into the lead position, and a new column with fresh ion-exchange media will be placed into the lag position. The TCCR process for cesium removal from Tank 10H is detailed in X-SOW-H- 00002. Demonstration of the system began in early calendar year 2019 with two batches of salt solution generated by dissolving saltcake in Tank 10H, followed by processing of these batches through the TCCR system. A third TCCR Tank 10H dissolved saltcake batch is scheduled for processing soon. Upon completion of the demonstration with Tank 10H dissolved saltcake, Tank 9H salt solution will be transferred to Tank 10H and subsequently processed through the TCCR unit with new CST media (referred to as R9120-B 30x60) added to new IX columns. The TCCR processing campaign of Tank 9H salt solution is referred to as TCCR-1A .

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Molten Salt Reactor Signatures and Modeling Study

Molten salt reactor (MSR) technologies, either liquid fueled and cooled or only liquid cooled, pose specific, unique challenges for safeguards of the special nuclear material during the operation, fueling, and maintenance of the reactor. MSRs are one type of Generation IV technologies being invested in and considered for U.S. domestic fabrication primarily for electricity and process heat production. These designs have generated growing commercial interest for several reasons, including high (≈40%) thermal efficiency, ease of fueling, improved use of uranium fuel, potential utilization of thorium fuel, and proposed inherent safety features. U.S. companies have several planned designs that differ in fuel, cooling, and neutron energy spectrum. Driven by commercial interest and the intent of licensing MSRs, the U.S. Nuclear Regulatory Commission (NRC) has developed a vision and strategy to accommodate non-light water reactors (LWR), which include MSRs (U.S. Nuclear Regulatory Commission 2019). In addition, the Department of Energy (DOE) through the Office of Nuclear Energy (NE) Office of Advanced Reactor Technologies (ART), …sponsors research, development and deployment (RD&D) activities through its Next Generation Nuclear Plant (NGNP), Advanced Reactor Concepts (ARC), and Advanced Small Modular Reactor (aSMR) programs to promote safety, technical, economical, and environmental advancements of innovative Generation IV nuclear energy technologies. Reactor types considering the use of salts, liquid metals, or gases for coolant fall under both ARC and aSMR. Therefore, Research Design & Development is being pursued by DOE-NE through national laboratories, universities, and international and industrial collaborations. Additionally, the U.S. is a member of the Gen IV International Forum (GIF). The GIF is a cooperative, multinational organization to guide and carry out research and development needed for the GEN IV reactor systems (Forum 2018). GIF evaluated numerous reactor concepts and down-selected to the six most feasible advanced reactor technologies: gas-cooled fast reactor (GFR), lead-cooled fast reactor (LFR), MSR, supercritical watercooled reactor (SCWR), sodium-cooled fast reactor (SFR), and very high temperature reactor (VHTR). In support of the growing interest domestically and internationally, the Materials Protection, Accounting, and Control Technologies (MPACT) campaign, under the DOE-NE Fuel Cycle Technologies (FCT) program, engages in R&D activities by developing advanced instrumentation and analysis for safeguards and security of modern, advanced nuclear fuel cycle (non-LWR) facilities. Because of the historic experience in the operation of the Aircraft Reactor Experiment (ARE) and the Molten Salt Reactor Experiment (MSRE) (Robertson, MSRE Design and Operations Report Part I 1965), Oak Ridge National Laboratory (ORNL) is heavily engaged in the various R&D activities through the DOE complex related to MSRs including national technical leadership of the DOE-NE MSR campaign. This report discusses and presents the outcomes of the FY19 MPACT MSR Safeguards task. The challenges presented by MSRs for nuclear material accountancy and control (NMAC) and associated safeguards will be investigated. The objective of this research is to explore and compile the safeguards requirements and identify measurement signatures through an initial high-level MSR design and develop complementary advanced simulation and modeling capabilities. A high-level ORNL-developed MSR design called the Molten Salt Demonstration Reactor (MSDR) (Bettis, Alexander and Watts 1972) was used as the target reactor design for this research. The MSDR model incorporates technology from the MSRE and the Molten Salt Breeder Reactor (Robertson, Conceptual Design of a Single-Fluid Molten-Salt Breeder Reactor 1971). But the MSDR is a 750 MWth graphite moderated liquid fueled (low-enriched uranium) MSR compared to the MSRE’s of 7.5 MWth. The focus of this report is to discuss the evaluation of novel signatures, correlations, and indicators to understand the applicability of current safeguards instrumentation to MSRs using the modeling results from the MSDR.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2020

Experimental and Kinetic Modeling Study of Laminar Burning Velocities of Cyclopentanone and Its Binary Mixtures with Ethanol and n-Propanol

Cyclopentanone is a promising biofuel that can enable more efficient engine operation and increase the fuel economy of the light duty fleet over current and planned technology developments. While the ignition of cyclopentanone has been investigated in detail, more studies on the laminar burning velocities of cyclopentanone are called for. In this work, the laminar burning velocities of cyclopentanone (C 5 H 8 O) have been measured using the heat flux and spherical flame methods at 1 atm, equivalence ratios from 0.7 to 1.6, and initial temperatures of 328, 353, and 428 K. To further investigate the relationship between the molecular structure and laminar burning velocity, identical experiments were also performed for binary mixtures of cyclopentanone with ethanol and n-propanol at 1:1 (mol). The consistency between the experimental data sets obtained in this work and literature data sets has been evaluated. Here, a recently published mechanism of cyclopentanone was used for simulation after adopting the submechanism of n-propanol. Good agreement has been seen between experimental and simulated results for all flames. To qualitatively explain the characteristics of the laminar burning velocity of cyclopentanone and the differences with those of ethanol and n-propanol, sensitivity analysis and reaction pathway analysis have been performed to compare the chemistry of the fuels under flame conditions, which revealed how the molecular structure of cyclopentanone could affect its laminar burning velocity. Compared to ethanol and n-propanol, cyclopentanone does not have primary carbon atoms in its molecule, leading to lower production of methyl radicals. Meanwhile, the carbonyl group in the cyclopentanone molecule is mostly released as CO in the decomposition of multiple intermediates accompanied by the production of unsaturated C 2 and C 4 species, especially C 2 H 4 and C 2 H 3 . Both features contribute to the high laminar burning velocity of cyclopentanone.

09 BIOMASS FUELS↗
NASA NTRS2004

Coating Development for GRCop-84 Liners for Reusable Launch Vehicles Aided by Modeling Studies

The design of the next generation of reusable launch vehicles calls for using GRCop-84 copper alloy liners based on a composition invented at the NASA Glenn Research Center. Despite its considerable advantage over other copper alloys, it is expected that GRCop-84 will suffer from environmental degradation depending on the type of rocket fuels used and on thermomechanical fatigue. Applying protective coatings on GRCop-84 substrates can minimize or eliminate many of these problems and extend the operational life of the combustion liner. This could increase component reliability, shorten depot maintenance turnaround times, and lower operating costs. Therefore, Glenn is actively pursuing the development of advanced coatings technology for GRCop-84 liners. Technology is being developed in four major areas: (1) new metallic coating compositions, (2) application techniques, (3) test methods, and (4) life prediction design methodology using finite element analysis. The role of finite element analysis in guiding the coating effort is discussed in this report. Thermal analyses were performed at Glenn for different combinations of top- and bondcoat compositions to determine the temperature variation across the coated cross section with the thickness of the top coat. These calculations were conducted for simulated LH2/LO2 booster engine conditions assuming that the bond coat had a constant thickness of 50 m. The preceding graphs show the predicted temperatures at the outer surface of the top coat (hot wall), at the top-coat/bond-coat interface, at the bond-coat/GRCop-84 interface, and at the GRCop-84 cold wall as a function of top-coat thickness for Cu- 26(wt%)Cr top coat (top graph), Ni-17(wt%)Cr-6%Al-0.5%Y top coat and Cu-26%Cr bond coat, and NiAl top coat and Ni bond coat. In all cases, the temperature of the top coat at the hot wall increased with increasing top-coat thickness and with corresponding decreases in the temperatures at the two interfaces and the cold wall. These temperatures are not acutely sensitive to the thermal conductivity of the top coat when it exceeds 25 and 50 W/m/K for low and high heat flux engines. This observation is significant for two reasons. First, several different top-coat compositions can be evaluated as potential protective coatings without loss in the heat-transfer efficiency of the coated system. Second, materials with thermal conductivities less than the critical values of 25 or 50 W/m/K are more likely to act as thermal barrier coatings. The deposition of overlay coatings on GRCop-84 substrates results in the development of residual stresses. The presence of these residual stresses influences the probability of coating spallation, the thermal cycling life, and the fatigue properties of the coated substrate during use. Since it is important to understand how these stresses develop during the vacuum-plasma-spraying coating deposition process, the nature and magnitudes of the cool-down residual stresses were calculated and compared with experimentally determined values across the coated cross section of a disk specimen. The calculations were conducted assuming that the specimen cools down to room temperature from vacuum plasma-spraying temperatures of either 250 or 650 C. The effects of coating the substrate with and without grit blasting were also theoretically examined. The final graph compares the predicted and the experimental results for a GRCop-84 disk coated with about a 50- m-thick Ni bond coat and a 75- to 100- m NiAl top coat, where the curves for NASA-2 assume the presence of a prior residual stress generated by grit blasting under conditions similar to the experimental situation. The predicted cool-down in-plane stresses were compressive in both the NiAl top coat and the Ni bond coat. They were also compressive in the substrate to a depth of about 0.25 mm from the Ni/GRCop-84 interface when the vacuum-plasma-spraying temperature was low. However, using a higher plasma spraying temperaturs likely to leave the substrate under a small tensile stress to counter the compressive stresses in the bond and top coats because of the relaxation of residual stresses generated in the substrate during the grit blasting of its surface prior to spraying. These results suggest that the NiAl and Ni coatings are unlikely to spall after spraying as confirmed by the microstructural observations shown in the following photomicrograph of an as-sprayed specimen. Finally, it is noted that the calculated and experimental results are not in complete agreement, which indicates that both the experimental and modeling techniques need further refinement.

Raj, Sai V.↗