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At least 37 records · Page 2

Thermochemistry of Rare Earth Silicates for Environmental Barrier Coatings

Rare earth silicates are promising candidates as environmental protective coatings (EBCs) for silica-forming ceramics and composites in combustion environments since they are predicted to have lower reactivity with the water vapor combustion products. The reactivity of rare earth silicates is assessed by the thermodynamic activity of the silica component which is best measured by Knudsen effusion mass spectrometry (KEMS). Here, we discuss a novel method based on a reducing agent to increase the partial pressure of SiO(g) which is then used to calculate thermodynamic activity of silica in Y2O3-SiO2 and Yb2O3-SiO2 systems. After the KEMS measurements, samples were probed by X-ray diffraction and their phase content was calculated from Rietveld refinement.

Rare Earth Silicates↗

Thermodynamic Modeling of the Vapor in Equilibrium With Apollo 17 Basalts.

Lunar mare basalts sampled during the Apollo 17 mission provide insight to the chemical evolution of mare basalt magmas and their associated vapor as these samples erupted and cooled rapidly at the lunar surface. We focus on minerals present on vesicle and vug surfaces in Apollo 17 basalts, such as 71036, which was opened as part of the Apollo Next Generation Sample Analysis (ANGSA) program. The mineral assemblage observed includes native Fe, SiO2, and a Mg-P mineral, possibly merrillite [1, 2]. The pet-rographic context of these phases suggests that they may have been deposited directly from the vapor phase after eruption. Here we use thermodynamic modeling to assess the plausibility of the vapor-phase deposition hypothesis.

D. L. Thompson↗

Updated Observations of Clouds By MODIS for Global Model Assessment

This paper describes a new global dataset of cloud properties observed by MODIS relying on the current (collection 6.1) processing of MODIS data and produced to facilitate comparison with results from the MODIS observational proxy used in climate models. The dataset merges observations from the two MODIS instruments into a single netCDF file. Statistics (mean, standard deviation, and number of observations) are accumulated over daily and monthly timescales on an equal-angle grid for viewing and illumination geometry, cloud detection, cloud-top pressure, and cloud properties (optical thickness, effective particle size, and water path) partitioned by thermodynamic phase and an assessment as to whether the underlying observations come from fully or partly cloudy pixels. Similarly partitioned joint histograms are available for (1) optical thickness and cloud-top pressure, (2) optical thickness and particle size, and (3) cloud water path and particle size. Differences with standard data products, caveats for data use, and guidelines for comparison to the MODIS simulator are described.

Robert Pincus↗

Cycling phosphorus on the Archean Earth: Part I. Continental weathering and riverine transport of phosphorus

Phosphorus (P) is the key nutrient thought to limit primary productivity on geological timescales. Phosphate levels in Archean marine sediments are low, but quantification of the P cycle and how it changed through a billion years of recorded Archean history remain a challenge, hindering our understanding of the role played by P in biosphere/geosphere co-evolution on the early Earth. Here, we design kinetic and thermodynamic models to quantitatively assess one key component of the early P cycle – continental weathering – by considering the emergence and elevation of continents, as well as the evolution of climate, the atmosphere, and the absence of macroscopic vegetation during the Archean Eon. Our results suggest that the weathering rate of apatite, the major P-hosting mineral in the rocks, was at least five times higher in the Archean Eon than today, attributable to high levels of pCO2,g. Despite this, the weathering flux of P to the oceans was negligible in the early Archean Eon, increasing to a level comparable to or greater than the modern by the end of eon, a consequence of accelerating continental emergence. Furthermore, our thermodynamic calculations indicate high solubilities of primary and secondary P-hosting minerals in the acidic weathering fluids on land, linking to high Archean pCO2,g. Thus, weathering of P was both kinetically and thermodynamically favorable on the Archean Earth, and river water could transport high levels of dissolved P to the oceans, as also supported by the observed P-depletion in our new compilation of Archean paleosols. Lastly, we evaluated the relative rates of physical erosion and chemical weathering of silicates during the Archean Eon. The results suggest that continental weathering on the early and middle Archean Earth might have been transport-limited due to low erosion rates associated with limited subaerial emergence and low plateau elevations; by the late Archean, however, continental weathering would have transited to kinetically-limited state because of continental emergence, increased plateau elevation, and weakening weathering rates. Overall, our weathering calculations together with paleosol evidence indicate an increasing flux of bioavailable P to the oceans through time, associated with late Archean continental emergence, reaching levels comparable to or higher than modern values by the end of the eon. Increased P fluxes could have fueled increasing rates of primary production, including oxygenic photosynthesis, through time, facilitating the irreversible oxidation of the Earth’s atmosphere early in the Proterozoic Eon.

Phosphorus↗

Progress of Stirling cycle analysis and loss mechanism characterization

An assessment of Stirling engine thermodynamic modeling and design codes shows a general deficiency; this deficiency is due to poor understanding of the fluid flow and heat transfer phenomena that occur in the oscillating flow and pressure level environment within the engines. Stirling engine thermodynamic loss mechanisms are listed. Several experimental and computational research efforts now underway to characterize various loss mechanisms are reviewed. The need for additional experimental rigs and rig upgrades is discussed. Recent developments and current efforts in Stirling engine thermodynamic modeling are also reviewed.

Tew, R. C., Jr.↗

Energetics of muscle contraction: the whole is less than the sum of its parts

Understanding muscle energetics is a problem in optimizing supply of ATP to the demands of ATPases. The complexity of reactions and their fluxes to achieve this balance is greatly reduced by recognizing constraints imposed by the integration of common metabolites at fixed stoichiometry among modular units. ATPase is driven externally. Oxidative phosphorylation and glycogenolysis are the suppliers. We focus on their regulation which involves different controls, but reduces to two principles that enable facile experimental analysis of the supply and demand fluxes. The ratio of concentration of phosphocreatine (PCr) to ATP, not their individual values, sets the range of achievable concentrations of ADP in resting and active muscle (at fixed pH) in different cell types. This principle defines the fraction of available flux of oxidative phosphorylation utilized (at fixed enzyme activities). Then the kinetics of PCr recovery defines the kinetics of oxygen supply and substrate utilization. The second principle is the constancy of PCr and H(+) (lactate) production by glycogenolysis due to the coupling of ATPase and glycolysis. This principle enables glycogenolytic flux to be measured from intracellular proton loads. Further simplification occurs because the magnitude of the interacting fluxes and metabolite concentrations are specified within narrow limits when both the resting and active fluxes are quantified. Thus there is a small set of rules for assessing and understanding the thermodynamics and kinetics of muscle energetics.

NASA Program Biomedical Research and Countermeasur↗

Calculation of Phase Equilibria in the Y2O3-Yb2O3-ZrO2 System

Rare earth oxide stabilized zirconias find a wide range of applications. An understanding of phase equilibria is essential to all applications. In this study, the available phase boundary data and thermodynamic data is collected and assessed. Calphad-type databases are developed to completely describe the Y2O3-ZrO2, Yb2O3-ZrO2, and Y2O3-Yb2O3 systems. The oxide units are treated as components and regular and subregular solution models are used. The resultant calculated phase diagrams show good agreement with the experimental data. Then the binaries are combined to form the database for the Y2O3-Yb2O3-ZrO2 psuedo-ternary.

Jacobson, Nathan S.↗

Evaluating Novel Approaches for In Situ Analysis in the Search for Extraterrestrial Life

Universal approaches to detect extraterrestrial life are required to determine whether life exists outside of earth. A significant limitation of current detection strategies is the absence of a reliable, universal approach. They do not provide mechanisms to detect life that has evolved distinctly from life on Earth. We hypothesize that the most basic, essential features of life that can be detected are that they decrease their internal entropy at the expense of free energy obtained from their surroundings and that they produce heat associated with metabolic reactions. We propose that by using a thermodynamic analysis of the energy associated with these fundamental components of life, one can readily quantify the degree of free energy difference between life forms or their remnants and their abiotic surroundings. Analysis of the free energy entropy term (and thus structural complexity) and enthalpy term (as a manifestation of the energy release caused by metabolic reactions) may provide definitive detection of the presence of life. As a part of our analysis we review data available in the literature about the thermodynamics of microbial growth to assess the extent microbial metabolism and growth may contribute to negative entropy of maintenance (metabolism) and structural complexity. Additionally, we evaluate the different mechanisms by which structural complexity can be measured using calorimetry. An experimental framework is considered using concepts from previous work that could be used to further validate the calorimetric methods for life detection by potentially differentiating between life forms or their remnants from an abiotic surrounding. Results obtained demonstrate the applications of this approach and indicate that modification of a microcalorimetric technique has potential for incorporation into a space exploration platform as a life-detection payload.

Life Detection, Calorimetry↗

Estimation of Thermodynamic and Dynamic Contributions to Sea Ice Growth in the Central Arctic Using ICESat-2 and MOSAiC SIMBA Buoy Data

The fine spatial resolution of the ICESat-2 (IS2) satellite altimeter allows monitoring the evolution of sea ice thickness with detailed dynamic information (e.g. ridges and leads). In this study, we first assess the ability of IS2 to estimate thermodynamic ice growth and dynamic thickening during the ice-growing season in the central Arctic Ocean. As an indicator of the thermodynamic ice growth, we use 10 thermistor string-based sea ice mass balance array (SIMBA) buoys deployed at a scale of ~ 50 km from the Icebreaker Polarstern during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition. We collect IS2 data within 20 km buffer distance from the individual buoys, and calculate the mode, median, and mean of the IS2-derived ice thickness. The IS2 modal thickness shows the least bias (−0.169 m) with the buoy ice thickness, representing level ice thickness. In addition, the increasing rate of the IS2 modal thickness is close to the thermodynamic ice growth with a small bias of −0.054 cm/day. However, the increasing rates of the IS2 median and mean thickness are greater than the thermodynamic ice growth by about 0.114 cm/day and 0.198 cm/day, respectively, because they also include ice growth caused by thickness redistribution during dynamic deformation. The dynamic contributions may account for 26.1 ± 10.3% and 34.4 ± 10.1% of the total increase of the IS2 median and mean thickness, respectively. Within a ~ 50 km radius area from the MOSAiC Central Observatory, IS2 measurements exhibit that the ridge fraction increased from <2% in November to ~ 4% in March (~0.029%/day of average increasing rate) and ridge height increased about 0.047 cm/day during the same period. However, lead formation does not show significant contributions to the dynamic ice thickening because leads are temporary features lasting only 2–3 days. Although there are considerable uncertainties in IS2 ice thickness estimation and IS2-buoy thickness comparison, this study emphasizes the importance of combining measurements by IS2 and SIMBA buoys to explain the regional sea ice mass balance with separating the thermodynamic and dynamic contributions.

satellite altimeter↗

Thermophysical properties of sodium

Assessment is given of physical and thermodynamic properties of sodium. FORTRAN subroutine computes enthalphy and entropy of sodium in given state, and composition, molecular weight, volume, and compressibility factor of corresponding vapor. Tabular results for saturated liquid and vapor are presented for a 500-2500 degree F range.

Golden, G. H.↗

The coal-fired gas turbine locomotive - A new look

Advances in turbomachine technology and novel methods of coal combustion may have made possible the development of a competitive coal fired gas turbine locomotive engine. Of the combustor, thermodynamic cycle, and turbine combinations presently assessed, an external combustion closed cycle regenerative gas turbine with a fluidized bed coal combustor is judged to be the best suited for locomotive requirements. Some merit is also discerned in external combustion open cycle regenerative systems and internal combustion open cycle regenerative gas turbine systems employing a coal gasifier. The choice of an open or closed cycle depends on the selection of a working fluid and the relative advantages of loop pressurization, with air being the most attractive closed cycle working fluid on the basis of cost.

Liddle, S. G.↗

Chondritic Models of 4 Vesta: Comparison of Data from the Dawn Mission with Predicted Internal Structure and Surface Composition/Mineralogy

While the HEDs provide an extremely useful basis for interpreting data from the Dawn mission, there is no guarantee that they provide a complete vision of all possible crustal (and possibly mantle) lithologies that are exposed at the surface of Vesta. With this in mind, an alternative approach is to identify plausible bulk compositions and use mass-balance and geochemical modelling to predict possible internal structures and crust/mantle compositions and mineralogies. While such models must be consistent with known HED samples, this approach has the potential to extend predictions to thermodynamically plausible rock types that are not necessarily present in the HED collection. Nine chondritic bulk compositions are considered (CI, CV, CO, CM, H, L, LL, EH, EL). For each, relative proportions and densities of the core, mantle, and crust are quantified. This calculation is complicated by the fact that iron may occur in metallic form (in the core) and/or in oxidized form (in the mantle and crust). However, considering that the basaltic crust has the composition of Juvinas and assuming that this crust is in thermodynamic equilibrium with the residual mantle, it is possible to calculate a single solution to this problem for a given bulk composition. Of the nine bulk compositions tested, solutions corresponding to CI and LL groups predicted a negative metal fraction and were not considered further. Solutions for enstatite chondrites imply significant oxidation relative to the starting materials and these solutions too are considered unlikely. For the remaining bulk compositions, the relative proportion of crust to bulk silicate is typically in the range 15 to 20% corresponding to crustal thicknesses of 15 to 20 km for a porosity-free Vesta-sized body. The mantle is predicted to be largely dominated by olivine (greater than 85%) for carbonaceous chondrites, but to be a roughly equal mixture of olivine and pyroxene for ordinary chondrite precursors. All bulk compositions have a significant core, but the relative proportions of metal and sulphide can be widely different. Using these data, total core size (metal+ sulphide) and average core densities can be calculated, providing a useful reference frame within which to consider geophysical/gravity data of the Dawn mission. Further to these mass-balance calculations, the MELTS thermodynamic calculator has been used to assess to what extent chondritic bulk compositions can produce Juvinas-like liquids at relevant degrees of partial melting/crystallization. This work will refine acceptable bulk compositions and predict the mineralogy and composition of the associated solid and liquid products over wide ranges of partial melting and crystallization, providing a useful and self-consistent reference frame for interpretation of the data from the VIR and GRaND instruments onboard the Dawn spacecraft.

Toplis, M. J.↗

Shock-tube pyrolysis of acetylene - Sensitivity analysis of the reaction mechanism for soot formation

The impact of thermodynamic parameters on the sensitivity of model predictions of soot formation by shock-tube pyrolysis of acetylene were assessed analytically. The pyrolysis process was treated as having three components: initiation, the initial pyrolysis stages; cyclization, formation of larger molecules and radicals and small aromatic molecules; and polymerization, further growth of aromatic rings. Rate equations are reviewed for each component. Thermodynamic effects were assessed by varying the C2H-H and C2H3-H bond energies and the Ct-(Ct) group additivity value. Any change in the C2H-H bond energy had a significant impact on the temperature and the maximum amount of the soot yield. The findings underscore the necessity of using accurate thermodynamic data for modeling high-temperature chemical kinetics.

Frenklach, M.↗

Internal Flow Thermal/Fluid Modeling of STS-107 Port Wing in Support of the Columbia Accident Investigation Board

As part of the aero-thermodynamics team supporting the Columbia Accident Investigation Board (CAB), the Marshall Space Flight Center was asked to perform engineering analyses of internal flows in the port wing. The aero-thermodynamics team was split into internal flow and external flow teams with the support being divided between shorter timeframe engineering methods and more complex computational fluid dynamics. In order to gain a rough order of magnitude type of knowledge of the internal flow in the port wing for various breach locations and sizes (as theorized by the CAB to have caused the Columbia re-entry failure), a bulk venting model was required to input boundary flow rates and pressures to the computational fluid dynamics (CFD) analyses. This paper summarizes the modeling that was done by MSFC in Thermal Desktop. A venting model of the entire Orbiter was constructed in FloCAD based on Rockwell International s flight substantiation analyses and the STS-107 reentry trajectory. Chemical equilibrium air thermodynamic properties were generated for SINDA/FLUINT s fluid property routines from a code provided by Langley Research Center. In parallel, a simplified thermal mathematical model of the port wing, including the Thermal Protection System (TPS), was based on more detailed Shuttle re-entry modeling previously done by the Dryden Flight Research Center. Once the venting model was coupled with the thermal model of the wing structure with chemical equilibrium air properties, various breach scenarios were assessed in support of the aero-thermodynamics team. The construction of the coupled model and results are presented herein.

Sharp, John R.↗

Turbofan forced mixer-nozzle internal flowfield. Volume 1: A benchmark experimental study

An experimental investigation of the flow field within a model turbofan forced mixer nozzle is described. Velocity and thermodynamic state variable data for use in assessing the accuracy and assisting the further development of computational procedures for predicting the flow field within mixer nozzles are provided. Velocity and temperature data suggested that the nozzle mixing process was dominated by circulations (secondary flows) of a length scale on the order the lobe dimensions which were associated with strong radial velocities observed near the lobe exit plane. The 'benchmark' model mixer experiment conducted for code assessment purposes is discussed.

Paterson, R. W.↗

Thermal diffusion in metal-sulfide liquids - Early results

Experiments were carried out to evaluate the Soret effect in liquid Fe-Ni-S-P alloys in order to gain a better understanding of the physical and thermodynamic properties of metallic liquids and to assess the possibility of systematic errors in Czochralski growth techniques. The metal-sulfide liquids were found to show a substantial Soret effect and, contrary to previous expectation, can be as large as that seen in the silicate system. The segregation is largely produced by S-Fe interactions. The P redistribution occurs to reduce activity gradients in P consequent upon S gradients, and P segregation can be approximately predicted in Fe-Ni-S liquids using the activity model of Jones and Malvin (1990). It is inferred that the sense of the Soret segregation, with P going to the cold end and S going to the hot end, is in accordance with the prediction of Malvin et al. (1986), who speculated that the crystal-pulling experiments of Sellamuthu and Goldstein (1985) was influenced by the Soret effect.

Jones, J. H.↗

Changes in Tropical Cyclone Intensity Over the Past 30 Years: A Global and Dynamic Perspective

The hurricane season of 2005 was the busiest on record and Hurricane Katrina (2005) is believed to be the costliest hurricane in U. S. history. There are growing concerns regarding whether this increased tropical cyclone activity is a result of global warming, as suggested by Emanuel(2005) and Webster et al. (2005), or just a natural oscillation (Goldenberg et al. 2001). This study examines the changes in tropical cyclone intensity to see what were really responsible for the changes in tropical cyclone activity over the past 30 years. Since the tropical sea surface temperature (SST) warming also leads to the response of atmospheric circulation, which is not solely determined by the local SST warming, this study suggests that it is better to take the tropical cyclone activities in the North Atlantic (NA), western North Pacific (WNP) and eastern North Pacific (ENP) basins as a whole when searching for the influence of the global-scale SST warming on tropical cyclone intensity. Over the past 30 years, as the tropical SST increased by about 0.5 C, the linear trends indicate 6%, 16% and 15% increases in the overall average intensity and lifetime and the annual frequency. Our analysis shows that the increased annual destructiveness of tropical cyclones reported by Emanuel(2005) resulted mainly from the increases in the average lifetime and annual frequency in the NA basin and from the increases in the average intensity and lifetime in the WNP basin, while the annual destructiveness in the ENP basin generally decreased over the past 30 years. The changes in the proportion of intense tropical cyclones reported by Webster et a1 (2005) were due mainly to the fact that increasing tropical cyclones took the tracks that favor for the development of intense tropical cyclones in the NA and WNP basins over the past 30 years. The dynamic influence associated with the tropical SST warming can lead to the impact of global warming on tropical cyclone intensity that may be very different from our current assessments, which were mainly based on the thermodynamic theory of tropical cyclone intensity.

Wu, Liguang↗

Inflow/Outflow Boundary Conditions with Application to FUN3D

Several boundary conditions that allow subsonic and supersonic flow into and out of the computational domain are discussed. These boundary conditions are demonstrated in the FUN3D computational fluid dynamics (CFD) code which solves the three-dimensional Navier-Stokes equations on unstructured computational meshes. The boundary conditions are enforced through determination of the flux contribution at the boundary to the solution residual. The boundary conditions are implemented in an implicit form where the Jacobian contribution of the boundary condition is included and is exact. All of the flows are governed by the calorically perfect gas thermodynamic equations. Three problems are used to assess these boundary conditions. Solution residual convergence to machine zero precision occurred for all cases. The converged solution boundary state is compared with the requested boundary state for several levels of mesh densities. The boundary values converged to the requested boundary condition with approximately second-order accuracy for all of the cases.

Carlson, Jan-Renee↗