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All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Kinetic Roughening Transition and Energetics of Tetragonal Lysozyme Crystal Growth

Interpretation of lysozyme crystal growth rates using well-established physical theories enabled the discovery of a phenomenon possibly indicative of kinetic roughening. For example, lysozyme crystals grown above a critical supersaturation sigma, (where supersaturation sigma = ln c/c(sub eq), c = the protein concentration and c(sub eq) = the solubility concentration) exhibit microscopically rough surfaces due to the continuous addition of growth units anywhere on the surface of a crystal. The rate of crystal growth, V(sub c), for the continuous growth process is determined by the continuous flux of macromolecules onto a unit area of the crystal surface, a, from a distance, xi, per unit time due to diffusion, and a probability of attachment onto the crystal surface, expressed. Based upon models applied, the energetics of lysozyme crystal growth was determined. The magnitudes of the energy barriers of crystal growth for both the (110) and (101) faces of tetragonal lysozyme crystals are compared. Finally, evidence supportive of the kinetic roughening hypothesis is presented.

Gorti, Sridhar↗
NASA NTRS2004

Numerical Simulation of Nanostructure Growth

Nanoscale structures, such as nanowires and carbon nanotubes (CNTs), are often grown in gaseous or plasma environments. Successful growth of these structures is defined by achieving a specified crystallinity or chirality, size or diameter, alignment, etc., which in turn depend on gas mixture ratios. pressure, flow rate, substrate temperature, and other operating conditions. To date, there has not been a rigorous growth model that addresses the specific concerns of crystalline nanowire growth, while demonstrating the correct trends of the processing conditions on growth rates. Most crystal growth models are based on the Burton, Cabrera, and Frank (BCF) method, where adatoms are incorporated into a growing crystal at surface steps or spirals. When the supersaturation of the vapor is high, islands nucleate to form steps, and these steps subsequently spread (grow). The overall bulk growth rate is determined by solving for the evolving motion of the steps. Our approach is to use a phase field model to simulate the growth of finite sized nanowire crystals, linking the free energy equation with the diffusion equation of the adatoms. The phase field method solves for an order parameter that defines the evolving steps in a concentration field. This eliminates the need for explicit front tracking/location, or complicated shadowing routines, both of which can be computationally expensive, particularly in higher dimensions. We will present results demonstrating the effect of process conditions, such as substrate temperature, vapor supersaturation, etc. on the evolving morphologies and overall growth rates of the nanostructures.

Hwang, Helen H.↗
NASA NTRS2004

Growth Modes and Energetics of 101 Face Lysozyme Crystal Growth

From analyses of lysozyme 101 face growth rate data using a 2D nucleation model for layer-by-layer growth, we find the effective barrier for crystal growth to be gamma = 1.0 +/- 0.2 x 10(exp -13) erg/molecule. The magnitude of the effective barrier is 2.4 +/- 0.5 k(sub beta)T, at 22 C. We also find that beyond a critical solution supersaturation, sigma(sub c), crystal growth rates are more accurately described by a kinetic roughening hypothesis. Beyond sigma(sub c), crystals grow by the continuous addition of molecules anywhere on the crystal surface rather than layer-by-layer. The magnitude of the critical supersaturation (sigma(sub c), = 1.7 +/- 0.2) for a crossover from a layer-by-layer to continuous growth is found to be statistically independent of the solution conditions that vary with buffer pH, temperature or precipitant concentration. Using the experimentally determined values for gamma and sigma(sub c), we find the crystal growth unit to be comprised of 7 +/- 3 molecules. The energy barrier, E(sub c), for the continuous addition of the growth Units is 6.2 +/- 0.3 x 10(exp -13) erg/molecule or 15 +/1 1 k(sub beta)T at 22C.

Gorti, Sridhar↗
NASA NTRS1999

Mathematical model to estimate risk of calcium-containing renal stones

BACKGROUND/AIMS: Astronauts exposed to microgravity during the course of spaceflight undergo physiologic changes that alter the urinary environment so as to increase the risk of renal stone formation. This study was undertaken to identify a simple method with which to evaluate the potential risk of renal stone development during spaceflight. METHOD: We used a large database of urinary risk factors obtained from 323 astronauts before and after spaceflight to generate a mathematical model with which to predict the urinary supersaturation of calcium stone forming salts. RESULT: This model, which involves the fewest possible analytical variables (urinary calcium, citrate, oxalate, phosphorus, and total volume), reliably and accurately predicted the urinary supersaturation of the calcium stone forming salts when compared to results obtained from a group of 6 astronauts who collected urine during flight. CONCLUSIONS: The use of this model will simplify both routine medical monitoring during spaceflight as well as the evaluation of countermeasures designed to minimize renal stone development. This model also can be used for Earth-based applications in which access to analytical resources is limited.

NASA Center JSC↗
NASA NTRS1997

Renal stone risk assessment during Space Shuttle flights

PURPOSE: The metabolic and environmental factors influencing renal stone formation before, during, and after Space Shuttle flights were assessed. We established the contributing roles of dietary factors in relationship to the urinary risk factors associated with renal stone formation. MATERIALS AND METHODS: 24-hr. urine samples were collected prior to, during space flight, and following landing. Urinary and dietary factors associated with renal stone formation were analyzed and the relative urinary supersaturation of calcium oxalate, calcium phosphate (brushite), sodium urate, struvite and uric acid were calculated. RESULTS: Urinary composition changed during flight to favor the crystallization of calcium-forming salts. Factors that contributed to increased potential for stone formation during space flight were significant reductions in urinary pH and increases in urinary calcium. Urinary output and citrate, a potent inhibitor of calcium-containing stones, were slightly reduced during space flight. Dietary intakes were significantly reduced for a number of variables, including fluid, energy, protein, potassium, phosphorus and magnesium. CONCLUSIONS: This is the first in-flight characterization of the renal stone forming potential in astronauts. With the examination of urinary components and nutritional factors, it was possible to determine the factors that contributed to increased risk or protected from risk. In spite of the protective components, the negative contributions to renal stone risk predominated and resulted in a urinary environment that favored the supersaturation of stone-forming salts. Dietary and pharmacologic therapies need to be assessed to minimize the potential for renal stone formation in astronauts during/after space flight.

STS Shuttle Project↗
NASA NTRS2006

Compositional Pathways and Capillary Effects during Early-stage Isothermal Precipitation in a Nondilute Ni-Al-Cr Alloy

For a Ni-5.2 Al-14.2 Cr at.% alloy with moderate solute supersaturations, the compositional pathways, as measured with atom-probe tomography, during early to later stage y'(LI2)-precipitation (R = 0.45-10 nm), aged at 873 K, are discussed in light of a multi-component coarsening model. Employing nondilute thermodynamics, detailed model analyses during quasistationary coarsening of the experimental data establish that the y/y' interfacial free-energy is 22- 23+/-7 mJ/sq m. Additionally, solute diffusivities are significantly slower than model estimates. Strong quantitative evidence indicates that an observed y'-supersaturation of Al results from the Gibbs-Thomson effect, providing the first experimental verification of this phenomenon. The Gibbs-Thomson relationship, for a ternary system, as well as differences in measured phase equilibria with CALPHAD assessments, are considered in great detail.

Sudbrack, Chantal K.↗
NASA NTRS2006

Temporal Evolution of the Nanostructure and Phase Compositions in a Model Ni-Al-Cr Alloy

In a Ni-5.2 Al-14.2 Cr at.% alloy with moderate solute supersaturations and a very small gamma/gamma prime lattice parameter misfit, the nanostructural and compositional pathways during gamma prime(L12) precipitation at 873 K are investigated using atom-probe tomography, conventional transmission electron microscopy, and hardness measurements. Nucleation of high number densities (N(sub v) greater than 10(sup 23) per cubic meters) of solute-rich precipitates (mean radius = [R] = 0.75 nm), with a critical nucleus composition of Ni-18.3 plus or minus 0.9 Al-9.3 plus or minus 0.7 Cr at.%, initiates between 0.0833 and 0.167 h. With increasing aging time (a) the solute concentrations decay in spheroidal precipitates ([R] less than 10 nm); (b) the observed early-stage coalescence peaks at maximum N(sub v) in coincidence with the smallest interprecipitate spacing; and (c) the reaction enters a quasi-stationary regime where growth and coarsening operate concomitantly. During this quasi-stationary regime, the c (face-centered cubic)-matrix solute supersaturations decay with a power-law dependence of about -1/3, while the dependencies of [R] and N(sub v) are 0.29 plus or minus 0.05 and -0.64 plus or minus 0.06 at a coarsening rate slower than model predications. Coarsening models allow both equilibrium phase compositions to be determined from the compositional measurements. The observed early-stage coalescence is discussed in further detail.

Sudbrack, Chantal K.↗
NASA NTRS2006

Use of In Situ Cloud Condensation Nuclei, Extinction, and Aerosol Size Distribution Measurements to Test a Method for Retrieving Cloud Condensation Nuclei Profiles From Surface Measurements

If the aerosol composition and size distribution below cloud are uniform, the vertical profile of cloud condensation nuclei (CCN) concentration can be retrieved entirely from surface measurements of CCN concentration and particle humidification function and surface-based retrievals of relative humidity and aerosol extinction or backscatter. This provides the potential for long-term measurements of CCN concentrations near cloud base. We have used a combination of aircraft, surface in situ, and surface remote sensing measurements to test various aspects of the retrieval scheme. Our analysis leads us to the following conclusions. The retrieval works better for supersaturations of 0.1% than for 1% because CCN concentrations at 0.1% are controlled by the same particles that control extinction and backscatter. If in situ measurements of extinction are used, the retrieval explains a majority of the CCN variance at high supersaturation for at least two and perhaps five of the eight flights examined. The retrieval of the vertical profile of the humidification factor is not the major limitation of the CCN retrieval scheme. Vertical structure in the aerosol size distribution and composition is the dominant source of error in the CCN retrieval, but this vertical structure is difficult to measure from remote sensing at visible wavelengths.

Ghan, Stephen J.↗
NASA NTRS2008

Use of Potassium Citrate to Reduce the Risk of Renal Stone Formation During Spaceflight

Introduction: NASA s Vision for Space Exploration centers on exploration class missions including the goals of returning to the moon and landing on Mars. One of NASA s objectives is to focus research on astronaut health and the development of countermeasures that will protect crewmembers during long duration voyages. Exposure to microgravity affects human physiology and results in changes in the urinary chemical composition favoring urinary supersaturation and an increased risk of stone formation. Nephrolithiasis is a multifactorial disease and development of a renal stone is significantly influenced by both dietary and environmental factors. Previous results from long duration Mir and short duration Shuttle missions have shown decreased urine volume, pH, and citrate levels and increased calcium. Citrate, an important inhibitor of calcium-containing stones, binds with urinary calcium reducing the amount of calcium available to form stones. Citrate inhibits renal stone recurrence by preventing crystal growth, aggregation, and nucleation and is one of the most common therapeutic agents used to prevent stone formation. Methods: Thirty long duration crewmembers (29 male, 1 female) participated in this study. 24-hour urines were collected and dietary monitoring was performed pre, in, and postflight. Crewmembers in the treatment group received two potassium citrate (KCIT) pills, 10 mEq/pill, ingested daily beginning 3 days before launch, all inflight days and through 14 days postflight. Urinary biochemical and dietary analyses were completed. Results: KCIT treated subjects exhibited decreased urinary calcium excretion and maintained the levels of calcium oxalate supersaturation risk at their preflight levels. The increased urinary pH levels in these subjects reduced the risk of uric acid stones. Discussion: The current study investigated the use of potassium citrate as a countermeasure to minimize the risk of stone formation during ISS missions. Results suggest that supplementation with potassium citrate decreases the risk of stone formation during and immediately after spaceflight.

Whitson, P. A.↗
NASA NTRS2009

Renal Stone Risk during Spaceflight: Assessment and Countermeasure Validation

NASA's Vision for Space Exploration centers on exploration class missions including the goals of returning to the moon and landing on Mars. One of NASA's objectives is to focus research on astronaut health and the development of countermeasures that will protect crewmembers during long duration voyages. Exposure to microgravity affects human physiology and results in changes in the urinary chemical composition favoring urinary supersaturation and an increased risk of stone formation. Nephrolithiasis is a multifactorial disease and development of a renal stone is significantly influenced by both dietary and environmental factors. Previous results from long duration Mir and short duration Shuttle missions have shown decreased urine volume, pH, and citrate levels and increased calcium. Citrate, an important inhibitor of calcium-containing stones, binds with urinary calcium reducing the amount of calcium available to form stones. Citrate inhibits renal stone recurrence by preventing crystal growth, aggregation, and nucleation and is one of the most common therapeutic agents used to prevent stone formation. Methods: Thirty long duration crewmembers (29 male, 1 female) participated in this study. 24-hour urines were collected and dietary monitoring was performed pre-, in-, and postflight. Crewmembers in the treatment group received two potassium citrate (KCIT) pills, 10 mEq/pill, ingested daily beginning 3 days before launch, all in-flight days and through 14 days postflight. Urinary biochemical and dietary analyses were completed. Results: KCIT treated subjects exhibited decreased urinary calcium excretion and maintained the levels of calcium oxalate supersaturation risk at their preflight levels. The increased urinary pH levels in these subjects reduced the risk of uric acid stones. Discussion: The current study investigated the use of potassium citrate as a countermeasure to minimize the risk of stone formation during ISS missions. Results suggest that supplementation with potassium citrate decreases the risk of stone formation during and immediately after spaceflight.

Whitson, Peggy A.↗
NASA NTRS2010

Ice Crystal Growth Rates Under Upper Troposphere Conditions

Atmospheric conditions for growth of ice crystals (temperature and ice supersaturation) are often not well constrained and it is necessary to simulate such conditions in the laboratory to investigate such growth under well controlled conditions over many hours. The growth of ice crystals from the vapour in both prism and basal planes was observed at temperatures of -60 C and -70 C under ice supersaturation up to 100% (200% relative humidity) at pressures derived from the standard atmosphere in a static diffusion chamber. Crystals grew outward from a vertical glass filament, thickening in the basal plane by addition of macroscopic layers greater than 2 m, leading to growth in the prism plane by passing of successive layers conveniently viewed by time lapse video.

Peterson, Harold S.↗
NASA NTRS2010

Ice Particle Growth Under Conditions of the Upper Troposphere

Atmospheric conditions for growth of ice crystals (temperature and ice supersaturation) are often not well constrained and it is necessary to simulate such conditions in the laboratory to investigate such growth under well controlled conditions over many hours. The growth of ice crystals from the vapour in both prism and basal planes was observed at temperatures of -60 C and -70 C under ice supersaturation up to 100% (200% relative humidity) at pressures derived from the standard atmosphere in a static diffusion chamber. Crystals grew outward from a vertical glass filament, thickening in the basal plane by addition of macroscopic layers greater than 2 microns, leading to growth in the prism plane by passing of successive layers conveniently viewed by time lapse video.

Peterson, Harold S.↗
NASA NTRS2010

Ice Particle Growth Rates Under Upper Troposphere Conditions

Atmospheric conditions for growth of ice crystals (temperature and ice supersaturation) are often not well constrained and it is necessary to simulate such conditions in the laboratory to investigate such growth under well controlled conditions over many hours. The growth of ice crystals from the vapour in both prism and basal planes was observed at temperatures of -60 C and -70 C under ice supersaturation up to 100% (200% relative humidity) at pressures derived from the standard atmosphere in a static diffusion chamber. Crystals grew outward from a vertical glass filament, thickening in the basal plane by addition of macroscopic layers greater than 2 m, leading to growth in the prism plane by passing of successive layers conveniently viewed by time lapse video.

Peterson, Harold↗
NASA NTRS2011

Crystalline Silicates in Comets: Modeling Irregularly-Shaped Forsterite Crystals and Its Implications on Condensation Conditions

Crystalline silicates in comets are a product of the condensation in the hot inner regions (T > or approx. equals 1400 K [1]) of our proto-planetary disk or annealing at somewhat lower temperatures (T > or approx. equals 1000-1200 K) [2, 3, 4] in shocks coupled with disk evolutionary processes that include radial transport of crystals from their formation locations out to the cold outer regions where comet nuclei formed. The grain shape of forsterite (crystals) could be indicative of their formation pathways at high temperatures through vapor-solid condensation or at lower temperatures through vapor-liquid-solid formation and growth [5, 6, 7]. Experiments demonstrate that crystals that formed from a rapidly cooled highly supersaturated silicate vapor are characterized by bulky, platy, columnar/needle and droplet shapes for values of temperature and supersaturation, T and sigma, of 1000-1450 C and < 97, 700-1000 C and 97-161, 580-820 C and 131-230, and <500 C and > 230, respectively [7]. The experimental columnar/needle shapes, which form by vapor-liquid-solid at lower temperatures (<820 C), are extended stacks of plates, where the extension is not correlated with an axial direction: columnar/needles may be extended in the c-axis or a-axis direction, can change directions, and/or are off-kilter or a bit askew extending in a combination of the a- and c-axis direction.

Wooden, Diane H.↗
NASA NTRS2012

Role of Transport and Kinetics in Growth of Renal Stones

Renal stone disease is not only a concern on earth but could conceivably pose as a serious risk to the astronauts health and safety in Space. In this paper, a combined transport-kinetics model for growth of calcium oxalate crystals is presented. The model is used to parametrically investigate the growth of renal calculi in urine with a focus on the coupled effects of transport and surface reaction on the ionic concentrations at the surface of the crystal and their impact on the resulting growth rates. It is shown that under nominal conditions of low solution supersaturation and low Damkohler number that typically exist on Earth, the surface concentrations of calcium and oxalate approach their bulk solution values in the urine and the growth rate is most likely limited by the surface reaction kinetics. But for higher solution supersaturations and larger Damkohler numbers that may be prevalent in the microgravity environment of Space, the calcium and oxalate surface concentrations tend to shift more towards their equilibrium or saturation values and thus the growth process may be limited by the transport through the medium. Furthermore, parametric numerical studies suggest that changes to the renal biochemistry of astronauts due in space may promote development of renal calculi during long duration space expeditions.

Kassemi, Mohammad↗
NASA NTRS2012

On the Ice Nucleation Spectrum

This work presents a novel formulation of the ice nucleation spectrum, i.e. the function relating the ice crystal concentration to cloud formation conditions and aerosol properties. The new formulation is physically-based and explicitly accounts for the dependency of the ice crystal concentration on temperature, supersaturation, cooling rate, and particle size, surface area and composition. This is achieved by introducing the concepts of ice nucleation coefficient (the number of ice germs present in a particle) and nucleation probability dispersion function (the distribution of ice nucleation coefficients within the aerosol population). The new formulation is used to generate ice nucleation parameterizations for the homogeneous freezing of cloud droplets and the heterogeneous deposition ice nucleation on dust and soot ice nuclei. For homogeneous freezing, it was found that by increasing the dispersion in the droplet volume distribution the fraction of supercooled droplets in the population increases. For heterogeneous ice nucleation the new formulation consistently describes singular and stochastic behavior within a single framework. Using a fundamentally stochastic approach, both cooling rate independence and constancy of the ice nucleation fraction over time, features typically associated with singular behavior, were reproduced. Analysis of the temporal dependency of the ice nucleation spectrum suggested that experimental methods that measure the ice nucleation fraction over few seconds would tend to underestimate the ice nuclei concentration. It is shown that inferring the aerosol heterogeneous ice nucleation properties from measurements of the onset supersaturation and temperature may carry significant error as the variability in ice nucleation properties within the aerosol population is not accounted for. This work provides a simple and rigorous ice nucleation framework where theoretical predictions, laboratory measurements and field campaign data can be reconciled, and that is suitable for application in atmospheric modeling studies.

Barahona, D.↗
NASA NTRS2013

Ice Nucleation and Dehydration in the Tropical Tropopause Layer

Optically thin cirrus near the tropical tropopause regulate the humidity of air entering the stratosphere, which in turn has a strong influence on the Earth's radiation budget and climate. Recent highaltitude, unmanned aircraft measurements provide evidence for two distinct classes of cirrus formed in the tropical tropopause region: (i) vertically extensive cirrus with low ice number concentrations, low extinctions, and large supersaturations (up to approx. 70%) with respect to ice; and (ii) vertically thin cirrus layers with much higher ice concentrations that effectively deplete the vapor in excess of saturation. The persistent supersaturation in the former class of cirrus is consistent with the long time-scales (several hours or longer) for quenching of vapor in excess of saturation given the low ice concentrations and cold tropical tropopause temperatures. The low-concentration clouds are likely formed on a background population of insoluble particles with concentrations less than 100 L−1 (often less than 20 L−1), whereas the high ice concentration layers (with concentrations up to 10,000 L−1) can only be produced by homogeneous freezing of an abundant population of aqueous aerosols. These measurements, along with past high-altitude aircraft measurements, indicate that the low-concentration cirrus occur frequently in the tropical tropopause region, whereas the high-concentration cirrus occur infrequently. The predominance of the low-concentration clouds means cirrus near the tropical tropopause may typically allow entry of air into the stratosphere with as much as approx. 1.7 times the ice saturation mixing ratio.

dehydration↗
NASA NTRS2013

Development of Two-Moment Cloud Microphysics for Liquid and Ice Within the NASA Goddard Earth Observing System Model (GEOS-5)

This work presents the development of a two-moment cloud microphysics scheme within the version 5 of the NASA Goddard Earth Observing System (GEOS-5). The scheme includes the implementation of a comprehensive stratiform microphysics module, a new cloud coverage scheme that allows ice supersaturation and a new microphysics module embedded within the moist convection parameterization of GEOS-5. Comprehensive physically-based descriptions of ice nucleation, including homogeneous and heterogeneous freezing, and liquid droplet activation are implemented to describe the formation of cloud particles in stratiform clouds and convective cumulus. The effect of preexisting ice crystals on the formation of cirrus clouds is also accounted for. A new parameterization of the subgrid scale vertical velocity distribution accounting for turbulence and gravity wave motion is developed. The implementation of the new microphysics significantly improves the representation of liquid water and ice in GEOS-5. Evaluation of the model shows agreement of the simulated droplet and ice crystal effective and volumetric radius with satellite retrievals and in situ observations. The simulated global distribution of supersaturation is also in agreement with observations. It was found that when using the new microphysics the fraction of condensate that remains as liquid follows a sigmoidal increase with temperature which differs from the linear increase assumed in most models and is in better agreement with available observations. The performance of the new microphysics in reproducing the observed total cloud fraction, longwave and shortwave cloud forcing, and total precipitation is similar to the operational version of GEOS-5 and in agreement with satellite retrievals. However the new microphysics tends to underestimate the coverage of persistent low level stratocumulus. Sensitivity studies showed that the simulated cloud properties are robust to moderate variation in cloud microphysical parameters. However significant sensitivity in ice cloud properties was found to variation in the dispersion of the ice crystal size distribution and the critical size for ice autoconversion. The implementation of the new microphysics leads to a more realistic representation of cloud processes in GEOS-5 and allows the linkage of cloud properties to aerosol emissions.

Aerosol-Cloud Interactions↗