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At least 163 records · Page 9

X-Ray Absorption Spectroscopy in High Temperature Oxidation of Metals and Alloys

An experimental technique is described that allows for the joint study of the kinetics and of the oxide structure during the high temperature oxidation of metal surfaces. Oxygen is supplied at the metal through an electrochemical oxygen pump and the oxygen pressure, at the metal surface, is measured during oxidation by a YSZ (yttria stabilized zirconia) oxygen sensor. XAS (x-ray absorption spectroscopy) is performed in fluorescence mode at the cation K edge and after each oxidation step. An appropriate analysis of the XAS spectra could provide information on both the oxidation kinetics and oxide structure. Experimental data on the high temperature oxidation of nickel, cobalt, and Fe(64%)Ni(36%) alloy, at low oxygen pressure, are reported and analyzed according to the proposed data reduction. These results indicate the presented technique to be particularly suitable for studying the hot corrosion of oxide film too thick for common surface spectroscopy (AUGER, ESCA) and too thin for conventional thermogravimetric technique.

Daniele Gozzi↗

A compilation of studies from Atmospheric Variability Experiment (AVE)

Five methods for obtaining the sign of vertical motion at various levels in the atmosphere were investigated to determine which gave the best explanation for areas of rain and no-rain in the southeastern United States during the period February 19-22, 1964. The methods used were the terrain-induced vertical motion, the kinematic method including the terrain effect, the adiabatic method, the omega equation, and the vorticity equation combined with Dines' Compensation Principle. Stability and moisture availability were considered but not as extensively as vertical motion. Values of vertical motion obtained by the kinetic method, including orographic lifting produced the best agreement with the observed areas. When terms in the omega equation were added through use of constant multipliers, results comparable to the adiabatic method were obtained. Without this addition large uncertainties occurred. Maps showing areas where terms of the omega equation would indicate positive vertical motion did not correlate well with the observed rainfall patterns.

Scoggins, J. R.↗

Hypersonic Flight and the Re-Entry Problem: The Twenty-First Wright Brothers Lecture

Up to this point the discussion of the problems of rocket vehicles has been confined to the effects of phenomena which have in the past been important ones for lower speed aircraft and will continue to be important for aircraft of all speeds. Now with considerable extension of both speed and altitude, other phenomena also become important. The nature of some problems will be altered, as a result, and new problems, of course, will be encountered. First, it is well to note that our interest in bluff bodies for ballistic vehicles in particular, and in rounded-nosed bodies generally, has changed our emphasis in aerodynamics. The detached bow waves which occur with such bodies at high supersonic speeds complicate the calculations of the flow-field characteristics. In the present period, much attention is being given to such studies. In addition, at the very high altitudes attained by most of the rocket-craft, the mean free path of air molecules can be of the same order, or long, compared to the dimensions of the vehicles. Thus, slip-flow and free-molecule-flow studies are of interest, particularly for satellite vehicles." The aerodynatnicist must deal with air having unfamiliar states and properties. Second, at hypersonic speeds where, for example, air is greatly decelerated, it may undergo considerable change in composition, the degree of change depending upon many factors. Dissociation of oxygen and nitrogen molecules can occur and, in addition, thermal ionization of many of the constituents. It is naturally to be expected that the convective heat transfer will, as a result, be altered from what it was for the "perfect" gas, and this has been the subject of much recent research effort. Moreover, the decelerated gas becomes capable of radiating energy and the radiative heat transfer must generally be considered for hypersonic vehicles, particularly for long-range ballistic rockets. It is not only the aerodynamic heating problems that are affected. The fact that at very high air temperature the gas becomes electrically conductive introduces new problems in radio wave transmission and reception. In addition, a conducting gas flow can, of course, be influenced by a magnetic field. The study of such flows, which has been termed "magneto gas dynamics," is still in too primitive a state to indicate how important a role it can play, but many interesting possibilities suggest themselves. Third, our experience with airplanes powered by air-breathing engines has naturally been restricted to the stratosphere, or lower. Our ignorance increases with altitude. For rockets, literally, "the sky's the limit," and it is not surprising that a great emphasis has now been placed on obtaining a more thorough understanding of the whole atmosphere. These studies are not aimed at an understanding of the chemical and physical characteristics alone, but also of the occurrence of high-energy particles, from meteors to cosmic rays, and the nature of the problems they will promote.

Wright Brother↗

A new criterion for bar-forming instability in rapidly rotating gaseous and stellar systems. 2: Nonaxisymmetric form

We have previously introduced the parameter alpha as an indicator of stability to m = 2 nonaxisymmetric modes in rotating, self-gravitating, axisymmetric, gaseous (alpha less than or approximately equal to 0.34) and stellar (alpha less than or approximately equal to 0.25) systems. This parameter can be written as alpha = (ft/2)(exp 1/2), where t is defined as T/(absolute value of W), T is the total rotational kinetic energy, W is the total gravitational potential energy, and f is a function characteristic of the topology/connectedness and the geometric shape of a system. In this paper, we extend the stability criterion to nonaxisymmetric equilibrium systems by determining empirically the appropriate form of the function f for ellipsoids and elliptical disks and cylinders. We test the validity of this extension of the stability indicator alpha by considering its predictions for previously published, gaseous and stellar, nonaxisymmetric models. The formulation and critical values account accurately for the stability properties of m =2 modes in gaseous Riemann S-type ellipsoids (including the Jacobi and Dedekind ellipsoids) and elliptical Riemann disks as well as in stellar elliptical Freeman disks and cylinders: all these systems are dynamically stable except the stellar elliptical Freeman disks that exhibit a relatively small region of m = 2 dynamical instability. A partial disagreement in the case of stellar Freeman ellipsoids in maximum rotation may be due to the fact that the region of instability has not been previously determined with sufficient accuracy.

Christodoulou, Dimitris M.↗

Salt modulates the stability and lipid binding affinity of the adipocyte lipid-binding proteins

Adipocyte lipid-binding protein (ALBP or aP2) is an intracellular fatty acid-binding protein that is found in adipocytes and macrophages and binds a large variety of intracellular lipids with high affinity. Although intracellular lipids are frequently charged, biochemical studies of lipid-binding proteins and their interactions often focus most heavily on the hydrophobic aspects of these proteins and their interactions. In this study, we have characterized the effects of KCl on the stability and lipid binding properties of ALBP. We find that added salt dramatically stabilizes ALBP, increasing its Delta G of unfolding by 3-5 kcal/mol. At 37 degrees C salt can more than double the stability of the protein. At the same time, salt inhibits the binding of the fluorescent lipid 1-anilinonaphthalene-8-sulfonate (ANS) to the protein and induces direct displacement of the lipid from the protein. Thermodynamic linkage analysis of the salt inhibition of ANS binding shows a nearly 1:1 reciprocal linkage: i.e. one ion is released from ALBP when ANS binds, and vice versa. Kinetic experiments show that salt reduces the rate of association between ANS and ALBP while simultaneously increasing the dissociation rate of ANS from the protein. We depict and discuss the thermodynamic linkages among stability, lipid binding, and salt effects for ALBP, including the use of these linkages to calculate the affinity of ANS for the denatured state of ALBP and its dependence on salt concentration. We also discuss the potential molecular origins and potential intracellular consequences of the demonstrated salt linkages to stability and lipid binding in ALBP.

NASA Discipline Cell Biology↗

A new criterion for bar-forming instability in rapidly rotating gaseous and stellar systems. 1: Axisymmetric form

We analyze previous results on the stability of uniformly and differentialy rotating, self-gravitating, gaseous and stellar, axisymmetric systems to derive a new stability criterion for the appearance of torodial, m = 2 intermediate or I-modes and bar modes. In the process, we demonstrate that the bar modes in stellar systems and the m = 2 I-modes in gaseous systems have many common physical characteristics and only one substantial difference: because of the anisotropy of the stress tensor, dynamical instability sets in at lower rotation in stellar systems. This difference is reflected also in the new stability criterion. The new stability parameter alpha equals (T(sub J))/(absolute value of W) is formulated first for uniformly rotating systems and is based on the angular momentum content rather than on the energy content of a system. (T(sub J) is defined as ((L)(Omega(sub J)))/2; L is the total angular momentum; Omega(sub J) is the Jeans frequency introduced by self-gravity; and W is the total gravitational potential energy.) For stability of stellar systems alpha less than or equal to 0.254-0.258 while alpha less than or equal to 0.341-0.354 for stability of gaseous systems. For uniform rotation, one can write alpha = ((ft)/2)(exp 1/2), where t is defined as T/(absolute value of W), T is the total kinetic energy due to rotation, and f is a function characteristic of the topology/connectedness and the geometric shape of a system. Equivalently, alpha equals t/(chi), where chi is defined as Omega/Omega(sub J) and Omega is the rotation frequency. Using these forms, alpha can be extended to and calculated for a variety of differentially rotating, gaseous and stellar, axisymmetric disk and spheroidal models whose equilibrium structures and stability characteristics are known. In this paper, we also estimate alpha for gaseous torodial models and for stellar disk systems embedded in an inert or responsive 'halo.' We find that the new stability criterion holds equally well for all these previously published axisymmetric models.

Christodoulou, Dimitris M.↗

Effect of gravity on halogenated hydrocarbon flame retardant effectiveness

Flammability limits, burning velocities, and minimum ignition energies under initially quiescent conditions were measured for stoichiometric and fuel-lean methane-, ethane-, and propane-air mixtures containing varying concentrations of Halon 1301. The characteristics of near-limit flames were strongly affected by fuel type but not Halon concentration. The conclusions were that the mechanism of the flammability limits was affected by fuel type but not Halon concentration, that the zero-g flammability limit is probably related to a stability criterion which is affected mostly by the molecular diffusion characteristics of the reactant gases and is mostly independent of chemical kinetics, and that the one-g upward flammability and ignition limits provide adequate criteria for safety at one-g and zero-g for both uninhibited and inhibited mixtures.

Ronney, P. D.↗

Effect of gravity on halogenated hydrocarbon flame retardant effectiveness

Flammability limits, burning velocities, and minimum ignition energies under initially quiescent conditions were measured for stoichiometric and fuel-lean methane-, ethane-, and propane-air mixtures containing varying concentrations of Halon 1301. The characteristics of near-limit flames were strongly affected by fuel type but not Halon concentration. The conclusions were that the mechanism of the flammability limits was affected by fuel type but not Halon concentration, that the zero-g flammability limit is probably related to a stability criterion which is affected mostly by the molecular diffusion characteristics of the reactant gases and is mostly independent of chemical kinetics, and that the one-g upward flammability and ignition limits provide adequate criteria for safety at one-g and zero-g for both uninhibited and inhibited mixtures.

Ronney, P. D.↗

Simulation of collisional transport processes and the stability of planetary rings

The utility of the phase-space fluid method for the study of planetary ring dynamics is presently demonstrated through the numerical solution of a model kinetic equation for a flattened Keplerian disk. Attention is given to ringlets composed of single-sized particles, as well as to ringlets composed of two different-sized particles; in the latter case, the ringlets evolve in such a way that the lighter particles are confined by the heavier ones. The results obtained indicate that some natural process may sharpen the optical depth profile of edges even without an external forcing mechanism, and that intermediate optical depths are dynamically preferred in some cases.

Brophy, Thomas G.↗

On the use of external burning to reduce aerospace vehicle transonic drag

The external combustion of hydrogen to reduce the transonic drag of aerospace vehicles is currently being investigated. A preliminary analysis based on a constant pressure control volume is discussed. Results indicate that the specific impulse of the external burning process rivals that of a turbojet and depends on the severity of the initial base drag as well as on the Mach flight number and the equivalence ratio. A test program was conducted to investigate hydrogen-air flame stability at the conditions of interest and to demonstrate drag reduction on a simple expansion ramp. Initial test results are presented and compared with the control-volume analysis. The expansion ramp surface pressure coefficient showed little variation with fuel pressure and altitude, in disagreement with the analysis. Flame stability results were encouraging and indicate that stable combustion is possible over an adequate range of conditions. Facility interference and chemical kinetics phenomena that make interpretation of subscale ground test data difficult are discussed.

Trefny, Charles J.↗

Fracture-tough, corrosion-resistant bearing steels

The fundamental principles allowing design of stainless bearing steels with enhanced toughness and stress corrosion resistance has involved both investigation of basic phenomena in model alloys and evaluation of a prototype bearing steel based on a conceptual design exercise. Progress in model studies has included a scanning Auger microprobe (SAM) study of the kinetics of interfacial segregation of embrittling impurities which compete with the kinetics of alloy carbide precipitation in secondary hardening steels. These results can define minimum allowable carbide precipitation rates and/or maximum allowable free impurity contents in these ultrahigh strength steels. Characterization of the prototype bearing steel designed to combine precipitated austenite transformation toughening with secondary hardening shows good agreement between predicted and observed solution treatment response including the nature of the high temperature carbides. An approximate equilibrium constraint applied in the preliminary design calculations to maintain a high martensitic temperature proved inadequate, and the solution treated alloy remained fully austenitic down to liquid nitrogen temperature rather than transforming above 200 C. The alloy can be martensitically transformed by cryogenic deformation, and material so processed will be studied further to test predicted carbide and austenite precipitation behavior. A mechanistically-based martensitic kinetic model was developed and parameters are being evaluated from available kinetic data to allow precise control of martensitic temperatures of high alloy steels in future designs. Preliminary calculations incorporating the prototype stability results suggest that the transformation-toughened secondary-hardening martensitic-stainless design concept is still viable, but may require lowering Cr content to 9 wt. pct. and adding 0.5 to 1.0 wt. pct. Al. An alternative design approach based on strain-induced martensitic transformation during cryogenic forming, thus removing the high martensitic constraint, may permit alloy compositions offering higher fracture roughness.

Olson, Gregory B.↗

On the use of external burning to reduce aerospace vehicle transonic drag

The external combustion of hydrogen to reduce the transonic drag of aerospace vehicles is currently being investigated. A preliminary analysis based on a constant pressure control volume is discussed. Results indicate that the specific impulse of the external burning process rivals that of a turbojet and depends on the severity of the initial base drag as well as on the Mach flight number and the equivalence ratio. A test program was conducted to investigate hydrogen-air flame stability at the conditions of interest and to demonstrate drag reduction on a simple expansion ramp. Initial test results are presented and compared with the control-volume analysis. The expansion ramp surface pressure coefficient showed little variation with fuel pressure and altitude, in disagreement with the analysis. Flame stability results were encouraging and indicate that stable combustion is possible over an adequate range of conditions. Facility interference and chemical kinetics phenomena that make interpretation of subscale ground test data difficult are discussed.

Trefny, Charles J.↗

Analytical and Numerical Modeling of Flame-Balls in Hydrogen-Air Mixtures

Flame-balls are stationary spherical premixed flames observed in certain near-limit mixtures. It is believed that radiative heat losses are an important stabilizing influence. Numerical solutions of flame balls are constructed for hydrogen-air mixtures using an accurate description of the chemical kinetics, diffusive transport, and radiation losses. A lean limit equivalence ratio of 0.0866 is predicted and a rich limit of 2,828. For any equivalence ratio between the two limits there are two solutions. One is characterized by a small flame, incomplete reactant consumption, and negligible radiation losses. The other by a large flame, complete consumption of one of the reactants, and significant radiation losses. The maximum temperature varies between 1200 and 900 K as the two solution branches are traversed. Much of our discussion is a reprise and modification of previously published analytical results, for these provide physical insight into the nature of the solutions, and suggest that a portion of the large flame branch near the lean limit is stable and so corresponds to observable flames.

Buckmaster, J.↗

Characterization of High-Frequency Excitation of a Wake by Simulation

Insights into the effects of high-frequency forcing on free shear layer evolution are gained through analysis of several direct numerical simulations. High-frequency forcing of a fully turbulent plane wake results in only a weak transient effect. On the other hand, significant changes in the developed turbulent state may result when high-frequency forcing is applied to a transitional wake. The impacts of varying the characteristics of the high-frequency forcing are examined, particularly, the streamwise wavenumber band in which forcing is applied and the initial amplitude of the forcing. The high-frequency excitation is found to increase the dissipation rate of turbulent kinetic energy, to reduce the turbulent kinetic energy production rate, and to reduce the turbulent kinetic energy suppression increases with forcing amplitude once a threshold level has been reached. For a given initial forcing energy, the largest reduction in turbulent kinetic energy density was achieved by forcing wavenumbers that are about two to three times the neutral wavenumber determined from linear stability theory.

Cain, Alan B.↗

Chemical Thermodynamics and the Mathematical Integration of Reaction Kinetics

Key advances in the development of numerical methods for non-reacting compressible flows have been enabled by translating physical requirements into concrete numerical guidelines, such as the satisfaction of entropy inequalities for shock-capturing techniques [Lax, Contributions to Nonlinear Functional Analysis (1971) 603-634]. In the present work, we present nonlinear numerical analysis tools that draw from Chemical Thermodynamics , the branch of Nonequilibrium Thermodynamics that deals with chemical reactions. Through Gibbs formalism, chemical thermodynamics provides a well-known theoretical expression for the chemical equilibrium constant of a reaction in terms of reduced chemical potentials. A less-known, yet extremely valuable result, due to [Krambeck, Arch. Ration. Mech. Anal. , 38 (1970) 317], states that when this expression is implemented, mass-action kinetic models are consistent with the dynamical prescriptions of the 2nd law of thermodynamics. For fixed-temperature ordinary differential equations modeling constant-volume reacting gas mixtures, this leads to a decreasing Helmholtz free energy. If the temperature is allowed to vary in accordance with conservation of energy (1st law), this leads to the statement of increasing entropy. These nonlinear prescriptions can, and should be, used to further develop temporal integration techniques for reaction kinetics. We demonstrate that Krambeck's result holds even when the equilibrium constants are approximated from data. We prove this result by constructing the implicit free energy and the implicit entropy inherent to a given approximation. This is first done for a 5-species, 17-reaction model problem for air. With this structure established, elements of discrete entropy-stability theory [Tadmor, Acta Numer. , 12 (2003) 451] are leveraged to examine the consistency of time-integration schemes with these prescriptions. Using chemical potentials, one can compute the respective contributions of the kinetics model and of the temporal scheme to free energy/entropy variations. We introduce a nonlinear-stable version of the Discontinuous-Galerkin (DG) scheme in time which shows robustness improvements over the standard linearly-stable version. Most notably, the maximum timestep that can be resolved with the nonlinearly-stable variant tends to grow with polynomial order, in contrast to the linearly-stable variant. We generalize our constructions to arbitrary systems of reversible chemical reactions, ultimately showing that the compressible reacting Euler system admits the opposite of the implicitly constructed thermodynamic entropy as a mathematical entropy . This lays important theoretical foundations towards robust scheme development [Harten, J. Comput. Phys. 49 (1983) 151-164].

STMD↗

Understanding thermal stability in doped zirconia aerogels for high temperature applications

The high porosities and low densities of ceramic aerogels offer outstanding insulative performance in applications where weight is a critical factor. The high surface-to-volume ratios and specific surface areas provide extremely low thermal conductivity, but also contribute to rapid densification of the pore structure at elevated temperatures. This densification diminishes their favorable properties and inhibits use of aerogels in high temperature applications. The purpose of this work is the establishment of a design framework for thermally stable, highly porous materials. Here we will review our recent studies on the effects of synthetic parameters and dopant chemistry on the evolution of zirconia-based aerogels. The structural evolution was studied to 1200 °C using nitrogen physisorption, scanning and transmission electron microscopy, and x-ray diffraction. The role of dopant identity and concentration in thermal stability was elucidated. In context of the design framework, dopant chemistry is an aggregate for many closely related material properties, each of which may contribute to aerogel structural evolution. To develop a truly predictive design framework for ceramic-based aerogels, systematic and comprehensive evaluation of thermodynamic and kinetic properties must be performed in conjunction with studies on structural evolution.

aerogel↗

Kinetic Monte Carlo Simulation of Cation Diffusion in Low-K Ceramics

Low thermal conductivity (low-K) ceramic materials are of interest to the aerospace community for use as the thermal barrier component of coating systems for turbine engine components. In particular, zirconia-based materials exhibit both low thermal conductivity and structural stability at high temperature, making them suitable for such applications. Because creep is one of the potential failure modes, and because diffusion is a mechanism by which creep takes place, we have performed computer simulations of cation diffusion in a variety of zirconia-based low-K materials. The kinetic Monte Carlo simulation method is an alternative to the more widely known molecular dynamics (MD) method. It is designed to study "infrequent-event" processes, such as diffusion, for which MD simulation can be highly inefficient. We describe the results of kinetic Monte Carlo computer simulations of cation diffusion in several zirconia-based materials, specifically, zirconia doped with Y, Gd, Nb and Yb. Diffusion paths are identified, and migration energy barriers are obtained from density functional calculations and from the literature. We present results on the temperature dependence of the diffusivity, and on the effects of the presence of oxygen vacancies in cation diffusion barrier complexes as well.

Good, Brian↗

Experimental determination of gap flow-conditioned forces at turbine stages and their effect on the running stability of simple rotors

Instabilities in turbine operation can be caused by forces which are produced in connection with motions involving the oil film in the bearings. An experimental investigation regarding the characteristics of such forces in the case of three typical steam turbine stages is conducted, taking into account the effect of various parameters. Supplementary kinetic tests are carried out to obtain an estimate of the flow forces which are proportional to the velocity. The measurements are based on the theoretical study of the damping characteristics of a vibrational model. A computational analysis of the effect of the measured fluid forces on the stability characteristics of simple rotor model is also conducted.

Wohlrab, R.↗