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At least 73 records · Page 4

Modeling Tetragonal Lysozyme Crystal Growth Rates

Tetragonal lysozyme 110 face crystal growth rates, measured over 5 orders of magnitude in range, can be described using a model where growth occurs by 2D nucleation on the crystal surface for solution supersaturations of c/c(sub eq) less than or equal to 7 +/- 2. Based upon the model, the step energy per unit length, beta was estimated to be approx. 5.3 +/- 0.4 x 10(exp -7) erg/mol-cm, which for a step height of 56 A corresponds to barrier of approx. 7 +/- 1 k(sub B)T at 300 K. For supersaturations of c/c(sub eq) > 8, the model emphasizing crystal growth by 2D nucleation not only could not predict, but also consistently overestimated, the highest observable crystal growth rates. Kinetic roughening is hypothesized to occur at a cross-over supersaturation of c/c(sub eq) > 8, where crystal growth is postulated to occur by a different process such as adsorption. Under this assumption, all growth rate data indicated that a kinetic roughening transition and subsequent crystal growth by adsorption for all solution conditions, varying in buffer pH, temperature and precipitant concentration, occurs for c/c(sub eq)(T, pH, NaCl) in the range between 5 and 10, with an energy barrier for adsorption estimated to be approx. 20 k(sub B)T at 300 K. Based upon these and other estimates, we determined the size of the critical surface nucleate, at the crossover supersaturation and higher concentrations, to range from 4 to 10 molecules.

Gorti, Sridhar↗

Kinetic Roughening and Energetics of Tetragonal Lysozyme Crystal Growth: A Preliminary Atomic Force Microscopy Investigation

We examined particulars of crystal growth from measurements obtained at both microscopic and molecular levels. The crystal growth measurements performed at the microscopic level are well characterized by a model that balances the flux of macromolecules towards the crystal surface with the flux of the crystal surface. Numerical evaluation of model with measurements of crystal growth, in time, provided accurate estimates for the average growth velocities. Growth velocities thus obtained were also interpreted using well-established phenomenological theories. Moreover, we find that microscopic measurements of growth velocity measurements obtained as a function of temperature best characterizes changes in crystal growth modes, when present. We also examined the possibility of detecting a change in crystal growth modes at the molecular level using atomic force microscopy, AFM. From preliminary AFM measurements performed at various supersaturations, we find that magnitude of surface height fluctuations, h(x), increases with supersaturation. Further examination of surface height fluctuations using methods established for fluctuation spectroscopy also enabled the discovery of the existence of a characteristic length, c, which may possibly determine the mode of crystal growth. Although the results are preliminary, we establish the non- critical divergence of 5 and the root-mean-square (rms) magnitude of height-height fluctuations as the kinetic roughening transition temperatures are approached. Moreover, we also examine approximate models for interpreting the non-critical behavior of both 6 and rms magnitude of height-height fluctuations, as the solution supersaturation is increased towards the kinetic roughening supersaturation.

Gorti, Sridhar↗

Measurements of upper troposheric humidity at low temperatures during CRYSTAL-FACE

Aircraft condensation trails (contrails) and thin cirrus were studied by instruments on the NASA WB-57F high-altitude aircraft during contrails and optically thing cirrus are contrasted by different levels of supersaturation with respect to ice. During the July 13, 2002, flight of the WB-57F aircraft intercepted visible contrails produced by both the WB-57F and ER-2 aircraft. These contrails were located immediately below the local tropopause, where ambient temperatures were very low (-76 degree C). The contrails were clearly indicated by an abrupt increase in NO and a simultaneous, abrupt decrease in ice supersaturation. With in the contrail, the relative humidity was close to 130% with respect to ice, higher than expected from theory. Outside the contrails was a persistent layer of subvisible currus extending from approximately 13 to 15 km altitude. This layer was characterized y significant supersaturations because the ambient concentrations of ice particles were insufficient to significantly deplete the ice supersaturation. We will discuss in situ measurements and models simulations of humidity.

water vapor↗

Vertical profiles of condensation nuclei

Condensation nuclei measurements using a low supersaturation (about 10%) thermal gradient diffusion cloud chamber (TGDCC) and a high supersaturation (about 200%) expansion type instrument were compared on a series of three balloon flights over Laramie, Wyoming. In general, the two instruments produced similar vertical profiles but some discrepancies remain unexplained. Agreement between the two would indicate that the low supersaturations used in the TGDCC were still large enough to cause the instrument to count essentially all of the particles present. The TGDCC condensation nuclei (CN) counter was flown at several sites in both the Northern and Southern Hemispheres. The results indicate the existence of a relative maximum in the CN mixing ratio associated with the upper equatorial troposphere and what appears to be a worldwide constant mixing ratio of CN above 20-25 km.

Rosen, J. M.↗

Ice crystal growth in a dynamic thermal diffusion chamber

Ice crystals were grown in a supersaturated environment produced by a dynamic thermal diffusion chamber, which employed two horizontal plates separated by a distance of 2.5 cm. Air was circulated between and along the 1.2 m length of the plates past ice crystals which nucleated and grew from a fiber suspended vertically between the two plates. A zoom stereo microscope with a magnification which ranged from 3X to 80X and both 35 mm still photographs and 16 mm time lapse cine films taken through the microscope were used to study the variation of the shape and linear growth rate of ice crystals as a function of the ambient temperature, the ambient supersaturation, and the forced ventilation velocity. The ambient growth conditions were varied over the range of temperature 0 to -40 C, over the range of supersaturation 4% to 50% with respect to ice, and over the range of forced ventilation velocities 0 cm/s to 20 cm/s.

Keller, V. W.↗

Convection phenomena during the growth of sodium chlorate crystals from solution

The paper examines convection phenomena during the growth of sodium chlorate crystals from solution. Schlieren observations of sodium chlorate crystals suspended in supersaturated solutions showed that with increase in supersaturation or crystal size, the boundary layer on the side faces was stable while the top boundary layer and emerging plume changed from stable to partially oscillatory. The transition was a function of the Grashof number, Gr sub top, and the crystal height. Gr sub top correlated with plume width, number of streamlines, eddy density, and plume velocity, but the oscillation period correlated with the weight increase growth rate. The mass transfer rate, the linear growth rate, and growth of vertical and horizontal faces are discussed, and an estimate of boundary layer flow vs growth rate for near-critical stable convection indicated that growth of side faces depleted over half of the excess solute in the boundary layer. Impulse energies greatly in excess of the threshold value caused transient separation of the boundary layer on the top face, and plume wavering due to background-induced fluid motion was observed only at the lowest supersaturations.

Chen, P. S.↗

Diffusion tube

The diffusion tube was designed to operate below about 0.25 percent of water supersaturation. It is simply a long tube lined on the inside with a damp chamois cloth, and heated isothermally to a few degrees centigrade above the incoming air. The diffusion coefficient for water vapor is slightly larger than that for heat, making it possible to supersaturate the airflow. This is the same principle by which transient supersaturations may occur in parallel plate cloud chambers. Only the diffusion of vapor and heat from the walls into the moving air are considered.

Leaitch, R.↗

Review of isothermal haze chamber performance

The theory of this method of characterizing cloud condensation nuclei (CCN) over the critical supersaturation range of about 0.01% to 0.2% was reviewed, and guidelines for the design and operation of IHC's are given. IHC data are presented and critically analyzed. Two of the four IHC's agree to about 40% over the entire range of critical. a third chamber shows similar agreement with the first two over the lower part of the critical supersaturation range but only a factor of two agreement at higher supersaturation. Some reasons for the discrepancies are given.

Fitzgerald, J. W.↗

An experimental study of the ice column habit transitions

The influence of supersaturation on column growth of ice crystals forming from atmospheric water vapor was investigated. A high density of crystals was generated on a glass fiber cooled by liquid N2 in a thermal diffusion chamber. Attention was focused on a neighbor-free hollow prism during a stepwise decrease in supersaturation while the crystal temperature was maintained constant. Another experiment involved epitaxial growth of ice crystals on CuS, where nonthickening crystals could only be grown below -7 C. A critical supersaturation was found to be necessary for growth of the basal plane. Beyound the critical value, surface kinetics do not control the growth rate, which is then dominated by the penetration of water molecules through the diffusion field surrounding the crystal.

Cho, N.↗

Theory of Ostwald ripening in a two-component system

When a two-component system is cooled below the minimum temperature for its stability, it separates into two or more immiscible phases. The initial nucleation produces grains (if solid) or droplets (if liquid) of one of the phases dispersed in the other. The dynamics by which these nuclei proceed toward equilibrium is called Ostwald ripening. The dynamics of growth of the droplets depends upon the following factors: (1) The solubility of the droplet depends upon its radius and the interfacial energy between it and the surrounding (continuous) phase. There is a critical radius determined by the supersaturation in the continuous phase. Droplets with radii smaller than critical dissolve, while droplets with radii larger grow. (2) The droplets concentrate one component and reject the other. The rate at which this occurs is assumed to be determined by the interdiffusion of the two components in the continuous phase. (3) The Ostwald ripening is constrained by conservation of mass; e.g., the amount of materials in the droplet phase plus the remaining supersaturation in the continuous phase must equal the supersaturation available at the start. (4) There is a distribution of droplet sizes associated with a mean droplet radius, which grows continuously with time. This distribution function satisfies a continuity equation, which is solved asymptotically by a similarity transformation method.

Baird, J. K.↗

Microgravity nucleation and particle coagulation experiments support

A hollow sphere model is developed to predict the range of supersaturation ratio values for refractory metal vapors in a proposed experimental nucleation apparatus. Since the experiments are to be carried out in a microgravity environment, the model neglects the effects of convection and assumes that the only transfer of vapors through an inert gas atmosphere is by conduction and molecular diffusion. A consistent set of physical properties data is assembled for the various candidate metals and inert ambient gases expected to be used in the nucleation experiments. Transient partial pressure profiles are computed for the diffusing refractory species for two possible temperature distributions. The supersaturation ratio values from both candidate temperature profiles are compared with previously obtained experimetnal data on a silver-hydrogen system. The model is used to simulate the diffusion of magnesium vapor through argon and other inert gas atmospheres over ranges of initial and boundary conditions. These results identify different combinations of design and operating parameters which are liekly to produce supersaturation ratio values high enough to induce homogeneous nucleation in the apparatus being designed for the microgravity nucleation experiments.

Lilleleht, L. U.↗

Growth rate study of canavalin single crystals

The dependence on supersaturation of the growth rate of single crystals of the protein canavalin is studied. In the supersaturation ranges studied, the rate-limiting step for growth is best described by a screw dislocation mechanism associated with interface attachment kinetics. Using a ln-ln plot, the growth-rate data is found to fit a predictive relationship of the form G = 0.012 x the supersaturation to the 6.66, which, together with the solubility curves, allows the growth rate to be estimated under a variety of conditions.

Demattei, R. C.↗

Mesoscale simulations of the November 25-26 and December 5-6 cirrus cases using the RAMS model

The Regional Atmospheric Modeling System (RAMS), developed at Colorado State University, was used during the First ISCCP (International Satellite Cloud Climatology Project) Regional Experiment (FIRE) 2 (13 Nov. through 6 Dec. 1991) to provide real time forecasts of cirrus clouds. Forecasts were run once a day, initializing with the 0000 UTC dataset provided by NOAA (Forecast Systems Laboratory (FSL) Mesoscale Analysis and Prediction System (MAPS)). In order to obtain better agreement with observations, a second set of simulations were done for the FIRE 2 cases that occurred on 25-26 Nov. and 5-6 Dec. In this set of simulations, a more complex radiation scheme was used, the Chen/Cotton radiation scheme, along with the nucleation of ice occurring at ice supersaturations as opposed to nucleation occurring at water supersaturations that was done in the actual forecast version. The runs using these more complex schemes took longer wall clock time (7-9 hours for the actual forecasts as compared to 12-14 hrs for the runs using the more complex schemes) however, the final results of the simulations were definitely improved upon. Comparisons between these two sets of simulations are given. Now underway are simulations of these cases using a closed analytical solution for the auto-conversion of ice from a pristine ice class (sizes less than about 50 microns in effective diameter) to a snow class (effective diameters on the order of several hundred microns). This solution is employed along with a new scheme for the nucleation of ice crystals due to Meyers et al and Demott et al. The scheme is derived assuming complete gamma distributions for both the pristine and snow classes. The time rate of change of the number concentration and mass mixing-ratio of each distribution is found by calculating either the flux of crystals that grow beyond a certain critical diameter by vapor deposition in an ice supersaturated regime or by calculating the flux of crystals that evaporate to sizes below that same critical effective diameter.

Harrington, J. L.↗

Nucleation and growth of crystals under cirrus and polar stratospheric cloud conditions

Laboratory studies examine phase changes of hygroscopic substances which occur as aerosol in stratosphere and troposphere (sodium chloride, ammonium sulfate, ammonium bisulfate, nitric acid, sulfuric acid), under controlled conditions, in samples volume 1 to 10(exp -4) ml. Crystallization of salts from supersaturated solutions is examined by slowly evaporating a solution drop on a substrate, under controlled relative humidity, until self nucleation occurs; controlled nucleation of ice in a mm capillary U-tube gives a measured ice crystallization velocity at known supercooling. Two states of crystallization occur for regions where hydrates exist. It is inferred that all of the materials readily exist as supersaturated/supercooled solutions; the degree of metastability appears to be slightly enhanced by inclusion of aircraft produced soot. The crystallization velocity is taken as a measure of viscosity. Results suggest an approach to a glass transition at high molality, supersaturation and/or supercooling within the range of atmospheric interest. It is hypothesized that surface reactions occur more readily on solidified particles - either crystalline or glass, whereas volume reactions are more important on droplets with sufficiently low viscosity and volume diffusivity. Implications are examined for optical properties of such particles in the atmosphere. In a separate experiment, crystal growth was examined in a modified thermal vapor diffusion chamber over the range of cirrus temperature (-30 to -70 C) and under controlled supersaturation and air pressure. The crystals grew at a velocity of 1-2 microns/s, thickness 60-70 micron, in the form of thin column crystals. Design criteria are given for a system to investigate particle growth down to -100 C, (PSC temperatures) where nitric acid particles can be grown under similar control and in the form of hydrate crystals.

Hallett, John↗

Grain formation around carbon stars. 1: Stationary outflow models

Asymptotic giant branch (AGB) stars are known to be sites of dust formation and undergo significant mass loss. The outflow is believed to be driven by radiation pressure on grains and momentum coupling between the grains and gas. While the physics of shell dynamics and grain formation are closely coupled, most previous models of circumstellar shells have treated the problem separately. Studies of shell dynamics typically assume the existence of grains needed to drive the outflow, while most grain formation models assume a constant veolcity wind in which grains form. Furthermore, models of grain formation have relied primarily on classical nucleation theory instead of using a more realistic approach based on chemical kinetics. To model grain formation in carbon-rich AGB stars, we have coupled the kinetic equations governing small cluster growth to moment equations which determine the growth of large particles. Phenomenological models assuming stationary outflow are presented to demonstrate the differences between the classical nucleation approach and the kinetic equation method. It is found that classical nucleation theory predicts nucleation at a lower supersaturation ratio than is predicted by the kinetic equations, resulting in significant differences in grain properties. Coagulation of clusters larger than monomers is unimportant for grain formation in high mass-loss models but becomes more important to grain growth in low mass-loss situations. The properties of the dust grains are altered considerably if differential drift velocities are ignored in modeling grain formation. The effect of stellar temperature, stellar luminosity, and different outflow velocities are investigated. The models indicate that changing the stellar temperature while keeping the stellar luminosity constant has little effect on the physical parameters of the dust shell formed. Increasing the stellar luminosity while keeping the stellar temperature constant results in large differences in grain properties. For small outflow velocities, grains form at lower supersaturation ratios and close to the stellar photosphere, resulting in larger but fewer grains. The reverse is true when grains form under high outflow velocities, i.e., they form at higher supersaturation ratios, farther from the star, and are much smaller but at larger quantities.

Egan, Michael P.↗

Solute Nucleation and Growth in Supercritical Fluid Mixtures

This research effort is directed toward two primary scientific objectives: (1) to determine the gravitational effect on the measurement of nucleation and growth rates near a critical point and (2) to investigate the nucleation process in supercritical fluids to aid in the evaluation and development of existing theoretical models and practical applications. A nucleation pulse method will be employed for this investigation using a rapid expansion to a supersaturated state that is maintained for approximately 1 ms followed by a rapid recompression to a less supersaturated state that effectively terminates nucleation while permitting growth to continue. Nucleation, which occurs during the initial supersaturated state, is decoupled from growth by producing rapid pressure changes. Thermodynamic analysis, condensation modeling, apparatus design, and optical diagnostic design necessary for the initiation of a theoretical and experimental investigation of naphthalene nucleation from supercritical CO2 have been completed.

Smedley, Gregory T.↗

Analysis of Ice Nucleating Aerosol Measurements during SUCCESS: April, May 1996

This section describes our research activities during year three of this effort. In the second year, preliminary archive data sets were submitted to the SUCCESS archive. After additional analyses, final versions were prepared and submitted. These are included on the SUCCESS CD-ROM data editions that were recently released by NASA Ames. Over the range of temperature and supersaturation conditions of our measurements (15 to -40 C, and from ice saturation to approximately 15% water supersaturation), IN concentrations ranged from less than 0.1 to approximately 500 per liter, being generally greater at colder temperatures and higher supersaturations. To estimate the potential of aircraft exhaust as a source of IN, we examined data from six days of the field project when the DC-8 was following closely behind other humidity conditions of our measurements. In April 1997, a microphysical workshop was convened at NCAR to select cases for in depth analyses and to address questions about the consistency of cloud ice crystal measurements (size distributions and mass concentrations) and aerosol size distributions. We attended this meeting and contributed to the discussions. A particular concern was identified in the CN measurements. On the DC-8, CN measurements were obtained by four different investigator groups, using commercially available instrumentation. The DC-8 SUCCESS CN data showed long periods where the measurements were in substantial agreement, but there were also periods with large discrepancies. Several possible factors were identified that could help explain these discrepancies, including minimum detectable particle size, response at reduced pressures, and location of sample inlet on the aircraft.

Rogers, D. C.↗

Characterization of Aircraft Produced Soot and Contrails Near the Tropopause

Participation in the SUCCESS project primarily involved development and deployment of specific instruments for characterizing jet aircraft exhaust emissions as particulates and their subsequent evolution as contrail particles, either liquid or solid, as cirrus. Observations can be conveniently considered in two categories - close or distant from the aircraft. Thus close to the aircraft the exhaust is mixing through the engine turbulence with a much drier and colder environment and developing water/ ice supersaturation along the trail depending on circumstances (near field), whereas distant from the aircraft (far field) the exhaust has cooled essentially to ambient temperature, the turbulence has decayed and any particle growth or evaporation is controlled by the prevailing ambient conditions. Intermediate between these two regions the main aircraft vortices form (one on each side of the aircraft) which tend to inhibit mixing under some conditions, a region extending from a few aircraft lengths to sometimes a hundred times this distance. Our approach to the problem lay in experience gained in characterizing the smoke from hydrocarbon combustion in terms of its cloud forming properties and its potential influence on the radiation properties of the smoke and subsequent cloud from the viewpoint of reduction (absorbtion and scattering ) of solar radiation flux leading to significant global cooling (Hudson et al 1991; Hallett and Hudson 1991). Engine exhaust contains a much smaller proportion of the fuel carbon than is sometimes present in ordinary combustion (less than 0.01% compared with 10%) and influences condensation in quite different ways, to be characterized by the Cloud Condensation Nucleus, CCN - supersaturation spectrum. The transition to ice is to be related to the dilution of solution droplets to freeze by homogeneous nucleation at temperatures somewhat below -40C (Pueschel et al 1998). The subsequent growth of ice particles depends critically on temperature, supersaturation and to some extent pressure, as is demonstrated in an NSF funded project being carried out in parallel with the work reported here. As will be discussed below, nucleation processes themselves and also exhaust impurities also influence the growth of ice particles and may control some aspects of growth of ice in contrails. Instrumentation was designed to give insight into these questions and to be flown on the NASA DC- 8 as a platform. In addition a modest program was undertaken to investigate the properties of laboratory produced smoke produced under controlled conditions from the viewpoint of forming both CCN and CN. The composition of the smoke could inferred from a thermal characterization technique; larger particles were captured by formvar replicator for detailed analysis; ice particles were captured and evaporated in flight on a new instrument, the cloudscope, to give their mass, density and impurity content.

Hallett, John↗