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At least 145 records · Page 8

Oxidation of Alumina-Forming MAX Phases in Turbine Environments

Protective coatings for high temperature turbine components are based on YSZ thermal barriers and oxidation resistant, alumina-forming NiAl or NiCoCrAlY bond coats. Ti2AlC and Cr2AlC MAX phases are thus of special interest because of good oxidation resistance and CTE that can match Al2O3 and YSZ. Their alumina scales grow according to cubic kinetics due to grain growth in the scale, with initial heating dominated by fast TiO2 growth. Protective cubic kinetics are also found in high pressure burner rig tests of MAXthal 211 Ti2AlC, but with reduced rates due to volatile TiO(OH)2 formation in water vapor. YSZ-coatings on bulk Ti2AlC exhibit remarkable durability up to 1300C in furnace tests and at least a 25x life advantage compared to superalloys. At another extreme, Cr2AlC is resistant to low temperature Na2SO4 hot corrosion and exhibits thermal cycling stability bonded to a superalloy disk material. Accordingly, sputtered Cr2AlC coatings on disk specimens prevented hot corrosion detriments on LCF. Breakaway oxidation (Ti2AlC), scale spallation (Cr2AlC), interdiffusion, and processing as coatings still present serious challenges. However the basic properties of MAX phases provide some unusual opportunities for use in high temperature turbines.

ceramics↗

Growth morphology with anisotropic surface kinetics

The morphological evolution of crystals growing from an incongruent vapor phase is studied using a Monte Carlo model, and the full range of growth morphologies is recovered. The diffusion in the bulk nutrient and the anisotropy in the interface kinetics are morphologically destabilizing and stabilizing, respectively. For a given set of simulation parameters and lattice symmetries there is a critical size, which scales linearly with the mean free path in the vapor, beyond which a crystal cannot retain its stable, macroscopically faceted growth shape. Surface diffusion stabilizes faceted growth on the shorter scale of the mean surface diffusion length. In simulations with a uniform drift superimposed on the random walk nutrient transport, crystal faces oriented toward the drift show enhanced morphological stability compared to the purely diffusive situation. Rotational drifts with periodic reversal of direction are morphologically stabilizing for all crystal facets.

Xiao, Rong-Fu↗

Effects of Convective Transport of Solute and Impurities on Defect-Causing Kinetics Instabilities in Protein Crystallization

The objective of the proposed research is to obtain further insight into the onset and development of the defect-causing instabilities that anise due to the coupling of the bulk transport and nonlinear-interfacial kinetics during growth in the mixed regime, utilizing the reduction of the convective contribution to the bulk transport under microgravity. These studies will build upon the data on the effects of quantitative variations of the forced convection velocity on the averaged and time-dependent kinetic behavior of protein crystal growth systems that have recently been obtained in our laboratory.

Vekilov, Peter G.↗

Kinetic Roughening and Energetics of Tetragonal Lysozyme Crystal Growth

Lysozyme crystal growth rates over 5 orders of magnitude in range can be described using a layer-by-layer model where growth occurs by 2D nucleation on the crystal surface. Based upon the 2D nucleation model of layer growth, the effective barrier for growth was determined to be gamma = 1.3 plus or minus 0.3 x 10(exp -13) erg/molecule, corresponding to a barrier of 3.2 plus or minus 0.7 k(sub B)T, at 22 C. For solution supersaturation, In c/c(sub eq) greater than or equal to 1.9 plus or minus 0.2, the nucleation model would not predict or consistently estimate the highest observable crystal growth rates. As such, a kinetic roughening hypothesis where crystal growth occurs by a continuous mode was implemented for all growth rate data obtained above In c(sub r)/c(sub eq) greater than or equal to 2. That is, independent of the solution conditions that vary with either buffer pH, temperature or precipitant concentration, crystal growth occurs by the continuous addition of molecules anywhere on the crystal surface, above a roughening solution supersaturation. The energy barrier, E(sub c), for the continuous growth process is determined as 6.1 plus or minus 0.4 x 10(exp -13) erg/molecule or 15 plus or minus 1 k(sub B)T at 22 C.

Gorti, Sridhar↗

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

The following list summarizes the most important results that have been consistently reported for glass forming melts in microgravity: (1) Glass formation is enhanced for melts prepared in space; (2) Glasses prepared in microgravity are more chemically homogeneous and contain fewer and smaller chemically heterogeneous regions than identical glasses prepared on earth; (3) Heterogeneities that are deliberately introduced such as Pt particles are more uniformly distributed in a glass melted in space than in a glass melted on earth; (4) Glasses prepared in microgravity are more resistant to crystallization and have a higher mechanical strength and threshold energy for radiation damage; and (5) Glasses crystallized in space have a different microstructure, finer grains more uniformly distributed, than equivalent samples crystallized on earth. The preceding results are not only scientifically interesting, but they have considerable practical implications. These results suggest that the microgravity environment is advantageous for developing new and improved glasses and glass-ceramics that are difficult to prepare on earth. However, there is no suitable explanation at this time for why a glass melted in microgravity will be more chemically homogeneous and more resistant to crystallization than a glass melted on earth. A fundamental investigation of melt homogenization, nucleation, and crystal growth processes in glass forming melts in microgravity is important to understanding these consistently observed, but yet unexplained results. This is the objective of the present research. A lithium disilicate (Li2O.2SiO2) glass will be used for this investigation, since it is a well studied system, and the relevant thermodynamic and kinetic parameters for nucleation and crystal growth at 1-g are available. The results from this research are expected to improve our present understanding of the fundamental mechanism of nucleation and crystal growth in melts and liquids, and to lead improvements in glass processing technology on earth, with the potential for creating new high performance glasses and glass-ceramics.

Day, Delbert E.↗

Kinetics of crystal nucleation and growth in Pd(40)Ni(40)P(20) glass

Samples of Pd(40)Ni(40)P(20) glass, produced by cooling the melt at 1 or 800 K/s, are heated in a differential scanning calorimeter to determine the crystallization kinetics. Optical microscopy shows that eutectic crystallization proceeds both by growth from the surface of the samples and by the growth of spherical regions around preexisting nuclei in the interior. A modified Kissinger (1957) analysis is used to obtain the activation energy for crystal growth (3.49 eV). The steady state homogeneous nucleation frequency at 590 K is about 10 million/cu m per sec. This is estimated to be the maximum nucleation frequency: it is too low to account for the observed population of quenched-in nuclei, which are therefore presumed to be heterogeneous. The major practical obstacle to glass formation in this system is heterogeneous nucleation.

Drehman, A. J.↗

Red light regulation of ethylene biosynthesis and gravitropism in etiolated pea stems

During gravitropism, the accumulation of auxin in the lower side of the stem causes increased growth and the subsequent curvature, while the gaseous hormone ethylene plays a modulating role in regulating the kinetics of growth asymmetries. Light also contributes to the control of gravitropic curvature, potentially through its interaction with ethylene biosynthesis. In this study, red-light pulse treatment of etiolated pea epicotyls was evaluated for its effect on ethylene biosynthesis during gravitropic curvature. Ethylene biosynthesis analysis included measurements of ethylene; the ethylene precursor 1-aminocyclopropane-1-carboxylic acid (ACC); malonyl-conjugated ACC (MACC); and expression levels of pea ACC oxidase (Ps-ACO1) and ACC synthase (Ps-ACS1, Ps-ACS2) genes by reverse transcriptase-polymerase chain reaction analysis. Red-pulsed seedlings were given a 6 min pulse of 11 micromoles m-2 s-1 red-light 15 h prior to horizontal reorientation for consistency with the timeline of red-light inhibition of ethylene production. Red-pulse treatment significantly reduced ethylene production and MACC levels in epicotyl tissue. However, there was no effect of red-pulse treatment on ACC level, or expression of ACS or ACO genes. During gravitropic curvature, ethylene production increased from 60 to 120 min after horizontal placement in both control and red-pulsed epicotyls. In red-pulsed tissues, ACC levels increased by 120 min after horizontal reorientation, accompanied by decreased MACC levels in the lower portion of the epicotyl. Overall, our results demonstrate that ethylene production in etiolated epicotyls increases after the initiation of curvature. This ethylene increase may inhibit cell growth in the lower portion of the epicotyl and contribute to tip straightening and reduced overall curvature observed after the initial 60 min of curvature in etiolated pea epicotyls.

Non-NASA Center↗

Inorganic and protein crystal growth - Similarities and differences

Transport and interface kinetic concepts for the design and control of inorganic crystal growth experiments are reviewed, and their applications and limitations in protein crystal growth are considered. It is suggested that the interfacial concentration gradients are steeper for faster crystallization, and that the interfacial concentration distributions for the protein and the precipitant can differ significantly. Results show that uniformity in crystal composition and steady-state conditions in growth kinetics are favored by larger sample size, since surface-tension gradients drive strong in microgravity experiments and in small samples on earth.

Rosenberger, F.↗

A study of the applicability of nucleation theory to quasi-thermodynamic transformations of second and higher Ehrenfest-order

Transient and steady-state phenomena in temperature, stress, and electric, field intensity in ferroelectric polymers were investigated. The application and extension of the theory in the primary stage to the polarization domain nucleation and growth in ferroelectric polymers were developed. The kinetics of this growth were investigated. Expressions describing nucleation under the influence of an electric field were found through the expansion of the Gibbs' free energy in a Maclaurin series. The series was expanded in the electric field strength rather than the degree of undercooling. The resulting expressions were manipulated and applied to the case of nucleation of polarized domains in ferroelectric polymers. The kinetics of the nucleation and growth of polarized domains are also investigated. This was accomplished through the modification of the Johnson-Mehl-Avrami treatment of crystallization kinetics to be applicable to the growth of polarization domains in ferroelectric materials.

Barker, R. E., Jr.↗

Integrated and spectral energetics studies of the GLAS general circulation model

Integrated and spectral energetics of the Goddard Laboratory for Atmospheric Sciences (GLAS) general circulation model are compared with observations and examined when subdivided beyond hemispheric integrals. In the monthly mean zonal averages, qualitative improvements are found over previous versions of the model in eddy kinetic energy and barotropic conversions although vertical shear above the subtropical jet remains weak. This paper traces this problem to the erroneous growth of kinetic energy above strong jets, shows that this difficulty is common to all orographic general circulation models, and suggests that this problem has significant effects on upper-level long-wave predictability. In particular, it is considered whether hemispherically integrated kinetic energy or low-wavenumber spectral coefficients retain any skill as the predictability limit. In the time-dependent comparisons, the model shows significant skill in predicting the hemispherically integrated eddy kinetic energy out to two weeks for one of two cases.

Tenenbaum, J.↗

Gravitational effects in dendritic growth

The theories of diffusion-controlled dendritic crystallization will be reviewed briefly, along with recently published critical experiments on the kinetics and morphology of dendritic growth in pure substances. The influence of the gravitational body force on dendrite growth kinetics will be shown to be highly dependent on the growth orientation with respect to the gravity vector and on the level of the thermal supercooling. In fact, an abrupt transition occurs at a critical supercooling, above which diffusional transport dominates the growth process and below which convective transport dominates. Our most recent work on binary mixtures shows that dilute solute additions influence the crystallization process indirectly, by altering the interfacial stability, rather than by directly affecting the transport mode. Directions for future studies in this field will also be discussed.

Glicksman, M. E.↗

Nonlinear Response of Layer Growth Dynamics in the Mixed Kinetics-Bulk-Transport Regime

In situ high-resolution interferometry on horizontal facets of the protein lysozyme reveal that the local growth rate R, vicinal slope p, and tangential (step) velocity v fluctuate by up to 80% of their average values. The time scale of these fluctuations, which occur under steady bulk transport conditions through the formation and decay of step bunches (macrosteps), is of the order of 10 min. The fluctuation amplitude of R increases with growth rate (supersaturation) and crystal size, while the amplitude of the v and p fluctuations changes relatively little. Based on a stability analysis for equidistant step trains in the mixed transport-interface-kinetics regime, we argue that the fluctuations originate from the coupling of bulk transport with nonlinear interface kinetics. Furthermore, step bunches moving across the interface in the direction of or opposite to the buoyancy-driven convective flow increase or decrease in height, respectively. This is in agreement with analytical treatments of the interaction of moving steps with solution flow. Major excursions in growth rate are associated with the formation of lattice defects (striations). We show that, in general, the system-dependent kinetic Peclet number, Pe(sub k) , i.e., the relative weight of bulk transport and interface kinetics in the control of the growth process, governs the step bunching dynamics. Since Pe(sub k) can be modified by either forced solution flow or suppression of buoyancy-driven convection under reduced gravity, this model provides a rationale for the choice of specific transport conditions to minimize the formation of compositional inhomogeneities under steady bulk nutrient crystallization conditions.

Vekilov, Peter G.↗

Symposium on Combustion /International/, 16th, Massachusetts Institute of Technology, Cambridge, Mass., August 15-20, 1976, Proceedings

Aspects of combustion technology in power systems are considered, taking into account a combustion in large boilers, the control of over-all thermal efficiency of combustion heating systems, a comparison of mathematical models of the radiative behavior of a large-scale experimental furnace, a concentric multiannular swirl burner, and the effects of water introduction on diesel engine combustion and emissions. Attention is also given to combustion and related processes in energy production from coal, spray and droplet combustion, soot formation and growth, the kinetics of elementary reactions, flame structure and chemistry, propellant ignition and combustion, fire and explosion research, mathematical modeling, high output combustion systems, turbulent flames and combustion, and ignition, optical, and electrical properties.

Source record↗

Two-stream Maxwellian kinetic theory of cloud droplet growth by condensation

A new growth rate formula (NGRF) is developed for the rate of growth of cloud droplets by condensation. The theory used is a modification of the Lees-Shankar theory in which the two-stream Maxwellian distribution function of Lees is used in Maxwell's method of moments to determine the transport of water vapor to and heat away from the droplet. Boundary conditions at the droplet are the usual conditions set in terms of accommodation coefficients, and the solution passes smoothly into diffusion flow in the far region. Comparisons are given between NGRF and the conventional formula showing close agreement (approximately 0.1%) for large radii with significant difference (approximately 5%) for small radii (not greater than 1 micron). Growth times for haze droplets in a Laktionov chamber are computed.

Robinson, N. F.↗

Heterogeneous atmospheric chemistry

The present conference on heterogeneous atmospheric chemistry considers such topics concerning clusters, particles and microparticles as common problems in nucleation and growth, chemical kinetics, and catalysis, chemical reactions with aerosols, electron beam studies of natural and anthropogenic microparticles, and structural studies employing molecular beam techniques, as well as such gas-solid interaction topics as photoassisted reactions, catalyzed photolysis, and heterogeneous catalysis. Also discussed are sulfur dioxide absorption, oxidation, and oxidation inhibition in falling drops, sulfur dioxide/water equilibria, the evidence for heterogeneous catalysis in the atmosphere, the importance of heterogeneous processes to tropospheric chemistry, soot-catalyzed atmospheric reactions, and the concentrations and mechanisms of formation of sulfate in the atmospheric boundary layer.

Schryer, D. R.↗

The first plants to fly on Shuttle

The methods and results are presented concerning experiments using the first plants to make a journey for scientific purposes in earth orbit on board Space Shuttles 2 and 3. These experiments were conducted in order to validate the culture system planned for use in a Spacelab-1 experiment involving the growth and kinetics of sunflower seedlings. The experimental flight package is described and the preparation steps taken prior to the flights are discussed. The conditions to which the plants were exposed during the flights are examined in detail, focusing on the temperature profile and the gravitational forces during reentry to landing.

Brown, A. H.↗

A study of interdiffusion in beta + gamma/gamma + gamma prime Ni-Cr-Al

Ternary diffusion in the NiCrAl system at 1200 C was studied with beta + gamma/gamma + gamma prime infinite diffusion couples. Interdiffusion resulted in the formation of complex, multiphase diffusion zones. Concentration/distance profiles for Cr and Al in the phases present in the diffusion zone were measured after 200 hr. The Ni-rich portion of the NiCrAl phase diagram (1200 C) was also determined. From these data, bulk Cr and Al profiles were calculated and translated to diffusion paths on the ternary isotherm. Growth layer kinetics of the layers present in the diffusion zone were also measured.

Carol, L. A.↗