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At least 109 records · Page 6

The stability of amino acids at submarine hydrothermal vent temperatures

It has been postulated that amino acid stability at hydrothermal vent temperatures is controlled by a metastable thermodynamic equilibrium rather than by kinetics. Experiments reported here demonstrate that the amino acids are irreversibly destroyed by heating at 240 C and that quasi-equilibrium calculations give misleading descriptions of the experimental observations. Equilibrium thermodynamic calculations are not applicable to organic compounds under high-temperature submarine vent conditions.

Bada, Jeffrey L.↗

Real-Gas Effects on Binary Mixing Layers

This paper presents a computational study of real-gas effects on the mean flow and temporal stability of heptane/nitrogen and oxygen/hydrogen mixing layers at supercritical pressures. These layers consist of two counterflowing free streams of different composition, temperature, and density. As in related prior studies reported in NASA Tech Briefs, the governing conservation equations were the Navier-Stokes equations of compressible flow plus equations for the conservation of total energy and of chemical- species masses. In these equations, the expressions for heat fluxes and chemical-species mass fluxes were derived from fluctuation-dissipation theory and incorporate Soret and Dufour effects. Similarity equations for the streamwise velocity, temperature, and mass fractions were derived as approximations to the governing equations. Similarity profiles showed important real-gas, non-ideal-mixture effects, particularly for temperature, in departing from the error-function profile, which is the similarity solution for incompressible flow. The temperature behavior was attributed to real-gas thermodynamics and variations in Schmidt and Prandtl numbers. Temporal linear inviscid stability analyses were performed using the similarity and error-function profiles as the mean flow. For the similarity profiles, the growth rates were found to be larger and the wavelengths of highest instability shorter, relative to those of the errorfunction profiles and to those obtained from incompressible-flow stability analysis. The range of unstable wavelengths was found to be larger for the similarity profiles than for the error-function profiles

Okong'o, Nora↗

Isolating the Surface Type Influence on Arctic Cloud Properties

In response to anthropogenic climate change, substantial declines in sea ice have been observed. An urgent question is whether and how clouds respond to the changing Arctic surface. Due to the important radiative influence of clouds, the response of clouds to sea ice cover change constitutes a potentially important climate feedback within the Arctic. The sign of this feedback is strongly influenced by the seasonality of the cloud response to sea ice loss. Given the importance of this phenomenon, previous research focused on using observations of inter-annual variability to quantify the cloud-sea ice relationship. However, the reliance on inter-annual variability to assess the covariance between clouds and sea ice make it challenging to control for the influence of large-scale meteorology on the clouds. We have devised an approach that applies an in situ, airborne observational strategy to quantify the influence of surface type on Arctic clouds to satellite data. Our event-based method composites cloud property differences for ocean, marginal ice zone, and sea ice surface types for >5000 MIZ crossing events. We find that cloud properties in non-summer months below ~1.5 km are influenced by surface type such that greater cloud fraction and water content are found over ocean relative to sea ice regions. Results are statistically significantly at the 95% confidence level. During summer, the surface type does not influence the cloud properties. The primary cause of the surface type dependent cloud property differences is the thermodynamic profiles differences that occur between the two surface types: namely, ocean footprints are warmer, moister, have more positive surface turbulent fluxes and are less stable than their sea ice counterparts. We find that the differences in thermodynamic profiles by surface type that correspond to the cloud property differences also explains a significant portion of the variability across events. Our analysis provides evidence that the influence of surface type on cloud properties fundamentally occurs due to the inherent surface temperature differences between the surface types. Significant surface type influences on cloud properties are only found in the presence of surface temperature differences between the surface types and only non-summer months meet this criterion. A conceptual model of this process is as follows, fundamental properties of the ocean and sea ice surface types (e.g., surface albedo, heat capacity/thermal inertia, surface roughness, and thermal conductance) lead to systematic differences in the surface temperature by surface type. In response to this surface temperature difference, atmosphere boundary layer processes (including turbulent mixing and radiation) communicate the surface temperature differences to the lower atmosphere driving the greater stability over sea ice than ocean. These differences in the background thermodynamic state profiles between the surface types yield atmospheric conditions that are more conducive to cloud development over ocean than sea ice. The details of these boundary layer processes are sensitive to the surface type but may not be fundamental to the resulting thermodynamic structure and cloud differences. Thus, our results indicate that to accurately model that cloud response to sea ice loss in climate models the surface type properties that yield the systematic differences in ocean and sea ice temperature (e.g., surface albedo, surface turbulent fluxes parameters, and thermal conductance) must be accurately represented.

Arctic radiation budget↗

Clustered or regular cumulus cloud fields - The statistical character of observed and simulated cloud fields

The spatial distribution of cumulus clouds is assumed to be the result of the effects of convective activity on the thermodynamic environment. The effects can be parameterized in terms of a stabilization function representing the time rate of change of convective available potential energy. Using these results, a new inhibition hypothesis explaining the expected characteristics of the spatial distribution of cumulus clouds is postulated. This paper performs a verification of the inhibition hypothesis on real and simulated cloud fields. In order to do so, an objective measure of the spatial characteristics of cumulus clouds is introduced. Multiple cloud experiments are performed with a three-dimensional numerical cloud model. Skylab pictures of real cumuli are also used in the verification. Results of applying this measure to simulated and observed cumulus cloud fields confirm the inhibition hypothesis.

Ramirez, Jorge A.↗

Efficient Flowline Simulations of Ice Shelf-Ocean Interactions: Sensitivity Studies with a Fully Coupled Model

Thermodynamic flowline and plume models for the ice shelf-ocean system simplify the ice and ocean dynamics sufficiently to allow extensive exploration of parameters affecting ice-sheet stability while including key physical processes. Comparison between geophysically and laboratory-based treatments of ice-ocean interface thermodynamics shows reasonable agreement between calculated melt rates, except where steep basal slopes and relatively high ocean temperatures are present. Results are especially sensitive to the poorly known drag coefficient, highlighting the need for additional field experiments to constrain its value. These experiments also suggest that if the ice-ocean interface near the grounding line is steeper than some threshold, further steepening of the slope may drive higher entrainment that limits buoyancy, slowing the plume and reducing melting; if confirmed, this will provide a stabilizing feedback on ice sheets under some circumstances.

polar oceanography↗

The effect of topography on the evolution of unstable disturbances in a baroclinic atmosphere

A two layer spectral quasi-geostrophic model is used to simulate the effects of topography on the equilibria, their stability, and the long term evolution of incipient unstable waves. The flow is forced by latitudinally dependent radiative heating. Dissipation is in the form of Rayleigh friction. An analytical solution is found for the propagating finite amplitude waves which result from baroclinic instability of the zonal winds when topography is absent. The appearance of this solution for wavelengths just longer than the Rossby radius of deformation and disappearance of ultra-long wavelengths is interpreted in terms of the Hopf bifurcation theory. Simple dynamic and thermodynamic criteria for the existence of periodic Rossby solutions are presented. A Floquet stability analysis shows that the waves are neutral. The nature of the form drag instability of high index equilibria is investigated. The proximity of the equilibrium shear to a resonant value is essential for the instability, provided the equilibrium occurs at a slightly stronger shear than resonance.

Clark, J. H. E.↗

Thermochemical analysis of the silicon carbide-alumina reaction with reference to liquid-phase sintering of silicon carbide

The stabilities of different phases in the Si-Al-C-O system are calculated from thermodynamic considerations with the objective of identifying the liquid phases formed during sintering of SiC in the presence of Al2O3. It is shown that a liquid phase can form at the sintering temperatures by the reaction of SiC with Al2O3. Depending on the carbon activity, the liquid can be either of the following: Al2O3 + Al4C3, SiC + Al4C3, or molten aluminum. The stability of the aluminosilicate melts that can form by the reaction of Al2O3 with the surface silica layer on SiC powders is also evaluated. Several factors that influence liquid-phase sintering, such as the solubility of SiC in the melts and the generation of gases during sintering, are discussed. The results of the thermodynamic analysis are compared with the observed sintering behavior for SiC.

Misra, Ajay K.↗

Stability and refrigeration of magnet cryosystems near 1.8 K using the thermomechanical effect

Magnet cryosystem options utilizing the thermomechanical effect of He II and the mechano-caloric effect for refrigeration (referred to as vortex refrigeration) are examined. The performance of the existing He II magnet refrigeration system is briefly reviewed, with attention given to superleak properties, vortex shedding, heat input, and thermodynamic cycle. It is concluded that the possibilities of magnet heat leak use for energetics and stability improvements are promising when He II is selected as magnet coolant.

Frederking, T. H. K.↗

Thermodynamic and Diffusion Model Estimates on Metamorphic Temperatures and Timescales for Basaltic Eucrite GRA 98098

Introduction: HED meteorites are thought to rep-resent igneous rocks from Vesta’s basaltic crust and preserve evidence of early crustal metamorphism. Determining the temperatures and timescales of thermal metamorphism is important for reconstructing crustal evolution in the early solar system. Here, we study basaltic eucrite Graves Nunataks (GRA) 98098, which has been identified as a highly metamorphosed eucrite [1]. We present new estimates on metamorphic temperatures determined via thermodynamic modeling as well as the initial results from diffusion models constraining timescales of thermal metamorphism. Sample Description: GRA 98098 is an unbrecciated eucrite with a granoblastic plagioclase and pyroxene mineralogy. Millimeter to cm-long lathes of tridymite cross-cut and poikilitically enclose plagioclase and pyroxene [1,this work]. Pyroxene grains have exsolved into Ca-rich (~Wo38En29Fs33) and Ca-poor (~Wo4.5En36Fs59.5) lamellae. Both unzoned and zoned plagioclase grains are observed. Unzoned plagioclase grains are found solely with tridymite laths. These grains have ~An92 compositions. The cores of the zoned plagioclase grains have the same composition and thin, relatively sodic rims (~An67), (Fig. 1). The bulk sample is unusually enriched in highly in-compatible elements and has one of the most fractionated REE patterns reported [1]. Maximum metamorphic temperatures of 985±78°C have been estimated using two-pyroxene thermometry [2]. Methods: Thermodynamic modeling. Thermodynamic models were constructed using the software Perple_X, which employs a Gibbs free energy minimization in order to determine the most stable phase assemblage for a given bulk rock composition [3]. Bulk composition was calculated using mineral com-positions acquired via EMPA (this study) and the observed abundancies present in the thin section. Two bulk compositions were estimated; 1) includes all phases present in the thin section, (assumes that all phases are present during metamorphism), 2) excludes tridymite from the bulk calculation (assumes that tridymite was not present during metamorphism). In order to determine whether metamorphic equilibria was achieved and estimate temperatures of metamorphism, we compared measured pyroxene compositions with thermodynamically predicted compositions [4, Fig. 2]. Diffusion Modeling. Several time-temperature de-pendent diffusion profiles were calculated in order to determine the best match for XAn chemical profiles observed at the edges of the zoned plagioclase (Fig. 3). We assumed that the start condition was a stepwise gradient at the plagioclase/pyroxene interface. We also assumed an average diffusion coefficient (D) and a constant temperature using the equation in [5]. D was determined for two temperatures (T = 1060ºC; near eucrite solidus [6] and T = 985ºC; metamorphism reported in [4]) and then XAn was calculated as a function of distance from plagioclase core to rim using an error function solution to Fick’s second law. Results: Thermodynamic model results are summarized in Fig. 2. For a bulk composition that includes all phases in the thin section, pyroxene endmember compositions plot in the following temperature ranges: Fs ~660-860ºC, En~1000ºC & 1150ºC, and Wo~760-900ºC (Fig. 2a). For a bulk composition that excludes tridymite from the peak metamorphic assemblage (i.e., the bulk composition minus the contribution from tridymite), a temperature range could not be determined for the Fs component of pyroxene. For Wo, T~760-900ºC and En, T~1000ºC & 1150ºC (Fig. 2b). Fig. 3 summarizes the diffusion model results. For T = 1060°C & 985°C, the most appropriate time interval was estimated based on which diffusion curve most matched (solid lines, Fig. 3) the EMPA data. For T = 1060°C, the best looking match was t = 500 ka. For T = 985°C, the best match was t = 7 Ma. Discussion and future work: Temperature estimates from thermodynamic models are not conclusive because the temperature ranges determined for pyroxene endmember stability do not overlap (colored fields in Fig. 2), thus implying that there is disequilibrium between pyroxene crystals and the bulk composition considered [4]. Thus, additional exploration is needed to define a metamorphically equilibrated do-main that accurately records peak temperature. The utility of defining metamorphically equilibrated do-mains to improve the accuracy and level of detail elucidated regarding the petrogenetic history of metamorphose samples has been demonstrated previously [4,7]. We suggest that in the case of Fig. 2a, the thin section composition is not representative of the length scales over which metamorphic equilibrium was achieve and in the case of Fig. 2b, the assumption that tridymite was not present during metamorphism was incorrect. However, results from thermodynamic models can provide insight into the relative timing of mineral and compositional textures. For example from texture alone, it is unclear whether tridymite was igneous in origin and represents the last bits of melt in a crystallizing magma chamber, or if it formed during (and possibly initiated) open system thermal metamorphism. The latter could be consistent with a partial melt hypothesis [8,9] while the former implies that simple fractional crystallization can yield the textures present in GRA 98098. The lack of coincidence be-tween pyroxene endmember compositions in Fig. 2b suggest that the bulk composition minus tridymite was not the assemblage in equilibrium with the pyroxene, suggesting that tridymite was present during metamorphism and formed during igneous crystallization. We conclude that the development of the Na-rich plagioclase rims likely occurred during or immediately after peak thermal metamorphism, because eucrites of similar metamorphic grade and texture have unzoned plagioclase (~An92) [2,4,8], and Na zoning is only observed in the plagioclase not included in the tridymite. This suggests that the zoning formed after tridymite formation, and therefore after igneous crystallization. Thus, the timescales calculated via diffusion modeling possibly represent the time interval over which thermal metamorphism occurred. Cooling rates approximated for the Vestan crust predict that the crust cooled below 300°C around 35-40 Ma after formation[10]. This is consistent with our modeling results that predict formation of the Na rich plagioclase rims occurring at higher temperatures over a period of 0.5 to 7 Ma years. Future work. Additional thermodynamic modeling work will focus on selecting an equilibrated bulk rock domain in which to elucidate metamorphic conditions. Diffusion models currently provide a minimum time-scale, since diffusion slows down as the system cools. Future work with will focus on integrating cooling into the diffusion models and constraining the depth at which thermal metamorphism occurs because it could be used to determine whether the range of time-scales calculated for thermal metamorphism are consistent with the geologic environment.

J S Gorce↗

Gas turbine combustor stabilization by heat recirculation

The feasibility of heat recirculation for stabilization of lean mixtures and emission reduction has been studied in detail for a typical aircraft gas turbine combustor. Thermodynamic calculations have indicated temperature and heat recirculation rates for operation of the combustor over a range of combustion zone equivalence ratios and for varying modes of desired engine operation. Calculations indicate the feasibility of stabilizing the combustion zone at equivalence ratios as low as 0.2 with achievable heat recirculation rates. Detailed chemical kinetic calculations suggest that combustor heat release is maintained with reaction completion substantially before the NO forming reactions, even though CO is rapidly oxidized in this same region.

Ganji, A.↗

Stabilization functions of unforced cumulus clouds - Their nature and components

The nature and the spatial distribution of cumuli within an unforced cumulus cloud field are investigated. The thermodynamic effects of convection are quantified as functions of changes of convective available potential energy (CAPE) induced by the convective overturning, and the time rate of change of CAPE is parameterized in terms of a kernel of influence or stabilization function. A three-dimensional cloud model is used to infer and quantify stabilization functions by performing single-cloud experiments. On the basis of the results obtained, a new hypothesis with respect to the spatial distribution of cumuli is postulated, which states that, under completely homogeneous external conditions and assuming a spatially random distribution of cloud-triggering mechanisms, the spatial distribution of cumuli in the resulting cloud field must be regular, as opposed to either random or clustered, because cumulus clouds tend to reduce the available energy for convection, thereby inhibiting further convection nearby.

Ramirez, Jorge A.↗

Thermodynamics of Volatile Silicon Hydroxides Studied

Silicon-based ceramics are promising candidate structural materials for heat engines. The long-term stability of these materials to environmental degradation is dependent on the formation and retention of a protective SiO2 layer. It is well known that SiO2 forms stable volatile hydroxides in the presence of water vapor at elevated temperatures. Combustion conditions, which characteristically are at high velocities, contain significant water vapor pressures, and high temperatures tend to promote continuous formation of these hydroxides with resulting material degradation. For the degradation of silicon-based ceramics to be predicted, accurate thermodynamic data on the formation of silicon hydroxides are needed.

Copland, Evan H.↗

Origin of strong magnetic fields.

A possible mechanism by which extremely strong magnetic fields in neutron stars and white dwarfs could originate involves the existence of thermodynamic equilibrium states (LOFER states) of an electron gas. The essence of the stability theory of a LOFER state is discussed. The extended electronic system considered is in contact with a thermal bath in the presence of an external magnetic field. It is found that it is not necessary to require absolute stability in order to realize a LOFER state in nature.

Canuto, V.↗

Thermodynamic considerations in the support of life for long space voyages

The essential requirements for the maintenance of life, particularly human life, on isolated space missions of long duration were investigated through the study of extended irreversible thermodynamics. The characterization of a four trophic level system was developed. Questions of stability are discussed.

Iberall, A. S.↗

Convective heat flow in space cryogenics plugs - Critical and moderate He II heat flux densities

Plug flow rates of entropy, heat and normal fluid in phase separators and in zero net mass flow systems are, to some extent, quite similar. A simplified analysis of critical conditions is presented in agreement with data trends. A critical temperature gradient arises on the basis of the He II two-fluid model at the stability limit constraining the thermohydrodynamics of the system. Thus, the question of critical thermodynamic fluctuations associated with nucleation versus the possibility of critical gradients in externally imposed parameters is answered in favor of the latter route toward turbulence. Furthermore, a similarity equation is presented which incorporates size dependent rates for moderate heat flow densities observed in experiments.

Yuan, S. W. K.↗

Phase relations in the Fe-Ni-Cr-S system and the sulfidation of an austenitic stainless steel

The stability fields of various sulfide phases that form on Fe-Cr, Fe-Ni, Ni-Cr and Fe-Cr-Ni alloys were developed as a function of temperature and the partial pressure of sulfur. The calculated stability fields in the ternary system were displayed on plots of log P sub S sub 2 versus the conjugate extensive variable which provides a better framework for following the sulfidation of Fe-Cr-Ni alloys at high temperatures. Experimental and estimated thermodynamic data were used in developing the sulfur potential diagrams. Current models and correlations were employed to estimate the unknown thermodynamic behavior of solid solutions of sulfides and to supplement the incomplete phase diagram data of geophysical literature. These constructed stability field diagrams were in excellent agreement with the sulfide phases and compositions determined during a sulfidation experiment.

Jacob, K. T.↗

Identification of thermodynamically stable ceramic reinforcement materials for iron aluminide matrices

Aluminide-base intermetallic matrix composites are currently being considered as potential high-temperature materials. One of the key factors in the selection of a reinforcement material is its chemical stability in the matrix. In this study, chemical interactions between iron aluminides and several potential reinforcement materials, which include carbides, oxides, borides, and nitrides, are analyzed from thermodynamic considerations. Several chemically compatible reinforcement materials are identified for the iron aluminides with Al concentrations ranging from 40 to 50 at. pct.

Misra, Ajay K.↗