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Sample records for nucleation heterogeneous multicomponent

  1. Heterogeneous nucleation or homogeneous nucleation?

    NASA Astrophysics Data System (ADS)

    Liu, X. Y.

    2000-06-01

    The generic heterogeneous effect of foreign particles on three dimensional nucleation was examined both theoretically and experimentally. It shows that the nucleation observed under normal conditions includes a sequence of progressive heterogeneous processes, characterized by different interfacial correlation function f(m,x)s. At low supersaturations, nucleation will be controlled by the process with a small interfacial correlation function f(m,x), which results from a strong interaction and good structural match between the foreign bodies and the crystallizing phase. At high supersaturations, nucleation on foreign particles having a weak interaction and poor structural match with the crystallizing phase (f(m,x)→1) will govern the kinetics. This frequently leads to the false identification of homogeneous nucleation. Genuine homogeneous nucleation, which is the up-limit of heterogeneous nucleation, may not be easily achievable under gravity. In order to check these results, the prediction is confronted with nucleation experiments of some organic and inorganic crystals. The results are in excellent agreement with the theory.

  2. Heterogeneous nucleation in multi-component vapor on a partially wettable charged conducting particle. II. The generalized Laplace, Gibbs-Kelvin, and Young equations and application to nucleation

    NASA Astrophysics Data System (ADS)

    Noppel, M.; Vehkamäki, H.; Winkler, P. M.; Kulmala, M.; Wagner, P. E.

    2013-10-01

    Based on the results of a previous paper [M. Noppel, H. Vehkamäki, P. M. Winkler, M. Kulmala, and P. E. Wagner, J. Chem. Phys. 139, 134107 (2013)], we derive a thermodynamically consistent expression for reversible or minimal work needed to form a dielectric liquid nucleus of a new phase on a charged insoluble conducting sphere within a uniform macroscopic one- or multicomponent mother phase. The currently available model for ion-induced nucleation assumes complete spherical symmetry of the system, implying that the seed ion is immediately surrounded by the condensing liquid from all sides. We take a step further and treat more realistic geometries, where a cap-shaped liquid cluster forms on the surface of the seed particle. We derive the equilibrium conditions for such a cluster. The equalities of chemical potentials of each species between the nucleus and the vapor represent the conditions of chemical equilibrium. The generalized Young equation that relates contact angle with surface tensions, surface excess polarizations, and line tension, also containing the electrical contribution from triple line excess polarization, expresses the condition of thermodynamic equilibrium at three-phase contact line. The generalized Laplace equation gives the condition of mechanical equilibrium at vapor-liquid dividing surface: it relates generalized pressures in neighboring bulk phases at an interface with surface tension, excess surface polarization, and dielectric displacements in neighboring phases with two principal radii of surface curvature and curvatures of equipotential surfaces in neighboring phases at that point. We also re-express the generalized Laplace equation as a partial differential equation, which, along with electrostatic Laplace equations for bulk phases, determines the shape of a nucleus. We derive expressions that are suitable for calculations of the size and composition of a critical nucleus (generalized version of the classical Kelvin-Thomson equation).

  3. Multicomponent dynamical nucleation theory and sensitivity analysis.

    PubMed

    Kathmann, Shawn M; Schenter, Gregory K; Garrett, Bruce C

    2004-05-15

    Vapor to liquid multicomponent nucleation is a dynamical process governed by a delicate interplay between condensation and evaporation. Since the population of the vapor phase is dominated by monomers at reasonable supersaturations, the formation of clusters is governed by monomer association and dissociation reactions. Although there is no intrinsic barrier in the interaction potential along the minimum energy path for the association process, the formation of a cluster is impeded by a free energy barrier. Dynamical nucleation theory provides a framework in which equilibrium evaporation rate constants can be calculated and the corresponding condensation rate constants determined from detailed balance. The nucleation rate can then be obtained by solving the kinetic equations. The rate constants governing the multistep kinetics of multicomponent nucleation including sensitivity analysis and the potential influence of contaminants will be presented and discussed. PMID:15267849

  4. Nonstoichiometric nucleation and growth of multicomponent nanocrystals in solution.

    PubMed

    Min, Yuho; Kwak, Junghyeok; Soon, Aloysius; Jeong, Unyong

    2014-10-21

    The ability to assemble nanoscale functional building blocks is a useful and modular way for scientists to design valuable materials with specific physical and chemical properties. Chemists expect multicomponent, heterostructured nanocrystals to show unique electrical, thermal, and optical properties not seen in homogeneous, single-phase nanocrystals. Although researchers have made remarkable advances in heterogeneous nucleation and growth, design of synthetic conditions for obtaining nanocrystals with a target composition and shape is still a big challenge. There are several outstanding issues that chemists need to address before they can successfully carry out the design-based synthesis of multicomponent nanocrystals. For instance, small changes in the reaction parameters, such as the precursor, solvent, surfactant, reducing agent, and the reaction temperature, often result in changes in the structure and chemical composition of the final product. Although scientists do not fully understand the mechanisms underlying the nucleation and growth processes involved in the synthesis of these multicomponent nanocrystals, recent progress in understanding of the thermodynamic and kinetic factors have improved our control over their final structure and chemical composition. In this Account, we summarize our recent advances in understanding of the nucleation and growth mechanisms involved in the solution-based synthesis of multicomponent nanocrystals. We also discuss the various challenges encountered in their synthesis, emphasizing what still needs special consideration. We first discuss the three different nucleation paths from a thermodynamics perspective: amorphous nucleation, crystalline nucleation, and two-step nucleation. Amorphous nucleation and two-step nucleation involve the generation of nonstoichiometric nuclei. We initiate this process mainly by introducing an imbalance in the concentrations of the reduced elements. When the nonstoichiometric nuclei grow, we

  5. Surface area controlled heterogeneous nucleation

    NASA Astrophysics Data System (ADS)

    Steer, Brian; Gorbunov, Boris; Rowles, Jonathan; Green, David

    2012-02-01

    Heterogeneous nucleation of liquid from a gas phase on nanoparticles has been studied under various saturation ratios and nuclei size. The probability of liquid droplet nucleation, especially at a low degree of deviation from equilibrium, was measured for both atmospheric aerosol particles and engineered nanoparticles Cr2O3. The concept of a critical saturation ratio and the validity of the one-to-one relationship between the nuclei number and the number of droplets were examined. A transient zone between no nucleation and established nucleation termed the surface area controlled nucleation was observed. In this zone, the probability of stable phase formation is determined by the surface area of nuclei. There are two distinctive features of the surface area controlled nucleation: the nucleation probability is much less than 1 and is proportional to the surface area of nuclei. For condensation particle counters (CPCs) counting nanoparticles, these features mean that counts measured are proportional to the surface area of nanoparticles and, therefore, the CPCs counts can be calibrated to measure the surface area.

  6. Heterogeneous nucleation in hypermonotectic aluminum alloys

    NASA Astrophysics Data System (ADS)

    Köhler, M.; Ratke, L.; Kaban, I.; Hoyer, W.

    2012-01-01

    Simple casting experiments were set up to solve the question, if heterogeneous nucleation of the liquid-liquid decomposition in monotectic systems is possible. Al-Pb alloys with different inoculants were solidified, and the resulting microstructure was analysed by SEM and X-ray microtomography. Pronounced changes in the distribution of the lead precipitations indicate that it is possible to trigger the nucleation.

  7. Effective binary theory of multi-component nucleation

    SciTech Connect

    Kalikmanov, V. I.

    2015-03-28

    Classical theory of multi-component nucleation [O. Hirschfelder, J. Chem. Phys. 61, 2690 (1974)] belongs to the class of the so-called intractable problems: it requires computational time which is an exponential function of the number of components N. For a number of systems of practical interest with N > 10, the brute-force use of the classical theory becomes virtually impossible and one has to resort to an effective medium approach. We present an effective binary model which captures important physics of multi-component nucleation. The distinction between two effective species is based on the observation that while all N components contribute to the cluster thermodynamic properties, there is only a part of them which trigger the nucleation process. The proposed 2D-theory takes into account adsorption by means of the Gibbs dividing surface formalism and uses statistical mechanical considerations for the treatment of small clusters. Theoretical predictions for binary-, ternary-, and 14-component mixtures are compared with available experimental data and other models.

  8. Heterogeneous nucleation of aspartame from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Kubota, Noriaki; Kinno, Hiroaki; Shimizu, Kenji

    1990-03-01

    Waiting times, the time from the instant of quenching needed for a first nucleus to appear, were measured at constant supercoolings for primary nucleation of aspartame (α-L-aspartyl-L-phenylalanine methylester) from aqueous solutions, which were sealed into glass ampoules (solution volume = 3.16 cm 3). Since the waiting time became shorter by filtering the solution prior to quenching, the nucleation was concluded to be heterogeneously induced. The measured waiting time consisted of two parts: time needed for the nucleus to grow to a detactable size (growth time) and stochastic time needed for nucleation (true waiting time). The distribution of the true waiting time, is well explained by a stochastic model, in which nucleation is regarded to occur heterogeneously and in a stochastic manner by two kinds of active sites. The active sites are estimated to be located on foreign particles in which such elements as Si, Al and Mg were contained. The amount of each element is very small in the order of magnitude of ppb (mass basis) of the whole solution. The growth time was correlated with the degree of supercooling.

  9. Heterogeneous nucleation of calcium oxalate on native oxide surfaces

    SciTech Connect

    Song, L.; Pattillo, M.J.; Graff, G.L.; Campbell, A.A.; Bunker, B.C.

    1994-12-31

    The aqueous deposition of calcium oxalate onto colloidal oxides has been studied as a model system for understanding heterogeneous nucleation processes of importance in biomimetic synthesis of ceramic thin films. Calcium oxalate nucleation has been monitored by measuring induction times for nucleation using Constant Composition techniques and by measuring nucleation densities on extended oxide surfaces using an atomic force microscope. Results show that the dependence of calcium oxalate nucleation on solution supersaturation fits the functional form predicted by classical nucleation theories. Anionic surfaces appear to promote nucleation better than cationic surfaces, lowering the effective energy barrier to heterogeneous nucleation.

  10. Ice nucleation on carbon surface supports the classical theory for heterogeneous nucleation.

    PubMed

    Cabriolu, Raffaela; Li, Tianshu

    2015-05-01

    The prevalence of heterogeneous nucleation in nature was explained qualitatively by the classical theory for heterogeneous nucleation established over more than 60 years ago, but the quantitative validity and the key conclusions of the theory have remained unconfirmed. Employing the forward flux sampling method and the coarse-grained water model (mW), we explicitly computed the heterogeneous ice nucleation rates in the supercooled water on a graphitic surface at various temperatures. The independently calculated ice nucleation rates were found to fit well according to the classical theory for heterogeneous nucleation. The fitting procedure further yields the estimate of the potency factor, which measures the ratio of the heterogeneous nucleation barrier to the homogeneous nucleation barrier. Remarkably, the estimated potency factor agrees quantitatively with the volumetric ratio of the critical nuclei between the heterogeneous and homogeneous nucleation. Our numerical study thus provides a strong support to the quantitative power of the theory and allows understanding ice nucleation behaviors under the most relevant freezing conditions. PMID:26066178

  11. A nanoscale temperature-dependent heterogeneous nucleation theory

    SciTech Connect

    Cao, Y. Y.; Yang, G. W.

    2015-06-14

    Classical nucleation theory relies on the hypothetical equilibrium of the whole nucleation system, and neglects the thermal fluctuations of the surface; this is because the high entropic gains of the (thermodynamically extensive) surface would lead to multiple stable states. In fact, at the nanometer scale, the entropic gains of the surface are high enough to destroy the stability of the thermal equilibrium during nucleation, comparing with the whole system. We developed a temperature-dependent nucleation theory to elucidate the heterogeneous nucleation process, by considering the thermal fluctuations based on classical nucleation theory. It was found that the temperature not only affected the phase transformation, but also influenced the surface energy of the nuclei. With changes in the Gibbs free energy barrier, nucleation behaviors, such as the nucleation rate and the critical radius of the nuclei, showed temperature-dependent characteristics that were different from those predicted by classical nucleation theory. The temperature-dependent surface energy density of a nucleus was deduced based on our theoretical model. The agreement between the theoretical and experimental results suggested that the developed nucleation theory has the potential to contribute to the understanding and design of heterogeneous nucleation at the nanoscale.

  12. Note: Heterogeneous ice nucleation on silver-iodide-like surfaces

    NASA Astrophysics Data System (ADS)

    Fraux, Guillaume; Doye, Jonathan P. K.

    2014-12-01

    We attempt to simulate the heterogeneous nucleation of ice at model silver-iodide surfaces and find relatively facile ice nucleation and growth at the Ag+ terminated basal face, but never see nucleation at the I- terminated basal face or the prism and normal faces. Water molecules strongly adsorb onto the Ag+ terminated face to give a well-ordered hexagonal ice-like bilayer that then acts as a template for further ice growth.

  13. Thermokinetics of heterogeneous droplet nucleation on conically textured substrates

    NASA Astrophysics Data System (ADS)

    Singha, Sanat K.; Das, Prasanta K.; Maiti, Biswajit

    2015-11-01

    Within the framework of the classical theory of heterogeneous nucleation, a thermokinetic model is developed for line-tension-associated droplet nucleation on conical textures considering growth or shrinkage of the formed cluster due to both interfacial and peripheral monomer exchange and by considering different geometric configurations. Along with the principle of free energy extremization, Katz kinetic approach has been employed to study the effect of substrate conicity and wettability on the thermokinetics of heterogeneous water droplet nucleation. Not only the peripheral tension is found to have a considerable effect on the free energy barrier but also the substrate hydrophobicity and hydrophilicity are observed to switch over their roles between conical crest and trough for different growth rates of the droplet. Besides, the rate of nucleation increases and further promotes nucleation for negative peripheral tension as it diminishes the free energy barrier appreciably. Moreover, nucleation inhibition can be achievable for positive peripheral tension due to the enhancement of the free energy barrier. Analyzing all possible geometric configurations, the hydrophilic narrower conical cavity is found to be the most preferred nucleation site. These findings suggest a physical insight into the context of surface engineering for the promotion or the suppression of nucleation on real or engineered substrates.

  14. Heterogeneous nucleation on surfaces of the ellipsoid of rotation

    NASA Astrophysics Data System (ADS)

    Li, Xiang-Ming; Liu, Qing-Hui

    2016-08-01

    This paper focusses on the heterogeneous nucleation on the surface with the non-constant curvature. The formation of a spherical nucleus on the ellipsoid of rotation is considered. Following the classical nucleation theory, the work of formation of a critical nucleus on the ellipsoid of rotation has been given, and the effects of geometry sizes and the material properties of the ellipsoid of rotation on the work of formation of a critical nucleus have been obtained. When the geometry size of the substrate is about value of the critical nucleus radius, there may exist twice nucleation on the ellipsoid of rotation for the case of the smaller value of λ and ϕ < π / 2. As the work of formation of a nucleus has only one extremum (the maximum), the nucleation on the oblate rotational ellipsoid is more easy than on the spherical surface, while nucleation on the prolate ellipsoid of rotation is more difficult than on the spherical surface. Furthermore, if the particles of the ellipsoid are added into the parent phase as nucleation agents or catalysts, for some geometry sizes, they would not have the effects on the heterogeneous nucleation.

  15. Heterogeneous Nucleation of Protein Crystals on Fluorinated Layered Silicate

    PubMed Central

    Ino, Keita; Udagawa, Itsumi; Iwabata, Kazuki; Takakusagi, Yoichi; Kubota, Munehiro; Kurosaka, Keiichi; Arai, Kazuhito; Seki, Yasutaka; Nogawa, Masaya; Tsunoda, Tatsuo; Mizukami, Fujio; Taguchi, Hayao; Sakaguchi, Kengo

    2011-01-01

    Here, we describe an improved system for protein crystallization based on heterogeneous nucleation using fluorinated layered silicate. In addition, we also investigated the mechanism of nucleation on the silicate surface. Crystallization of lysozyme using silicates with different chemical compositions indicated that fluorosilicates promoted nucleation whereas the silicates without fluorine did not. The use of synthesized saponites for lysozyme crystallization confirmed that the substitution of hydroxyl groups contained in the lamellae structure for fluorine atoms is responsible for the nucleation-inducing property of the nucleant. Crystallization of twelve proteins with a wide range of pI values revealed that the nucleation promoting effect of the saponites tended to increase with increased substitution rate. Furthermore, the saponite with the highest fluorine content promoted nucleation in all the test proteins regardless of their overall net charge. Adsorption experiments of proteins on the saponites confirmed that the density of adsorbed molecules increased according to the substitution rate, thereby explaining the heterogeneous nucleation on the silicate surface. PMID:21818343

  16. Heterogeneous nucleation of protein crystals on fluorinated layered silicate.

    PubMed

    Ino, Keita; Udagawa, Itsumi; Iwabata, Kazuki; Takakusagi, Yoichi; Kubota, Munehiro; Kurosaka, Keiichi; Arai, Kazuhito; Seki, Yasutaka; Nogawa, Masaya; Tsunoda, Tatsuo; Mizukami, Fujio; Taguchi, Hayao; Sakaguchi, Kengo

    2011-01-01

    Here, we describe an improved system for protein crystallization based on heterogeneous nucleation using fluorinated layered silicate. In addition, we also investigated the mechanism of nucleation on the silicate surface. Crystallization of lysozyme using silicates with different chemical compositions indicated that fluorosilicates promoted nucleation whereas the silicates without fluorine did not. The use of synthesized saponites for lysozyme crystallization confirmed that the substitution of hydroxyl groups contained in the lamellae structure for fluorine atoms is responsible for the nucleation-inducing property of the nucleant. Crystallization of twelve proteins with a wide range of pI values revealed that the nucleation promoting effect of the saponites tended to increase with increased substitution rate. Furthermore, the saponite with the highest fluorine content promoted nucleation in all the test proteins regardless of their overall net charge. Adsorption experiments of proteins on the saponites confirmed that the density of adsorbed molecules increased according to the substitution rate, thereby explaining the heterogeneous nucleation on the silicate surface. PMID:21818343

  17. From embryos to precipitates: A study of nucleation and growth in a multicomponent ferritic steel

    NASA Astrophysics Data System (ADS)

    Zhang, Z. W.; Liu, C. T.; Wang, X.-L.; Littrell, K. C.; Miller, M. K.; An, K.; Chin, B. A.

    2011-11-01

    The nucleation and growth of nanoscale precipitates in a new class of high-strength, multicomponent, ferritic steels has been studied with complementary state-of-the-art microstructural characterization techniques of atom probe tomography for individual embryos and precipitates and small-angle neutron scattering for their statistical averages. Both techniques revealed a bimodal size distribution, with subnanometer embryos, and nanoscale precipitates. The embryos, which have a radius of ˜0.4 nm, are enriched in Cu and served as preferential sites for nucleation. The critical radius for nucleation was determined to be ˜0.7 nm. Subsequent growth of the precipitates is dictated by volumetric diffusion, as predicted by the Lifshitz-Slyozov-Wagner theory.

  18. Dimple-assisted dewetting: heterogeneous nucleation in undercooled wetting films

    NASA Astrophysics Data System (ADS)

    Blossey, Ralf

    2001-09-01

    Undercooled wetting films near a first-order wetting transition exhibit an unusually long lifetime: the thermal nucleation barrier for formation of a critical hole in a film of thickness F diverges according to exp (c/kBT) where the excess free energy c F with ≥ 2. Localized perturbations of the liquid-vapor interface (dimples) are shown to be a useful tool in reducing in a controlled way: they act as heterogeneous nucleation centers for thermal critical nuclei. For 4He wetting films on weak-binding alkali substrates (Cs, Rb) dimples can be generated either by vortices in a superfluid film or by surface electrons. The theory of the heterogeneous nucleation process initiated by the presence of surface dimples (dimple-assisted dewetting) is developed, accompanied by quantitative predictions for experiment.

  19. Heterogeneous nucleation of ice on model carbon surfaces

    NASA Astrophysics Data System (ADS)

    Molinero, V.; Lupi, L.; Hudait, A.

    2014-12-01

    Carbonaceous particles account for 10% of the particulate matter in the atmosphere. The experimental investigation of heterogeneous freezing of water droplets by carbonaceous particles reveals widespread ice freezing temperatures. The origin of the soot and its oxidation and aging modulate its ice nucleation ability, however, it is not known which structural and chemical characteristics of soot account for the variability in ice nucleation efficiency. We find that atomically flat carbon surfaces promote heterogeneous nucleation of ice, while molecularly rough surfaces with the same hydrophobicity do not. We investigate a large set of graphitic surfaces of various dimensions and radii of curvature consistent with those of soot in experiments, and find that variations in nanostructures alone could account for the spread in the freezing temperatures of ice on soot in experiments. A characterization of the nanostructure of soot is needed to predict its ice nucleation efficiency. Atmospheric oxidation and aging of soot modulates its ice nucleation ability. It has been suggested that an increase in the ice nucleation ability of aged soot results from an increase in the hydrophilicity of the surfaces upon oxidation. Oxidation, however, also impacts the nanostructure of soot, making it difficult to assess the separate effects of soot nanostructure and hydrophilicity in experiments. We investigate the effect of changes in hydrophilicity of model graphitic surfaces on the freezing temperature of ice. Our results indicate that the hydrophilicity of the surface is not in general a good predictor of ice nucleation ability. We find a correlation between the ability of a surface to promote nucleation of ice and the layering of liquid water at the surface. The results of this work suggest that ordering of liquid water in contact with the surface plays an important role in the heterogeneous ice nucleation mechanism. References: L. Lupi, A. Hudait and V. Molinero, J. Am. Chem. Soc

  20. An adsorption model of the heterogeneous nucleation of solidification

    SciTech Connect

    Kim, W.T.; Cantor, B. . Oxford Centre for Advanced Materials and Composites)

    1994-09-01

    An adsorption model has been developed to describe the heterogeneous nucleation of solidification in an A-B eutectic or monotectic alloy system. The interface between A-rich [alpha] solid and B-rich liquid is treated as a mixture of A solid, B solid, A liquid and B liquid atoms, randomly distributed as a monolayer between the two phases. The interfacial energy is calculated by summing pairwise bonding energies, and is then minimized to determine the equilibrium interface solid fraction and composition. With decreasing temperature, the interface monolayer changes sharply from liquid to solid, with a composition close to pure B. This sharp onset of interface adsorption of solid B atoms corresponds to [alpha] acting as a catalyst for the heterogeneous nucleation of B-rich [beta] solid. Adsorption close to the eutectic temperature and therefore efficient nucleation catalysis is promoted by a large difference between the melting points of A and B, and a small difference between the solid and liquid immiscibilities of A and B. Predicted undercoolings for the onset of adsorption and nucleation catalysis can be obtained directly from simple phase diagram data, and give good agreement with previous measurements in the Ag-Pb and Al-Sn alloy systems.

  1. Molecular simulations of heterogeneous ice nucleation. I. Controlling ice nucleation through surface hydrophilicity

    SciTech Connect

    Cox, Stephen J.; Kathmann, Shawn M.; Slater, B.; Michaelides, Angelos

    2015-05-14

    Ice formation is one of the most common and important processes on earth and almost always occurs at the surface of a material. A basic understanding of how the physicochemical properties of a material’s surface affect its ability to form ice has remained elusive. Here, we use molecular dynamics simulations to directly probe heterogeneous ice nucleation at a hexagonal surface of a nanoparticle of varying hydrophilicity. Surprisingly, we find that structurally identical surfaces can both inhibit and promote ice formation and analogous to a chemical catalyst, it is found that an optimal interaction between the surface and the water exists for promoting ice nucleation.We use our microscopic understanding of the mechanism to design a modified surface in silico with enhanced ice nucleating ability. C 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

  2. Elastic and plastic effects on heterogeneous nucleation and nanowire formation

    NASA Astrophysics Data System (ADS)

    Boussinot, G.; Schulz, R.; Hüter, C.; Brener, E. A.; Spatschek, R.

    2014-02-01

    We investigate theoretically the effects of elastic and plastic deformations on heterogeneous nucleation and nanowire formation. In the first case, the influence of the confinement of the critical nucleus between two parallel misfitting substrates is investigated using scaling arguments. We present phase diagrams giving the nature of the nucleation regime as a function of the driving force and the degree of confinement. We complement this analytical study by amplitude equations simulations. In the second case, the influence of a screw dislocation inside a nanowire on the development of the morphological surface instability of the wire, related to the Rayleigh-Plateau instability, is examined. Here the screw dislocation provokes a torsion of the wire known as Eshelby twist. Numerical calculations using the finite element method and the amplitude equations are performed to support analytical investigations. It is shown that the screw dislocation promotes the Rayleigh-Plateau instability.

  3. Heterogeneous Nucleation of Naphthalene Vapor on Water Surface

    PubMed

    Smolík; Schwarz

    1997-01-15

    The evaporation of a water drop into a ternary gaseous mixture of air, steam, and naphthalene vapor was investigated. The experimental results were compared with a theoretical prediction based on a numerical solution of coupled boundary layer equations for heat and mass transfer from a drop moving in ternary gas. In the experiments the naphthalene vapor condensed on the water drop as a supercooled liquid even at temperatures far below the melting point of naphthalene. The condensation on drop surface is discussed in terms of classical theory of heterogeneous nucleation on smooth surfaces. PMID:9028892

  4. Alteration of Heterogeneous Ice Nucleation Properties Induced by Particle Aging

    NASA Astrophysics Data System (ADS)

    Sullivan, R. C.; Polen, M.; Beydoun, H.; Lawlis, E.; Ahern, A.; Jahn, L.; Hill, T. C. J.

    2015-12-01

    Aerosol particles that can serve as ice nuclei frequently experience rapid and extensive chemical aging during atmospheric transport. This is known to significantly alter some ice nucleation modes of the few types of ice nucleation particle systems where aging effects have been simulated, such as for mineral dust. Yet much of our understanding of atmospheric particle freezing properties is derived from measurements of fresh or unaged particles. We know almost nothing regarding how atmospheric aging might alter the freezing properties of biomass burning aerosol or biological particle nucleants. We have investigated the effects of simulated aging using a chamber reactor on the heterogeneous ice nucleation properties of biomass burning aerosol (BBA) and ice-active bacteria particles. Some types of aging were found to enhance the freezing ability of BBA, exhibited as a shift in a portion of the droplet freezing curve to warmer temperatures by a few °C. Ice-active bacteria were found to consistently loose their most ice-active nucleants after repeated aging cycles. The bacterial systems always retained significantly efficient ice active sites that still allowed them to induce freezing at mild/warm temperatures, despite this decrease in freezing ability. A comprehensive series of online single-particle mass spectrometry and offline spectromicroscopic analysis of individual particles was used to determine how the aging altered the aerosol's composition, and gain mechanistic insights into how this in turn altered the freezing properties. Our new ice nucleation framework that uses a continuous distribution of ice active site ability (contact angle) was used to interpret the droplet freezing spectra and understand how aging alters the internal and external variability, and rigidity, of the ice active sites.

  5. Impurity-stimulated heterogeneous nucleation of supercooled H2 clusters.

    PubMed

    Knuth, Eldon; Schaper, Sven; Toennies, J Peter

    2004-01-01

    The sizes and mass spectra of large (N=1900-13,700 molecules) cold (approximately 3.1 K) H2 clusters have been measured after scattering from CO molecules. Cluster-size measurements after between 2 and 8 collisions indicate that 7% of the H2 molecules are evaporated. This loss agrees with calculations for the number of H2 molecules evaporated by the heat released in the transition from an initial liquid state to a final solid state. Even though heterogeneous nucleation is initiated after only a few collisions with CO molecules, the mass spectra show that additional captured CO molecules coagulate to form large CO clusters with up to n=11 molecules, suggesting that the outer layer is sufficiently liquidlike to facilitate mobility of the CO molecules. Since the calculated H2 cluster temperature (approximately 3.1 K) is below the superfluid transition temperature predicted for pH2 with density between 40% and 80% of the triple-point density, a shell-like region of low density near the cluster surface can be expected to be superfluid. PMID:15267283

  6. Heterogeneous ice nucleation: exploring the transition from stochastic to singular freezing behavior

    NASA Astrophysics Data System (ADS)

    Niedermeier, D.; Shaw, R. A.; Hartmann, S.; Wex, H.; Clauss, T.; Voigtländer, J.; Stratmann, F.

    2011-08-01

    Heterogeneous ice nucleation, a primary pathway for ice formation in the atmosphere, has been described alternately as being stochastic, in direct analogy with homogeneous nucleation, or singular, with ice nuclei initiating freezing at deterministic temperatures. We present an idealized, conceptual model to explore the transition between stochastic and singular ice nucleation. This "soccer ball" model treats particles as being covered with surface sites (patches of finite area) characterized by different nucleation barriers, but with each surface site following the stochastic nature of ice embryo formation. The model provides a phenomenological explanation for seemingly contradictory experimental results obtained in our research groups. Even with ice nucleation treated fundamentally as a stochastic process this process can be masked by the heterogeneity of surface properties, as might be typical for realistic atmospheric particle populations. Full evaluation of the model findings will require experiments with well characterized ice nucleating particles and the ability to vary both temperature and waiting time for freezing.

  7. Godunov Method for Calculating Multicomponent Heterogeneous Medium Flows

    NASA Astrophysics Data System (ADS)

    Surov, V. S.

    2014-03-01

    The modified Godunov method intended for integrating the nondivergent systems that describe a multivelocity heterogeneous mixture flow is presented. The linearized Riemann solver has been used in solving the Riemann problems.

  8. Line-tension effects on heterogeneous nucleation on a spherical substrate and in a spherical cavity.

    PubMed

    Iwamatsu, Masao

    2015-04-01

    The line-tension effects on heterogeneous nucleation are considered when a spherical lens-shaped nucleus is nucleated on top of a spherical substrate and on the bottom of the wall of a spherical cavity. The effect of line tension on the nucleation barrier can be separated from the usual volume term. As the radius of the substrate increases, the nucleation barrier decreases and approaches that of a flat substrate. However, as the radius of the cavity increases, the nucleation barrier increases and approaches that of a flat substrate. A small spherical substrate is a less active nucleation site than a flat substrate, and a small spherical cavity is a more active nucleation site than a flat substrate. In contrast, the line-tension effect on the nucleation barrier is maximum when the radii of the nucleus and the substrate or cavity become comparable. Therefore, by tuning the size of the spherical substrate or spherical cavity, the effect of the line tension can be optimized. These results will be useful in broad range of applications from material processing to understanding of global climate, where the heterogeneous nucleation plays a vital role. PMID:25775383

  9. Heterogeneous ice nucleation on particles composed of humic-like substances impacted by O3

    NASA Astrophysics Data System (ADS)

    Wang, Bingbing; Knopf, Daniel A.

    2011-02-01

    Heterogeneous ice nucleation plays important roles in cirrus and mixed-phase cloud formation, but the efficiency of organic particles to act as ice nuclei (IN) is still not well understood. Furthermore, the effect of particle oxidation by O3 on corresponding IN efficiencies has not yet been sufficiently assessed. We present heterogeneous ice nucleation on kaolinite, Suwannee River standard fulvic acid (SRFA), and leonardite standard humic acid particles as a function of particle temperature (Tp), relative humidity with respect to ice (RHice), nucleation mode, and O3 exposure. Ice nucleation and water uptake were studied for Tp >203 K and RHice up to water saturation using a novel ice nucleation apparatus. This study shows that SRFA, leonardite, and corresponding O3-exposed particles can nucleate ice via different modes at relevant atmospheric conditions. These particles nucleated ice via deposition mode at Tp ≤ 231 K, and for higher Tp water was taken up or ice was nucleated via deposition or immersion mode. Oxidation of leonardite and SRFA particles by O3 led to a decrease in deposition nucleation efficiency and to water uptake at lower temperatures for the former and to an increase in the lowest temperature at which deposition nucleation was observed for the latter. Activated IN fractions and heterogeneous ice nucleation rate coefficients (Jhet) were derived, and corresponding contact angles (θ) were calculated. A parameterization of θ as a function of RHice is presented which allows derivation of Jhet for various deposition IN and corresponding ice crystal production rates for application in cloud-resolving models.

  10. Heterogeneous ice nucleation on atmospheric aerosols: a review of results from laboratory experiments

    NASA Astrophysics Data System (ADS)

    Hoose, C.; Möhler, O.

    2012-10-01

    A small subset of the atmospheric aerosol population has the ability to induce ice formation at conditions under which ice would not form without them (heterogeneous ice nucleation). While no closed theoretical description of this process and the requirements for good ice nuclei is available, numerous studies have attempted to quantify the ice nucleation ability of different particles empirically in laboratory experiments. In this article, an overview of these results is provided. Ice nucleation "onset" conditions for various mineral dust, soot, biological, organic and ammonium sulfate particles are summarized. Typical temperature-supersaturation regions can be identified for the "onset" of ice nucleation of these different particle types, but the various particle sizes and activated fractions reported in different studies have to be taken into account when comparing results obtained with different methodologies. When intercomparing only data obtained under the same conditions, it is found that dust mineralogy is not a consistent predictor of higher or lower ice nucleation ability. However, the broad majority of studies agrees on a reduction of deposition nucleation by various coatings on mineral dust. The ice nucleation active surface site (INAS) density is discussed as a simple and empirical normalized measure for ice nucleation activity. For most immersion and condensation freezing measurements on mineral dust, estimates of the temperature-dependent INAS density agree within about two orders of magnitude. For deposition nucleation on dust, the spread is significantly larger, but a general trend of increasing INAS densities with increasing supersaturation is found. For soot, the presently available results are divergent. Estimated average INAS densities are high for ice-nucleation active bacteria at high subzero temperatures. At the same time, it is shown that INAS densities of some other biological aerosols, like certain pollen grains, fungal spores and diatoms

  11. Competitive heterogeneous nucleation onto a microscopic impurity in a Potts model

    NASA Astrophysics Data System (ADS)

    Asuquo, Cletus C.; McArthur, Danielle; Bowles, Richard K.

    2016-08-01

    Many metastable systems can nucleate to multiple competing stable or intermediate metastable states. In this work, a Potts model, subject to external fields, is used to study the competitive nucleation of two phases attempting to grow on a microscopic impurity. Monte Carlo simulations are used to calculate the free energy surfaces for the system under different conditions, where the relative stability of the phases is adjusted by changing the interaction parameters, and the nucleation rates obtained using multicomponent transition state theory (TST) are compared with the rates measured using the survival probability method. We find that the two methods predict similar nucleation rates when the free energy barrier used in the transition state theory is defined as the work required to form a critical embryo from the metastable phase. An analysis of the free energy surfaces also reveals that the competition between the nucleating phases leads to an effective drying of the impurity which slows down the nucleation rate compared to the single phase case.

  12. Improved Success of Sparse Matrix Protein Crystallization Screening with Heterogeneous Nucleating Agents

    PubMed Central

    Thakur, Anil S.; Robin, Gautier; Guncar, Gregor; Saunders, Neil F. W.; Newman, Janet; Martin, Jennifer L.; Kobe, Bostjan

    2007-01-01

    Background Crystallization is a major bottleneck in the process of macromolecular structure determination by X-ray crystallography. Successful crystallization requires the formation of nuclei and their subsequent growth to crystals of suitable size. Crystal growth generally occurs spontaneously in a supersaturated solution as a result of homogenous nucleation. However, in a typical sparse matrix screening experiment, precipitant and protein concentration are not sampled extensively, and supersaturation conditions suitable for nucleation are often missed. Methodology/Principal Findings We tested the effect of nine potential heterogenous nucleating agents on crystallization of ten test proteins in a sparse matrix screen. Several nucleating agents induced crystal formation under conditions where no crystallization occurred in the absence of the nucleating agent. Four nucleating agents: dried seaweed; horse hair; cellulose and hydroxyapatite, had a considerable overall positive effect on crystallization success. This effect was further enhanced when these nucleating agents were used in combination with each other. Conclusions/Significance Our results suggest that the addition of heterogeneous nucleating agents increases the chances of crystal formation when using sparse matrix screens. PMID:17971854

  13. The interface of heterogeneous nucleation on single crystal substrates

    NASA Astrophysics Data System (ADS)

    Yang, L.; Xia, M.; Li, J.

    2016-03-01

    Under controlled nucleation process was achieved by solidifying a high purity Al droplet on a single crystal Al2O3 substrate in a high vacuum chamber. The following X-Ray Diffraction (XRD) analysis and measured undercooling prove that the nucleation was triggered by the substrate. Various lattice mismatches between new crystal and substrate (C/S) were obtained through this approach. Combining XRD patterns and high resolution transmission electron microscope analysis we found that the morphology of interface was affected by lattice misfit. An epitaxial layer was found at C/S interface with larger lattice misfit, as in Al(100)//Al2O3(0001) system. Further experiments on introduced alloying element, Sb, into liquid Al shows a suppressed epitaxial layer of Al. Chemical reaction between liquid and substrate also contributes to the formation of the interface. The nucleation of Al on the MgO substrates was actually nucleated on MgAl2O4, chemical reaction product of Al and MgO, rather than MgO.

  14. Heterogeneous nucleation of ice from supercooled NaCl solution confined in porous cement paste

    NASA Astrophysics Data System (ADS)

    Zeng, Qiang; Li, Kefei; Fen-Chong, Teddy

    2015-01-01

    Clarifying the nucleation process of chloride-based deicing salt solution (e.g., NaCl solution) confined in cement-based porous materials remains an important issue to understand its detrimental effects on material substrates. In this study, the pore structures of hardened cement pastes were characterized by mercury-intrusion and nitrogen-sorption porosimetry. The ice nucleation temperature of NaCl solution of different concentrations confined in the hardened cement pastes was measured and analyzed by classical heterogeneous nucleation theory. The kinetic factor, contact-angle factor including the contact angle between ice and the substrate were evaluated. The results revealed that the contact angle between ice and the substrate showed the minimum value when adding 3% NaCl into water. The heterogeneous ice nucleation rates were found to be proportional to the water activity shifts.

  15. Heterogeneous Nucleation of Ice on Anthropogenic Organic Particles Collected in Mexico City

    SciTech Connect

    Knopf, Daniel A.; Wang, BingBing; Laskin, Alexander; Moffet, Ryan C.; Gilles, Marry K.

    2010-06-05

    This study reports on heterogeneous ice nucleation activity of predominantly organic or coated with organic material anthropogenic particles sampled within and around the polluted environment of Mexico City. The onset of heterogeneous ice nucleation was observed as a function of particle temperature (Tp), relative humidity (RH), nucleation mode, and chemical composition of particles influenced by their photochemical atmospheric aging. Particle analyses was conducted using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). In contrast to the majority of laboratory studies employing proxies of organic aerosol, we show that anthropogenic organic particles collected in Mexico City have can potentially induce ice nucleation at experimental conditions relevant to cirrus formation. The reported results suggest a new paradigm for the potential impact of organic particles on ice cloud formation and climate.

  16. Heterogeneous nucleation of ice on anthropogenic organic particles collected in Mexico City

    SciTech Connect

    Knopf, D.A.; Wang, B.; Laskin, A.; Moffet, R.C.; Gilles, M.K.

    2010-06-20

    This study reports on heterogeneous ice nucleation activity of predominantly organic (or coated with organic material) anthropogenic particles sampled within and around the polluted environment of Mexico City. The onset of heterogeneous ice nucleation was observed as a function of particle temperature (Tp), relative humidity (RH), nucleation mode, and particle chemical composition which is influenced by photochemical atmospheric aging. Particle analyses included computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). In contrast to most laboratory studies employing proxies of organic aerosol, we show that anthropogenic organic particles collected in Mexico City can potentially induce ice nucleation at experimental conditions relevant to cirrus formation. The results suggest a new precedent for the potential impact of organic particles on ice cloud formation and climate.

  17. Molecular Simulations of Heterogeneous Ice Nucleation. II. Peeling back the Layers

    SciTech Connect

    Cox, Stephen J.; Kathmann, Shawn M.; Slater, B.; Michaelides, Angelos

    2015-05-14

    Coarse grained molecular dynamics simulations are presented in which the sensitivity of the ice nucleation rate to the hydrophilicity of a graphene nanoflake is investigated. We find that an optimal interaction strength for promoting ice nucleation exists, which coincides with that found previously for a face centered cubic (111) surface. We further investigate the role that the layering of interfacial water plays in heterogeneous ice nucleation and demonstrate that the extent of layering is not a good indicator of ice nucleating ability for all surfaces. Our results suggest that to be an efficient ice nucleating agent, a surface should not bind water too strongly if it is able to accommodate high coverages of water.

  18. Heterogeneous ice nucleation and water uptake by field-collected atmospheric particles below 273 K

    SciTech Connect

    Wang, Bingbing; Laskin, Alexander; Roedel, Tobias R.; Gilles, Marry K.; Moffet, Ryan C.; Tivanski, Alexei V.; Knopf, Daniel A.

    2012-09-25

    Atmospheric ice formation induced by particles with complex chemical and physical properties through heterogeneous nucleation is not well understood. Heterogeneous ice nucleation and water uptake by ambient particles collected from urban environments in Los Angeles and Mexico City are presented. Using a vapour controlled cooling system equipped with an optical microscopy, the range of onset conditions for ice nucleation and water uptake by the collected particles was determined as a function of temperature (200{273 K) and relative humidity with respect to ice (RHice) up to water saturation. Three distinctly different types of authentic atmospheric particles were investigated including soot particles associated with organics/inorganics, inorganic particles of marine origin coated with organic material, and Pb/Zn containing inorganic particles apportioned to anthropogenic emissions relevant to waste incineration. Single particle characterization was provided by micro-spectroscopic analyses using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and scanning transmission X-ray microscopy with near edge X-ray absorption ne structure spectroscopy (STXM/NEXAFS). Above 230 K, signicant differences in water uptake and immersion freezing effciencies of the different particle types were observed. Below 230 K, the particles exhibited high deposition ice nucleation effciencies and formed ice at RHice values well below homogeneous ice nucleation limits. The data show that the chemical composition of these eld{collected particles plays an important role in determining water uptake and immersion freezing. Heterogeneous ice nucleation rate coeffcients, cumulative ice nuclei (IN) spectrum, and IN activated fraction for deposition ice nucleation are derived. The presented ice nucleation data demonstrate that anthropogenic and marine particles comprising of various chemical and physical properties exhibit distinctly different ice

  19. Heterogeneous nucleation of ice particles on glassy aerosols modifies TTL cirrus

    NASA Astrophysics Data System (ADS)

    Wilson, T. W.; Murray, B. J.; Dobbie, S.; Al-Jumur, S. M.; Cui, Z.; Wagner, R.; Moehler, O.; Schnaiter, M.; Benz, S.; Niemand, M.; Saathoff, H.; Skrotzki, J.; Ebert, V.; Wagner, S.; Karcher, B.

    2010-12-01

    Experiments at the AIDA chamber, Karlsruhe Institute of Technology, have shown that glassy aqueous citric acid aerosol can nucleate ice at temperatures relevant to the tropical tropopause layer (TTL)(1). Modelling suggests this new route to the formation of TTL cirrus can provide an explanation for the very low ice particle number density observed in cirrus clouds in this region and may lead to high in-cloud supersaturations(1). Nucleation of ice on glassy aerosol is consistent with the absence of traditional ice nuclei in sampled TTL cirrus residue(2). In addition, we will present new data from experiments performed in July 2010 at the AIDA chamber using glassy aerosols composed of other atmospherically relevant compounds (levoglucosan, raffinose) and an internal mixture of five dicarboxylic acids and ammonium sulphate (raffinose/M5AS)(3). All four systems tested nucleate ice when in a glassy state. This indicates that heterogeneous ice nucleation is a general property of glassy aerosols and that natural aerosols which are composed of similar molecules will also nucleate ice if glassy. Glassy aqueous levoglucosan and raffinose/M5AS aerosol nucleated ice at temperatures similar to those found for glassy aqueous citric acid aerosol (<202 K). Whereas raffinose, which forms a glass at much higher temperatures, nucleated ice heterogeneously at up to ~220 K. This activity at higher temperatures suggests that ice nucleation by glassy aerosol may also play a role in the formation of warmer ice clouds. (1)B. J. Murray et al., Heterogeneous nucleation of ice particles on glassy aerosols under cirrus conditions, Nature Geosci, 2010, 3, 233-237. (2)K. D. Froyd et al., Aerosols that form subvisible cirrus at the tropical tropopause, Atmos. Chem. Phys., 2010, 10, 209-218. (3)B. Zobrist et al., Do atmospheric aerosols form glasses?, Atmos. Chem. Phys., 2008, 8, 5221-5244.

  20. Heterogeneous ice nucleation on atmospheric aerosols: a review of results from laboratory experiments

    NASA Astrophysics Data System (ADS)

    Hoose, C.; Möhler, O.

    2012-05-01

    A small subset of the atmospheric aerosol population has the ability to induce ice formation at conditions under which ice would not form without them (heterogeneous ice nucleation). While no closed theoretical description of this process and the requirements for good ice nuclei is available, numerous studies have attempted to quantify the ice nucleation ability of different particles empirically in laboratory experiments. In this article, an overview of these results is provided. Ice nucleation onset conditions for various mineral dust, soot, biological, organic and ammonium sulphate particles are summarized. Typical temperature-supersaturation regions can be identified for the onset of ice nucleation of these different particle types, but the various particle sizes and activated fractions reported in different studies have to be taken into account when comparing results obtained with different methodologies. When intercomparing only data obtained under the same conditions, it is found that dust mineralogy is not a consistent predictor of higher or lower ice nucleation ability. However, the broad majority of studies agrees on a reduction of deposition nucleation by various coatings on mineral dust. The ice nucleation active surface site (INAS) density is discussed as a normalized measure for ice nucleation activity. For most immersion and condensation freezing measurements on mineral dust, estimates of the temperature-dependent INAS density agree within about two orders of magnitude. For deposition nucleation on dust, the spread is significantly larger, but a general trend of increasing INAS densities with increasing supersaturation is found. For soot, the presently available results are divergent. Estimated average INAS densities are high for ice-nucleation active bacteria at high subzero temperatures. At the same time, it is shown that some other biological aerosols, like certain pollen grains and fungal spores, are not intrinsically better ice nuclei than dust

  1. FOREWORD: Heterogenous nucleation and microstructure formation—a scale- and system-bridging approach Heterogenous nucleation and microstructure formation—a scale- and system-bridging approach

    NASA Astrophysics Data System (ADS)

    Emmerich, H.

    2009-11-01

    Scope and aim of this volume. Nucleation and initial microstructure formation play an important role in almost all aspects of materials science [1-5]. The relevance of the prediction and control of nucleation and the subsequent microstructure formation is fully accepted across many areas of modern surface and materials science and technology. One reason is that a large range of material properties, from mechanical ones such as ductility and hardness to electrical and magnetic ones such as electric conductivity and magnetic hardness, depend largely on the specific crystalline structure that forms in nucleation and the subsequent initial microstructure growth. A very demonstrative example for the latter is the so called bamboo structure of an integrated circuit, for which resistance against electromigration [6] , a parallel alignment of grain boundaries vertical to the direction of electricity, is most favorable. Despite the large relevance of predicting and controlling nucleation and the subsequent microstructure formation, and despite significant progress in the experimental analysis of the later stages of crystal growth in line with new theoretical computer simulation concepts [7], details about the initial stages of solidification are still far from being satisfactorily understood. This is in particular true when the nucleation event occurs as heterogenous nucleation. The Priority Program SPP 1296 'Heterogenous Nucleation and Microstructure Formation—a Scale- and System-Bridging Approach' [8] sponsored by the German Research Foundation, DFG, intends to contribute to this open issue via a six year research program that enables approximately twenty research groups in Germany to work interdisciplinarily together following this goal. Moreover, it enables the participants to embed themselves in the international community which focuses on this issue via internationally open joint workshops, conferences and summer schools. An outline of such activities can be found

  2. Heterogeneous ice nucleation in aqueous solutions: the role of water activity.

    PubMed

    Zobrist, B; Marcolli, C; Peter, T; Koop, T

    2008-05-01

    Heterogeneous ice nucleation experiments have been performed with four different ice nuclei (IN), namely nonadecanol, silica, silver iodide and Arizona test dust. All IN are either immersed in the droplets or located at the droplets surface. The IN were exposed to various aqueous solutions, which consist of (NH4)2SO4, H2SO4, MgCl2, NaCl, LiCl, Ca(NO3)2, K2CO3, CH3COONa, ethylene glycol, glycerol, malonic acid, PEG300 or a NaCl/malonic acid mixture. Freezing was studied using a differential scanning calorimeter and a cold finger cell. The results show that the heterogeneous ice freezing temperatures decrease with increasing solute concentration; however, the magnitude of this effect is solute dependent. In contrast, when the results are analyzed in terms of the solution water activity a very consistent behavior emerges: heterogeneous ice nucleation temperatures for all four IN converge each onto a single line, irrespective of the nature of the solute. We find that a constant offset with respect to the ice melting point curve, Deltaaw,het, can describe the observed freezing temperatures for each IN. Such a behavior is well-known for homogeneous ice nucleation from supercooled liquid droplets and has led to the development of water-activity-based ice nucleation theory. The large variety of investigated solutes together with different general types of ice nuclei studied (monolayers, ionic crystals, covalently bound network-forming compounds, and a mixture of chemically different crystallites) underlines the general applicability of water-activity-based ice nucleation theory also for heterogeneous ice nucleation in the immersion mode. Finally, the ice nucleation efficiencies of the various IN, as well as the atmospheric implication of the developed parametrization are discussed. PMID:18363389

  3. Heterogeneous ice nucleation and water uptake by field-collected atmospheric particles below 273 K

    NASA Astrophysics Data System (ADS)

    Wang, Bingbing; Laskin, Alexander; Roedel, Tobias; Gilles, Mary K.; Moffet, Ryan C.; Tivanski, Alexei V.; Knopf, Daniel A.

    2012-09-01

    Ice formation induced by atmospheric particles through heterogeneous nucleation is not well understood. Onset conditions for heterogeneous ice nucleation and water uptake by particles collected in Los Angeles and Mexico City were determined as a function of temperature (200-273 K) and relative humidity with respect to ice (RHice). Four dominant particle types were identified including soot associated with organics, soot with organic and inorganics, inorganic particles of marine origin coated with organic material, and Pb/Zn-containing particles apportioned to emissions relevant to waste incineration. Single particle characterization was provided by micro-spectroscopic analyses using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Above 230 K, significant differences in onsets of water uptake and immersion freezing of different particle types were observed. Below 230 K, particles exhibited high deposition ice nucleation efficiencies and formed ice atRHicewell below homogeneous ice nucleation limits. The data suggest that water uptake and immersion freezing are more sensitive to changes in particle chemical composition compared to deposition ice nucleation. The data demonstrate that anthropogenic and marine influenced particles, exhibiting various chemical and physical properties, possess distinctly different ice nucleation efficiencies and can serve as efficient IN at atmospheric conditions typical for cirrus and mixed-phase clouds.

  4. Heterogeneous ice nucleation and water uptake by field-collected atmospheric particles below 273 K

    NASA Astrophysics Data System (ADS)

    Wang, Bingbing; Laskin, Alexander; Roedel, Tobias; Gilles, Mary K.; Moffet, Ryan C.; Tivanski, Alexei V.; Knopf, Daniel A.

    2011-11-01

    Ice formation induced by atmospheric particles through heterogeneous nucleation is not well understood. Onset conditions for heterogeneous ice nucleation and water uptake by particles collected in Los Angeles and Mexico City were determined as a function of temperature (200-273 K) and relative humidity with respect to ice (RHice). Four dominant particle types were identified including soot associated with organics, soot with organic and inorganics, inorganic particles of marine origin coated with organic material, and Pb/Zn-containing particles apportioned to emissions relevant to waste incineration. Single particle characterization was provided by micro-spectroscopic analyses using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Above 230 K, significant differences in onsets of water uptake and immersion freezing of different particle types were observed. Below 230 K, particles exhibited high deposition ice nucleation efficiencies and formed ice atRHicewell below homogeneous ice nucleation limits. The data suggest that water uptake and immersion freezing are more sensitive to changes in particle chemical composition compared to deposition ice nucleation. The data demonstrate that anthropogenic and marine influenced particles, exhibiting various chemical and physical properties, possess distinctly different ice nucleation efficiencies and can serve as efficient IN at atmospheric conditions typical for cirrus and mixed-phase clouds.

  5. Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of α-pinene

    NASA Astrophysics Data System (ADS)

    Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Garimella, Sarvesh; Dias, Antonio; Frege, Carla; Höppel, Niko; Tröstl, Jasmin; Wagner, Robert; Yan, Chao; Amorim, Antonio; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Tomé, Antonio; Virtanen, Annele; Worsnop, Douglas; Stratmann, Frank

    2016-05-01

    There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from -38 to -10 °C at 5-15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -39.0 and -37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.

  6. Heterogeneous nucleation in a glass-forming alloy

    NASA Astrophysics Data System (ADS)

    Wall, J. J.; Liu, C. T.; Rhim, W.-K.; Li, J. J. Z.; Liaw, P. K.; Choo, H.; Johnson, W. L.

    2008-06-01

    Nucleation in the undercooled liquid state in the bulk metallic glass-forming composition Zr52.5Cu17.9Ni14.6Al10Ti5 (VIT-105), produced using high purity (PA) and commercial purity (CA) raw materials was investigated using electrostatic levitation and ex situ neutron diffraction. The CA material was observed to have a lower density than the PA sample and crystallized at relatively shallow undercooling. The densities of the samples at temperatures above the solidus showed an oxygen-dependent hysteresis associated with the state change, indicating the presence of oxygen-stabilized intermetallics. The PA alloy exhibited three distinct crystallization modes dependent on the thermal history of the melt, one of which showed a net volume expansion.

  7. Heterogeneous Crystal Nucleation: The Effect of Lattice Mismatch

    NASA Astrophysics Data System (ADS)

    Tóth, Gyula I.; Tegze, György; Pusztai, Tamás; Gránásy, László

    2012-01-01

    A simple dynamical density functional theory is used to investigate freezing of an undercooled liquid in the presence of a crystalline substrate. We find that the adsorption of the crystalline phase on the substrate, the contact angle, and the height of the nucleation barrier are nonmonotonic functions of the lattice constant of the substrate. We show that the free-growth-limited model of particle-induced freezing by Greer et al. [Acta Mater. 48, 2823 (2000)ACMAFD1359-645410.1016/S1359-6454(00)00094-X] is valid for larger nanoparticles and a small anisotropy of the interface free energy. Faceting due to the small size of the foreign particle or a high anisotropy decouples free growth from the critical size of homogeneous nuclei.

  8. On the heterogeneous nucleation of mesospheric ice on meteoric smoke particles: Microphysical modeling

    NASA Astrophysics Data System (ADS)

    Asmus, Heiner; Wilms, Henrike; Strelnikov, Boris; Rapp, Markus

    2014-10-01

    Meteor smoke particles (MSP), which are thought to be the nucleation germs for mesospheric ice, are currently discussed to consist of highly absorbing materials such as magnesiowüstite, hematite or magnesium-iron-silicates and may therefore be warmer than the ambient atmosphere. In order to quantify the temperature difference between MSP and the atmosphere we developed a model to calculate the MSP equilibrium temperature in radiational and collisional balance. The temperature difference between MSP and the surrounding atmosphere strongly depends on the composition of the MSP, especially on the relative iron content, where a higher iron content leads to warmer MSP. We then derive an expression of the nucleation rate of mesospheric ice particles which explicitly accounts for this temperature difference. We find that the nucleation rate is strongly reduced by several orders of magnitude if the germ temperature is increased by only a few Kelvin. Implementing this nucleation rate depending on the germ temperature into CARMA, the Community Aerosol and Radiation Model for Atmospheres, we find that fewer but larger ice particles are formed compared to a reference scenario with no temperature difference between MSP and ambient atmosphere. This may indicate that iron-rich MSP are not ideal ice nuclei and that either other MSP-types or other nucleation pathways (e.g. wave induced heterogeneous nucleation or even homogeneous nucleation) are responsible for ice formation at the mesopause.

  9. Inclusion of line tension effect in classical nucleation theory for heterogeneous nucleation: A rigorous thermodynamic formulation and some unique conclusions

    SciTech Connect

    Singha, Sanat K.; Das, Prasanta K. Maiti, Biswajit

    2015-03-14

    A rigorous thermodynamic formulation of the geometric model for heterogeneous nucleation including line tension effect is missing till date due to the associated mathematical hurdles. In this work, we develop a novel thermodynamic formulation based on Classical Nucleation Theory (CNT), which is supposed to illustrate a systematic and a more plausible analysis for the heterogeneous nucleation on a planar surface including the line tension effect. The appreciable range of the critical microscopic contact angle (θ{sub c}), obtained from the generalized Young’s equation and the stability analysis, is θ{sub ∞} < θ{sub c} < θ′ for positive line tension and is θ{sub M} < θ{sub c} < θ{sub ∞} for negative line tension. θ{sub ∞} is the macroscopic contact angle, θ′ is the contact angle for which the Helmholtz free energy has the minimum value for the positive line tension, and θ{sub M} is the local minima of the nondimensional line tension effect for the negative line tension. The shape factor f, which is basically the dimensionless critical free energy barrier, becomes higher for lower values of θ{sub ∞} and higher values of θ{sub c} for positive line tension. The combined effect due to the presence of the triple line and the interfacial areas (f{sup L} + f{sup S}) in shape factor is always within (0, 3.2), resulting f in the range of (0, 1.7) for positive line tension. A formerly presumed appreciable range for θ{sub c}(0 < θ{sub c} < θ{sub ∞}) is found not to be true when the effect of negative line tension is considered for CNT. Estimation based on the property values of some real fluids confirms the relevance of the present analysis.

  10. Recent Developments in Modeling Heteroepitaxy/Heterogeneous Nucleation by Dynamical Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Podmaniczky, Frigyes; Tóth, Gyula I.; Tegze, György; Gránásy, László

    2015-11-01

    Crystallization of supersaturated liquids usually starts by epitaxial growth or by heterogeneous nucleation on foreign surfaces. Herein, we review recent advances made in modeling heteroepitaxy and heterogeneous nucleation on flat/modulated surfaces and nanoparticles within the framework of a simple dynamical density functional theory, known as the phase-field crystal model. It will be shown that the contact angle and the nucleation barrier are nonmonotonous functions of the lattice mismatch between the substrate and the crystalline phase. In continuous cooling studies for substrates with lattice mismatch, we recover qualitatively the Matthews-Blakeslee mechanism of stress release via the misfit dislocations. The simulations performed for particle-induced freezing will be confronted with recent analytical results, exploring thus the validity range of the latter. It will be demonstrated that time-dependent studies are essential, as investigations based on equilibrium properties often cannot identify the preferred nucleation pathways. Modeling of these phenomena is essential for designing materials on the basis of controlled nucleation and/or nano-patterning.

  11. A technique for quantifying heterogeneous ice nucleation in microlitre supercooled water droplets

    NASA Astrophysics Data System (ADS)

    Whale, T. F.; Murray, B. J.; O'Sullivan, D.; Umo, N. S.; Baustian, K. J.; Atkinson, J. D.; Morris, G. J.

    2014-09-01

    The ice content of mixed phase clouds, which contain both supercooled water and ice, affects both their lifetime and radiative properties. In many clouds, the formation of ice requires the presence of particles capable of nucleating ice. One of the most important features of ice nucleating particles (INPs) is that they are rare in comparison to cloud condensation nuclei. However, the fact that only a small fraction of aerosol particles can nucleate ice means that detection and quantification of INPs is challenging. This is particularly true at temperatures above about -20 °C since the population of particles capable of serving as INPs decreases dramatically with increasing temperature. In this paper, we describe an experimental technique in which droplets of microlitre volume containing ice nucleating material are cooled down at a controlled rate and their freezing temperatures recorded. The advantage of using large droplet volumes is that the surface area per droplet is vastly larger than in experiments focused on single aerosol particles or cloud-sized droplets. This increases the probability of observing the effect of less common, but important, high temperature INPs and therefore allows the quantification of their ice nucleation efficiency. The potential artefacts which could influence data from this experiment, and other similar experiments, are mitigated and discussed. Experimentally determined heterogeneous ice nucleation efficiencies for K-feldspar (microcline), kaolinite, chlorite, Snomax®, and silver iodide are presented.

  12. A technique for quantifying heterogeneous ice nucleation in microlitre supercooled water droplets

    NASA Astrophysics Data System (ADS)

    Whale, T. F.; Murray, B. J.; O'Sullivan, D.; Wilson, T. W.; Umo, N. S.; Baustian, K. J.; Atkinson, J. D.; Workneh, D. A.; Morris, G. J.

    2015-06-01

    In many clouds, the formation of ice requires the presence of particles capable of nucleating ice. Ice-nucleating particles (INPs) are rare in comparison to cloud condensation nuclei. However, the fact that only a small fraction of aerosol particles can nucleate ice means that detection and quantification of INPs is challenging. This is particularly true at temperatures above about -20 °C since the population of particles capable of serving as INPs decreases dramatically with increasing temperature. In this paper, we describe an experimental technique in which droplets of microlitre volume containing ice-nucleating material are cooled down at a controlled rate and their freezing temperatures recorded. The advantage of using large droplet volumes is that the surface area per droplet is vastly larger than in experiments focused on single aerosol particles or cloud-sized droplets. This increases the probability of observing the effect of less common, but important, high-temperature INPs and therefore allows the quantification of their ice nucleation efficiency. The potential artefacts which could influence data from this experiment, and other similar experiments, are mitigated and discussed. Experimentally determined heterogeneous ice nucleation efficiencies for K-feldspar (microcline), kaolinite, chlorite, NX-illite, Snomax® and silver iodide are presented.

  13. Probabilistic aspects of polymorph selection by heterogeneous nucleation on microporous hydrophobic membrane surfaces

    NASA Astrophysics Data System (ADS)

    Curcio, Efrem; Di Profio, Gianluca; Drioli, Enrico

    2008-12-01

    In this work, probabilistic aspects related to the heterogeneous nucleation on microporous hydrophobic surfaces, i.e. polymeric membranes, have been theoretically investigated to understand the ability of this innovative crystallization technique to promote the formation of different polymorphs. The theoretical results, which clarify the effects of physicochemical properties of membranes (i.e. porosity, contact angle between supersaturated solution, and polymeric substrate) on the nucleation process of polymorphs, have been used to discuss the experimentally observed selective crystallization of forms I and II of paracetamol.

  14. High variability of the heterogeneous ice nucleation potential of oxalic acid dihydrate and sodium oxalate

    NASA Astrophysics Data System (ADS)

    Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Leisner, T.

    2010-04-01

    The heterogeneous ice nucleation potential of airborne oxalic acid dihydrate and sodium oxalate particles in the deposition and condensation mode has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 244 and 228 K. Previous laboratory studies have highlighted the particular role of oxalic acid dihydrate as the only species amongst a variety of other investigated dicarboxylic acids to be capable of acting as a heterogeneous ice nucleus in both the deposition and immersion mode. We could confirm a high deposition mode ice activity for 0.03 to 0.8 μm sized oxalic acid dihydrate particles that were either formed by nucleation from a gaseous oxalic acid/air mixture or by rapid crystallisation of highly supersaturated aqueous oxalic acid solution droplets. The critical saturation ratio with respect to ice required for deposition nucleation was found to be less than 1.1 and the size-dependent ice-active fraction of the aerosol population was in the range from 0.1 to 22%. In contrast, oxalic acid dihydrate particles that had crystallised from less supersaturated solution droplets and had been allowed to slowly grow in a supersaturated environment from still unfrozen oxalic acid solution droplets over a time period of several hours were found to be much poorer heterogeneous ice nuclei. We speculate that under these conditions a crystal surface structure with less-active sites for the initiation of ice nucleation was generated. Such particles partially proved to be almost ice-inactive in both the deposition and condensation mode. At times, the heterogeneous ice nucleation ability of oxalic acid dihydrate significantly changed when the particles had been processed in preceding cloud droplet activation steps. Such behaviour was also observed for the second investigated species, namely sodium oxalate. Our experiments address the atmospheric scenario that coating layers

  15. High variability of the heterogeneous ice nucleation potential of oxalic acid dihydrate and sodium oxalate

    NASA Astrophysics Data System (ADS)

    Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Leisner, T.

    2010-08-01

    The heterogeneous ice nucleation potential of airborne oxalic acid dihydrate and sodium oxalate particles in the deposition and condensation mode has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 244 and 228 K. Previous laboratory studies have highlighted the particular role of oxalic acid dihydrate as the only species amongst a variety of other investigated dicarboxylic acids to be capable of acting as a heterogeneous ice nucleus in both the deposition and immersion mode. We could confirm a high deposition mode ice activity for 0.03 to 0.8 μm sized oxalic acid dihydrate particles that were either formed by nucleation from a gaseous oxalic acid/air mixture or by rapid crystallisation of highly supersaturated aqueous oxalic acid solution droplets. The critical saturation ratio with respect to ice required for deposition nucleation was found to be less than 1.1 and the size-dependent ice-active fraction of the aerosol population was in the range from 0.1 to 22%. In contrast, oxalic acid dihydrate particles that had crystallised from less supersaturated solution droplets and had been allowed to slowly grow in a supersaturated environment from still unfrozen oxalic acid solution droplets over a time period of several hours were found to be much poorer heterogeneous ice nuclei. We speculate that under these conditions a crystal surface structure with less-active sites for the initiation of ice nucleation was generated. Such particles partially proved to be almost ice-inactive in both the deposition and condensation mode. At times, the heterogeneous ice nucleation ability of oxalic acid dihydrate significantly changed when the particles had been processed in preceding cloud droplet activation steps. Such behaviour was also observed for the second investigated species, namely sodium oxalate. Our experiments address the atmospheric scenario that coating layers

  16. Heterogeneous Formation of Polar Stratospheric Clouds- Part 1: Nucleation of Nitric Acid Trihydrate (NAT)

    NASA Technical Reports Server (NTRS)

    Hoyle, C. R.; Engel, I.; Luo, B. P.; Pitts, M. C.; Poole, L. R.; Grooss, J.-U.; Peter, T.

    2013-01-01

    Satellite-based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid-December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled a thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed polar stratospheric clouds (PSCs) very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

  17. Heterogeneous formation of polar stratospheric clouds - Part 1: Nucleation of nitric acid trihydrate (NAT)

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Engel, I.; Luo, B. P.; Pitts, M. C.; Poole, L. R.; Grooß, J.-U.; Peter, T.

    2013-09-01

    Satellite-based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid-December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled a thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed polar stratospheric clouds (PSCs) very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

  18. Heterogeneous formation of polar stratospheric clouds - Part 1: Nucleation of nitric acid trihydrate (NAT)

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Engel, I.; Luo, B. P.; Pitts, M. C.; Poole, L. R.; Grooß, J.-U.; Peter, T.

    2013-03-01

    Satellite based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarisation (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled the thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed PSCs very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

  19. Nitride precipitation in compositionally heterogeneous alloys: Nucleation, growth and coarsening during nitriding

    NASA Astrophysics Data System (ADS)

    Van Landeghem, H. P.; Gouné, M.; Redjaïmia, A.

    2012-02-01

    A theoretical approach is proposed to take into the account nucleation, growth and coarsening of nitrides in alloys featuring heterogeneous nitrogen content. It is based on physical considerations and accounts for both bulk nitrogen diffusion, which results from the nitriding process and nitrides precipitation kinetics. It predicts local information such as average particle density, radius and volume fraction of nitrides as a function of depth. The work presented in this paper leads to two important conclusions. First, the precipitation rate is not so high that precipitation can be considered as infinitely faster than the diffusion of nitrogen into the bulk. Second, the precipitation state at a given depth depends on the local interaction between nucleation, growth and coarsening phenomena, themselves depending on the local nitrogen content. Finally, the precipitation in alloys with heterogeneous nitrogen content induced by nitriding is radically different from classical precipitation in a single phase where the driving force for precipitation is consumed.

  20. Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of α-pinene

    NASA Astrophysics Data System (ADS)

    Ignatius, K.; Kristensen, T. B.; Järvinen, E.; Nichman, L.; Fuchs, C.; Gordon, H.; Herenz, P.; Hoyle, C. R.; Duplissy, J.; Garimella, S.; Dias, A.; Frege, C.; Höppel, N.; Tröstl, J.; Wagner, R.; Yan, C.; Amorim, A.; Baltensperger, U.; Curtius, J.; Donahue, N. M.; Gallagher, M. W.; Kirkby, J.; Kulmala, M.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Tomé, A.; Virtanen, A.; Worsnop, D.; Stratmann, F.

    2015-12-01

    There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate deposition ice nucleation and thus influence cirrus cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from -38 to -10 °C at 5-15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA in the deposition mode for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -36.5 and -38.3 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nuclei (IN) budget.

  1. Heterogeneous ice nucleation and phase transition of viscous α-pinene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Virtanen, Annele; Stratmann, Frank

    2016-04-01

    There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate deposition ice nucleation and thus influence cirrus cloud properties. Global model simulations of monoterpene SOA particles suggest that viscous biogenic SOA are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle (INP) budget. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles at the CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (Ignatius et al., 2015, Järvinen et al., 2015). In the CLOUD chamber, the SOA particles were produced from the ozone initiated oxidation of α-pinene at temperatures in the range from -38 to -10° C at 5-15 % relative humidity with respect to water (RHw) to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. As the RHw was increased to between 35 % at -10° C and 80 % at -38° C, a transition to spherical shape was observed with a new in-situ optical method. This transition confirms previous modelling of the viscosity transition conditions. The ice nucleation ability of SOA particles was investigated with a new continuous flow diffusion chamber SPIN (Spectrometer for Ice Nuclei) for different SOA particle sizes. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA in the deposition mode for ice saturation ratios between 1.3 and 1.4, significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -36.5 and -38.3° C ranged from 6 to 20 % and did not depend on the particle surface area. References Ignatius, K. et al., Heterogeneous ice

  2. A novel approach to the theory of homogeneous and heterogeneous nucleation.

    PubMed

    Ruckenstein, Eli; Berim, Gersh O; Narsimhan, Ganesan

    2015-01-01

    A new approach to the theory of nucleation, formulated relatively recently by Ruckenstein, Narsimhan, and Nowakowski (see Refs. [7-16]) and developed further by Ruckenstein and other colleagues, is presented. In contrast to the classical nucleation theory, which is based on calculating the free energy of formation of a cluster of the new phase as a function of its size on the basis of macroscopic thermodynamics, the proposed theory uses the kinetic theory of fluids to calculate the condensation (W(+)) and dissociation (W(-)) rates on and from the surface of the cluster, respectively. The dissociation rate of a monomer from a cluster is evaluated from the average time spent by a surface monomer in the potential well as obtained from the solution of the Fokker-Planck equation in the phase space of position and momentum for liquid-to-solid transition and the phase space of energy for vapor-to-liquid transition. The condensation rates are calculated using traditional expressions. The knowledge of those two rates allows one to calculate the size of the critical cluster from the equality W(+)=W(-) as well as the rate of nucleation. The developed microscopic approach allows one to avoid the controversial application of classical thermodynamics to the description of nuclei which contain a few molecules. The new theory was applied to a number of cases, such as the liquid-to-solid and vapor-to-liquid phase transitions, binary nucleation, heterogeneous nucleation, nucleation on soluble particles and protein folding. The theory predicts higher nucleation rates at high saturation ratios (small critical clusters) than the classical nucleation theory for both solid-to-liquid as well as vapor-to-liquid transitions. As expected, at low saturation ratios for which the size of the critical cluster is large, the results of the new theory are consistent with those of the classical one. The present approach was combined with the density functional theory to account for the density

  3. AIDA experiments on heterogeneous ice nucleation in warm mixed-phase clouds

    NASA Astrophysics Data System (ADS)

    Möhler, Ottmar; Benz, Stefan; Leisner, Thomas; Niemand, Monika; Oehm, Caroline; Saathoff, Harald; Schnaiter, Martin; Wagner, Robert

    2010-05-01

    Clouds are important regulators of the Earth's temperature, because they scatter shortwave radiation from the sun back to space (cooling effect) and absorb long wave terrestrial radiation from the Earth surface (warming effect). About 60% of the Earth's surface is covered with clouds at any time. The response of cloud characteristics and precipitation processes to changing natural and anthropogenic aerosol sources is one of the largest uncertainties in the current understanding of climate change. Cloud development and precipitation are related to a complex chain of microphysical processes which in many cases starts with the formation of the ice phase. The occurrence and abundance of the ice phase in tropospheric clouds is strongly linked to the freezing properties of cloud droplets and aerosol solution particles as well as the abundance and properties of insoluble aerosol particles which selectively act as heterogeneous ice nuclei. Field and laboratory work have demonstrated that in particular mineral dust and bological particles can act as heterogeneous ice nuclei in mixed-phase clouds. Little is known however about the ice nucleation impact of organic matter, which has been found as a prominent compound of tropospheric aerosol particles and has the potential to form surface coatings to other aerosol particles during their transport through the atmosphere. The AIDA (Aerosol Interaction and Dynamics in the Atmosphere) facility at the Karlsruhe Institute of Technology has been used to investigate the heterogeneous ice nucleation efficiency of various dust and biological particles. The temperature, pressure and humidity conditions in the cloud chamber can be varied in a wide range of natural cloud systems. This is achieved by expansion cooling induced by strong pumping to the chamber volume. This talk will summarise AIDA experiments and results on the ice nucleation behaviour of bacteria, mineral dust particles, and dust particles coated with sulphuric acid and

  4. Strain heterogeneity and damage nucleation at grain boundaries during monotonic deformation in commercial purity titanium.

    SciTech Connect

    Bieler, T. R.; Crimp, M. A.; Yang, Y.; Wang, L.; Eisenlohr, P.; Mason, D. E.; Liu, W.; Ice, G. E.; Michigan State Univ.; Air Force Office of Scientific Research

    2009-01-01

    Heterogeneous strain was analyzed in polycrystalline, commercial-purity titanium using many experimental techniques that provide information about microstructure, dislocation arrangement, grain orientation, orientation gradients, surface topography, and local strain gradients. The recrystallized microstructure with 50-200 {micro}m grains was extensively characterized before and after deformation using 4-point bending to strains between 2% and 15%. Extremely heterogeneous deformation occurred along some grain boundaries, leading to orientation gradients exceeding 10{sup o} over 10-20 {micro}m. Patches of highly characterized micro-structure were modeled using crystal plasticity finite element (CPFE) analysis to simulate the deformation to evaluate the ability of the CPFE model to capture local deformation processes. Damage nucleation events were identified that are associated with twin interactions with grain boundaries. Progress toward identifying fracture initiation criteria based upon slip and twin interactions with grain boundaries is illustrated with related CPFE simulations of deformation in a TiAl alloy.

  5. Heterogeneous ice nucleation activity of bacteria: new laboratory experiments at simulated cloud conditions

    NASA Astrophysics Data System (ADS)

    Möhler, O.; Georgakopoulos, D. G.; Morris, C. E.; Benz, S.; Ebert, V.; Hunsmann, S.; Saathoff, H.; Schnaiter, M.; Wagner, R.

    2008-10-01

    The ice nucleation activities of five different Pseudomonas syringae, Pseudomonas viridiflava and Erwinia herbicola bacterial species and of Snomax™ were investigated in the temperature range between -5 and -15°C. Water suspensions of these bacteria were directly sprayed into the cloud chamber of the AIDA facility of Forschungszentrum Karlsruhe at a temperature of -5.7°C. At this temperature, about 1% of the Snomax™ cells induced immersion freezing of the spray droplets before the droplets evaporated in the cloud chamber. The living cells didn't induce any detectable immersion freezing in the spray droplets at -5.7°C. After evaporation of the spray droplets the bacterial cells remained as aerosol particles in the cloud chamber and were exposed to typical cloud formation conditions in experiments with expansion cooling to about -11°C. During these experiments, the bacterial cells first acted as cloud condensation nuclei to form cloud droplets. Then, only a minor fraction of the cells acted as heterogeneous ice nuclei either in the condensation or the immersion mode. The results indicate that the bacteria investigated in the present study are mainly ice active in the temperature range between -7 and -11°C with an ice nucleation (IN) active fraction of the order of 10-4. In agreement to previous literature results, the ice nucleation efficiency of Snomax™ cells was much larger with an IN active fraction of 0.2 at temperatures around -8°C.

  6. Heterogeneous nucleation of calcium oxalate crystals in the presence of membrane vesicles

    NASA Astrophysics Data System (ADS)

    Khan, Saeed R.; Whalen, Patrick O.; Glenton, Patricia A.

    1993-12-01

    Membrane-assisted crystallization of calcium oxalate was studied in vitro, using constant composition methodology. Rat renal tubular brush border membrane vesicles were incubated in supersaturated solution of calcium oxalate. Calcium and oxalate depletion started much earlier in the presence of the vesicles than in their absence; within 8, 32, or 258 min of the incubation of vesicles in calcium oxalate solutions of relative supersaturation of 12, 10 or 6 respectively. Thin plate-like crystals with jagged edges formed in association with the membrane vesicles. Since crystal nucleation in the presence of membrane vesicles started within 8 min at a relative supersaturation as low as 12, it will start significantly earlier in the urine of stone formers which is known to have higher relative supersaturation with respect to calcium oxalate. These results demonstrate that cellular membranes can efficiently induce nucleation of calcium oxalate crystals from a metastable solution in an vitro system. Similar membrane induced heterogeneous nucleation of calcium oxalate in vivo within the renal tubules is a distinct possibility.

  7. Heterogeneous Ice Nucleation During Ozonolysis of Organic Thin Films on Aqueous Solution Droplets

    NASA Astrophysics Data System (ADS)

    Wicks, G.; Cantrell, W.

    2005-12-01

    The mechanism by which ice is created affects cloud properties and processes. Although homogeneous ice nucleation is reasonably well understood, both experimentally and theoretically, heterogeneous ice nucleation is not. Since deep convection in the tropics lofts organic materials high into the atmosphere, it is important to achieve an understanding of heterogeneous nucleation by these materials and how it affects cirrus cloud formation. Sources of atmospheric organic compounds include combustion, biomass burning, emissions from vegetation, and sea spray which contains organic material from the ocean's surface. Fatty acids such as stearic acid and oleic acid are common organic constituents. The reaction of oleic acid with atmospheric ozone has recently become a model for understanding how atmospheric oxidation processes affect organic particles. Over the past six years, more than twenty publications have described reactive uptake coefficients, primary products, secondary reactions, mechanisms, and other aspects of this oxidation. With this background information in mind, we built an ozonolysis apparatus in tandem with a solution drop freezer to study the freezing point of 10-microliter, 0.25 M sodium chloride solution droplets coated with thin layers of 18-carbon fatty acids or alcohols. We determined the freezing points before and after ozonolysis for solution droplets coated with stearic acid, oleic acid, cis-13-octadecenoic acid, oleyl alcohol, and 1-octadecanol. During the experiments, temperature cycling was controlled by a computer-driven temperature controller. Results showed little change in mean freezing temperature before and after ozonolysis for all of the organic compounds studied except oleyl alcohol. The lack of a significant temperature change for oleic acid may be good news for atmospheric modelers since the well-studied reaction of ozone with oleic acid is known to give a complex mixture of products.

  8. Size-dependent surface-induced heterogeneous nucleation driven phase-change in Ge2Sb2Te5 nanowires.

    PubMed

    Lee, Se-Ho; Jung, Yeonwoong; Agarwal, Ritesh

    2008-10-01

    By combining electron microscopy and size-dependent electrical measurements, we demonstrate surface-induced heterogeneous nucleation-dominant mechanism for recrystallization of amorphous phase-change Ge2Sb2Te5 nanowires. Heterogeneous nucleation theory quantitatively predicts the nucleation rates that vary by 5 orders of magnitude from 190 to 20 nm lengthscales. Our work demonstrates that increasing the surface-to-volume ratio of nanowires has two effects: lowering of the activation energy barrier due to phonon instability and providing nucleation sites for recrystallization. The systematic study of the effect of surface in phase-change behavior is critical for understanding nanoscale phase-transitions and design of nonvolatile memory devices. PMID:18778106

  9. Shear zone nucleation and deformation transient: effect of heterogeneities and loading conditions in experimentally deformed calcite

    NASA Astrophysics Data System (ADS)

    Morales, L. F. G.; Rybacki, E.; Dresen, G. H.; Kilian, R.

    2015-12-01

    In the Earth's middle to lower crust, strain is frequently localized along ductile shear zones, which commonly nucleate at structural and material heterogeneities. To investigate shear zone nucleation and development due to heterogeneities, we performed constant strain-rate (CSR) and constant stress (CS) simple shear (torsion) deformation experiments on Carrara marble samples containing weak (limestone) inclusions. The experiments were conducted in a Paterson-type gas deformation apparatus at 900 °C temperature and 400 MPa confining pressure and maximum bulk shear strains of 3. Peak shear stress was about 20 MPa for all the samples, followed by smooth weakening and steady state behavior. The strain is predominantly localized in the host marble within the process zone in front of the inclusion, defined by a zone of intense grain size reduction due to dynamic recrystallization. In CS tests a narrow shear zone developed in front of the inclusion, whereas in CSR experiments the deformation is more heterogeneously distributed, up to g=3.. In the later, secondary foliations oblique to the process zone and alternating thin, high-strain layers are common. In samples deformed at the same shear strain (g=1), the average recrystallized grain size in the process zone is similar for CS and CSR conditions. Crystallographic preferred orientation (CPO) measurements shows that different grain sizes have slightly different CPO patterns. CPO strength varies for different grain sizes, with a CPO strength peak between 40-50 μm, decreasing progressively within smaller grain size, but with secondary peaks for different coarse-grained sizes. Our observations suggest that the initial formation and transient deformation of shear zones is strongly affected by loading conditions.

  10. Revealing heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys

    PubMed Central

    Li, Jiehua; Hage, Fredrik S.; Liu, Xiangfa; Ramasse, Quentin; Schumacher, Peter

    2016-01-01

    The heterogeneous nucleation of primary Si and eutectic Si can be attributed to the presence of AlP. Although P, in the form of AlP particles, is usually observed in the centre of primary Si, there is still a lack of detailed investigations on the distribution of P within primary Si and eutectic Si in hypereutectic Al-Si alloys at the atomic scale. Here, we report an atomic-scale experimental investigation on the distribution of P in hypereutectic Al-Si alloys. P, in the form of AlP particles, was observed in the centre of primary Si. However, no significant amount of P was detected within primary Si, eutectic Si and the Al matrix. Instead, P was observed at the interface between the Al matrix and eutectic Si, strongly indicating that P, in the form of AlP particles (or AlP ‘patch’ dependent on the P concentration), may have nucleated on the surface of the Al matrix and thereby enhanced the heterogeneous nucleation of eutectic Si. The present investigation reveals some novel insights into heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys and can be used to further develop heterogeneous nucleation mechanisms based on adsorption. PMID:27120994

  11. Revealing heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys.

    PubMed

    Li, Jiehua; Hage, Fredrik S; Liu, Xiangfa; Ramasse, Quentin; Schumacher, Peter

    2016-01-01

    The heterogeneous nucleation of primary Si and eutectic Si can be attributed to the presence of AlP. Although P, in the form of AlP particles, is usually observed in the centre of primary Si, there is still a lack of detailed investigations on the distribution of P within primary Si and eutectic Si in hypereutectic Al-Si alloys at the atomic scale. Here, we report an atomic-scale experimental investigation on the distribution of P in hypereutectic Al-Si alloys. P, in the form of AlP particles, was observed in the centre of primary Si. However, no significant amount of P was detected within primary Si, eutectic Si and the Al matrix. Instead, P was observed at the interface between the Al matrix and eutectic Si, strongly indicating that P, in the form of AlP particles (or AlP 'patch' dependent on the P concentration), may have nucleated on the surface of the Al matrix and thereby enhanced the heterogeneous nucleation of eutectic Si. The present investigation reveals some novel insights into heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys and can be used to further develop heterogeneous nucleation mechanisms based on adsorption. PMID:27120994

  12. Revealing heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys

    NASA Astrophysics Data System (ADS)

    Li, Jiehua; Hage, Fredrik S.; Liu, Xiangfa; Ramasse, Quentin; Schumacher, Peter

    2016-04-01

    The heterogeneous nucleation of primary Si and eutectic Si can be attributed to the presence of AlP. Although P, in the form of AlP particles, is usually observed in the centre of primary Si, there is still a lack of detailed investigations on the distribution of P within primary Si and eutectic Si in hypereutectic Al-Si alloys at the atomic scale. Here, we report an atomic-scale experimental investigation on the distribution of P in hypereutectic Al-Si alloys. P, in the form of AlP particles, was observed in the centre of primary Si. However, no significant amount of P was detected within primary Si, eutectic Si and the Al matrix. Instead, P was observed at the interface between the Al matrix and eutectic Si, strongly indicating that P, in the form of AlP particles (or AlP ‘patch’ dependent on the P concentration), may have nucleated on the surface of the Al matrix and thereby enhanced the heterogeneous nucleation of eutectic Si. The present investigation reveals some novel insights into heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys and can be used to further develop heterogeneous nucleation mechanisms based on adsorption.

  13. Heterogeneous-nucleation and glass-formation studies of 56Ga2O3-44CaO

    NASA Technical Reports Server (NTRS)

    Ethridge, Edwin C.; Curreri, Peter A.; Pline, David

    1987-01-01

    Glass formation and heterogeneous crystallization are described for the reluctant-glass-forming 56Ga2O3-44CaO eutectic composition. The times and temperatures for nucleation at various cooling rates and experimental conditions were measured and empirical continuous-cooling-crystallization boundaries were constructed for various heterogeneous nucleation processes. A definition for an empirical critical cooling rate to form a glass from reluctant borderline glass formers is proposed, i.e., the cooling rate that results in glass formation in 95 percent of the quenching experiments.

  14. Epitaxy versus oriented heterogeneous nucleation of organic crystals on ionic substrates

    NASA Astrophysics Data System (ADS)

    Sarma, K. R.; Shlichta, P. J.; Wilcox, W. R.; Lefever, R. A.

    1997-04-01

    It is plausible to assume that epitaxy is a special case of heterogeneous nucleation in which a restrictive crystallographic relationship exists between substrate and deposit orientations. This would mean that epitaxial substrates should always induce a perceptible reduction in the critical supercooling for nucleation of the deposit. To test this hypothesis, the critical supercoolings of six organic compounds were measured on glass and 11 single-crystal cleaved substrates including (0001) graphite, (001) mica, (111) BaF 2, SrF 2, and CaF 2, and (100) KCl, KBr, KI, NaCl, NaF, and LiF. Reductions in supercooling (with reference to glass substrates) were checked many times for repeatability and reproducibility and shown in almost all cases to have a standard deviation of 1 C or less. Acetanilide, benzoic acid, and p-bromochlorobenzene showed a wide range of supercooling reductions and were oriented on all crystalline substrates. Naphthalene and p-dibromobenzene showed only slight supercooling reductions but were oriented on all substrates, including glass. Benzil showed strong supercooling reductions only for mica and KI but was oriented not only in these cases but also with KI, BaF 2, CaF 2, and graphite. There was little correlation between degree of lattice match and either supercooling reduction or degree of preferred orientation. These results suggest that, for the systems and geometry studied, forces such as molecular dipole binding and growth anisotropy had a stronger effect than lattice match.

  15. ZnO nanoparticles favours heterogeneous nucleation in PET-ZnO nanocomposites

    NASA Astrophysics Data System (ADS)

    Agrawal, Harshita; Awasthi, Kamlendra; Saraswat, Yogendra K.; Saraswat, Vibhav K.

    2015-07-01

    The structural and chemical properties with non-isothermal crystallization kinetics of PET-ZnO nanocomposites have been reported in this article. ZnO nanoparticles have been synthesized via chemical route with average diameter 19 nm which made confirm by transmission electron microscopy and X-ray diffractometer (XRD) techniques. PET-ZnO nanocomposites have been prepared by solution casting method. The structural and chemical changes occurred in poly (ethylene terephthalate) after inclusion of ZnO nanoparticles have been studied with the help of XRD and Fourier transform infrared spectroscopy, respectively. It was observed from differential scanning calorimeter that ZnO nanoparticles work as nucleating agent for heterogeneous nucleation in PET matrix under non-isothermal crystallization process. The combined Avrami and Ozawa models have been proved adequate to explain non-isothermal crystallization kinetics of PET-ZnO nanocomposites, and also, ZnO nanoparticles have been caused to reduce crystallization activation energy in pristine PET as per the applied Kissinger model.

  16. Heterogeneous nucleation of Al melt in symmetrical or asymmetrical confined nanoslits.

    PubMed

    Zhou, Xuyan; Liu, Sida; Wang, Long; Li, Yifan; Wu, Weikang; Duan, Yunrui; Li, Hui

    2016-06-16

    MD simulations are performed to study the solidification of Al melt in confined nanoslits (NSs) constructed by identical or different substrates, as well as on Fe substrates. Compared to the single substrate, the confined NS could promote the crystallization of Al melt, and its size has a significant impact on the solidified structure. In symmetrical NSs, liquid Al atoms would stack based on the atomic arrangement mode of the substrate, however in asymmetrical confined NSs, the atomic arrangement mode of liquid Al is governed by the constitution of asymmetrical substrates. Specifically, for the NS formed by Fe(110) and Fe(111) substrates, the induced region from the Fe(110) substrate is much bigger than that from Fe(111). Moreover, the freezing of liquid Al in asymmetrical NSs constructed from copper and iron has also been studied. These results throw light on heterogeneous nucleation in confined space. PMID:27272439

  17. A case of type I polar stratospheric cloud formation by heterogeneous nucleation

    NASA Technical Reports Server (NTRS)

    Pueschel, R. F.; Ferry, G. V.; Snetsinger, K. G.; Goodman, J.; Dye, J. E.; Baumgardner, D.; Gandrud, B. W.

    1992-01-01

    The NASA ER-2 aircraft flew on January 24, 1989, from Stavanger to Spitsbergen, Norway, at the 430-440 K potential temperature surface (19.2-19.8 km pressure altitude). Aerosols were sampled continuously by an optical particle counter (PMS-FSSP300) for concentration and size analyses, and during five 10-min intervals by four wire and one replicator impactor for concentration, size, composition, and phase analysis. During sampling, the air saturation of H2O with respect to ice changed from 20 to 100 percent, and of HNO3 with respect to nitric acid trihydrate (NAT) from subsaturation to supersaturation. Data from both instruments indicate a condensation of hydrochloric acid and, later, nitric acid on the background aerosol particles as the ambient temperature decreases along the flight track. This heterogeneous nucleation mechanism generates type I polar stratospheric cloud particles of 10-fold enhanced optical depth, which could play a role in stratospheric ozone depletion.

  18. Heterogeneous nucleation of Al melt in symmetrical or asymmetrical confined nanoslits

    NASA Astrophysics Data System (ADS)

    Zhou, Xuyan; Liu, Sida; Wang, Long; Li, Yifan; Wu, Weikang; Duan, Yunrui; Li, Hui

    2016-06-01

    MD simulations are performed to study the solidification of Al melt in confined nanoslits (NSs) constructed by identical or different substrates, as well as on Fe substrates. Compared to the single substrate, the confined NS could promote the crystallization of Al melt, and its size has a significant impact on the solidified structure. In symmetrical NSs, liquid Al atoms would stack based on the atomic arrangement mode of the substrate, however in asymmetrical confined NSs, the atomic arrangement mode of liquid Al is governed by the constitution of asymmetrical substrates. Specifically, for the NS formed by Fe(110) and Fe(111) substrates, the induced region from the Fe(110) substrate is much bigger than that from Fe(111). Moreover, the freezing of liquid Al in asymmetrical NSs constructed from copper and iron has also been studied. These results throw light on heterogeneous nucleation in confined space.

  19. Strain Heterogeneity and Damage Nucleation at Grain Boundaries during Monotonic Deformation in Commercial Purity Titanium

    SciTech Connect

    Bieler, T. R.; Crimp, M. A.; Yang, Y.; Eisenlohr, P.; Mason, D. E.; Liu, W.; Ice, Gene E

    2009-01-01

    Heteroeneous strain was analyzed in polycrystalline, commercial-purity titanium using many experimental techniques that provide information about microstructure, dislocation arrangement, grain orientation, orientation gradients, surface topography, and local strain gradients. The recrystallized microstructure with 50-200 ?m grains was extensively characterized before and after deformation using 4-point bending to strains between 2% and 15%. Extremely heterogeneous deformation occurred along some grain boundaries, leading to orientation gradients exceeding 10{sup o} over 10-20 {micro}m. Patches of highly characterized microstructure were modeled using crystal plasticity finite element (CPFE) analysis to simulate the deformation to evaluate the ability of the CPFE model to capture local deformation processes. Damage nucleation events were identified that are associated with twin interactions with grain boundaries. Progress toward identifying fracture initiation criteria based upon slip and twin interactions with grain boundaries is illustrated with related CPFE simulations of deformation in a TiAl alloy.

  20. Transformation of truncated gold octahedrons into triangular nanoprisms through the heterogeneous nucleation of silver.

    PubMed

    Gilroy, K D; Sundar, A; Hajfathalian, M; Yaghoubzade, A; Tan, T; Sil, D; Borguet, E; Hughes, R A; Neretina, S

    2015-04-21

    Described is a straightforward procedure for forming organized substrate-immobilized nanoprisms which are single crystalline, surfactant-free and which form a heteroepitaxial relationship with the underlying substrate. The devised route utilizes truncated Au octahedrons formed through solid state dewetting techniques as high temperature heterogeneous nucleation sites for Ag adatoms which are arriving to the substrate surface in the vapour phase. Observed is a morphological and compositional transformation of the Au structures to triangular nanoprisms comprised of a homogeneous AuAg alloy. During this transformation, the localized surface plasmon resonance red-shifts, broadens and increases in strength. The shape transformation, which cannot be rationalized using thermodynamic arguments dependent on the surface energy minimization, is described in terms of a kinetically driven growth mode, previously predicted by molecular dynamic simulations. The so-formed structures, when coated with a thin layer of Pd, are demonstrated as plasmonic sensing elements for hydrogen detection. PMID:25807181

  1. Transformation of truncated gold octahedrons into triangular nanoprisms through the heterogeneous nucleation of silver

    NASA Astrophysics Data System (ADS)

    Gilroy, K. D.; Sundar, A.; Hajfathalian, M.; Yaghoubzade, A.; Tan, T.; Sil, D.; Borguet, E.; Hughes, R. A.; Neretina, S.

    2015-04-01

    Described is a straightforward procedure for forming organized substrate-immobilized nanoprisms which are single crystalline, surfactant-free and which form a heteroepitaxial relationship with the underlying substrate. The devised route utilizes truncated Au octahedrons formed through solid state dewetting techniques as high temperature heterogeneous nucleation sites for Ag adatoms which are arriving to the substrate surface in the vapour phase. Observed is a morphological and compositional transformation of the Au structures to triangular nanoprisms comprised of a homogeneous AuAg alloy. During this transformation, the localized surface plasmon resonance red-shifts, broadens and increases in strength. The shape transformation, which cannot be rationalized using thermodynamic arguments dependent on the surface energy minimization, is described in terms of a kinetically driven growth mode, previously predicted by molecular dynamic simulations. The so-formed structures, when coated with a thin layer of Pd, are demonstrated as plasmonic sensing elements for hydrogen detection.Described is a straightforward procedure for forming organized substrate-immobilized nanoprisms which are single crystalline, surfactant-free and which form a heteroepitaxial relationship with the underlying substrate. The devised route utilizes truncated Au octahedrons formed through solid state dewetting techniques as high temperature heterogeneous nucleation sites for Ag adatoms which are arriving to the substrate surface in the vapour phase. Observed is a morphological and compositional transformation of the Au structures to triangular nanoprisms comprised of a homogeneous AuAg alloy. During this transformation, the localized surface plasmon resonance red-shifts, broadens and increases in strength. The shape transformation, which cannot be rationalized using thermodynamic arguments dependent on the surface energy minimization, is described in terms of a kinetically driven growth mode

  2. Line-tension-induced scenario of heterogeneous nucleation on a spherical substrate and in a spherical cavity

    NASA Astrophysics Data System (ADS)

    Iwamatsu, Masao

    2015-07-01

    Line-tension-induced scenario of heterogeneous nucleation is studied for a lens-shaped nucleus with a finite contact angle nucleated on a spherical substrate and on the bottom of the wall of a spherical cavity. The effect of line tension on the free energy of a critical nucleus can be separated from the usual volume term. By comparing the free energy of a lens-shaped critical nucleus of a finite contact angle with that of a spherical nucleus, we find that a spherical nucleus may have a lower free energy than a lens-shaped nucleus when the line tension is positive and large, which is similar to the drying transition predicted by Widom [B. Widom, J. Phys. Chem. 99, 2803 (1995)]. Then, the homogeneous nucleation rather than the heterogeneous nucleation will be favorable. Similarly, the free energy of a lens-shaped nucleus becomes negative when the line tension is negative and large. Then, the barrier-less nucleation with no thermal activation called athermal nucleation will be realized.

  3. Heterogeneous nucleation as the predominant mode of crystallization in natural magmas: numerical model and implications for crystal-melt interaction

    NASA Astrophysics Data System (ADS)

    Špillar, Václav; Dolejš, David

    2015-01-01

    Crystallization of natural magmas is inherently a disequilibrium process, which involves nucleation and growth kinetics, melt-crystal mechanical interactions and subsolidus modifications, which are all recorded in the resulting rock texture. We use a new high-resolution three-dimensional numerical model to address the significance and consequences of homogeneous versus heterogeneous crystal nucleation in silicate magmas. With increasing amount of heterogeneous nuclei during crystallization, initially equigranular textures evolve to porphyritic, bimodal and spherulitic types. The corresponding crystal size distributions (CSDs) become concave-up curved, the clustering index progressively decreases, and the grain contact relationships record increased clustering. Concave-up curved CSDs previously interpreted as resulting from multistage crystallization, mixing of crystal populations, grain agglomeration, or size-dependent growth are now predicted, consistently with other size, spatial and clustering parameters, to form by heterogeneous crystal nucleation. Correlation relationships between various textural parameters and the fraction of heterogeneous nuclei are calibrated and used on representative volcanic and plutonic rocks, including cumulate rocks, to deduce the fraction of heterogeneous nuclei. The results indicate that ~60 to ~99 % of all nuclei are heterogeneous. For plutonic and cumulate rocks, the estimate of the heterogeneous nuclei fraction based on the clustering index is significantly lower than other estimates. Such discrepancies, in general, point to the occurrence of other processes, and here, the results imply that crystal-mush compaction and interstitial melt extraction were involved during the magma solidification. Formation of crystals in clusters, implicit for heterogeneous nucleation, implies that greater efficiency of crystal-melt separation is expected in these situations.

  4. Effect of Manganese Sulphide Size on the Precipitation of Tin Heterogeneous Nucleation in as-Cast Steel

    NASA Astrophysics Data System (ADS)

    Sun, Guilin; Song, Bo; Tao, Sufen; Cai, Zeyun

    2015-05-01

    Tramp elements in steels such as tin have been thought harmful because of the hot brittleness at grain boundaries and will be enriched in new steels because of difficulty of removal. It has been an important and difficult matter for metallurgist to use these elements. In the present paper, the as-cast steel containing high concentration of tin is prepared in laboratory and tin precipitates at the manganese sulphide inclusions have been found. A theoretical model is established to calculate the size of manganese sulphide inclusions acted as the heterogeneous nucleation site of tin precipitation. The results show that the inclusions with the smaller contact angle between tin precipitate is more advantageous to be the nucleus of tin heterogeneous nucleation. In this experiment, the manganese sulphide inclusions whose size is 2~4 μm in diameter can act as the nuclei of the nucleation of tin precipitation.

  5. Laboratory Measurements on Heterogeneous Nucleation and Growth of Water Vapor on Meteor Smoke Particle Analogues under Conditions of the Mesopause

    NASA Astrophysics Data System (ADS)

    Duft, D.; Nachbar, M.; Wilms, H.; Rapp, M.; Leisner, T.

    2014-12-01

    Heterogeneous nucleation of water vapor on charged nanometer sized (radius< 2nm) meteor smoke particles (MSP) is believed to be the dominating nucleation process in the mesopause region leading to the formation of polar mesospheric clouds (PMC). However, application of classical nucleation theory to the cold conditions of the polar summer mesopause comprises large uncertainties giving rise to strongly variant model predictions of PMC formation. To reduce these uncertainties laboratory measurements of nucleation and growth rates are required. We use an electrodynamic trap to investigate the nucleation and growth of water vapor on singly charged sub-3nm MSP analogues in the laboratory under mesospheric conditions typical during PMC growth initiation. The particles are created in a microwave plasma particle source and stored in a quadrupole ion trap under mesospheric pressure and temperature, where they are subjected to the high supersaturation necessary for nucleation and growth on nanometer sized particles. The particle mass and mass change by water accretion is monitored with a time-of-flight mass spectrometer as a function of residence time under supersaturated conditions. In this contribution we present for the first time measurements of nucleation and growth rates of water vapor on MSP analogues with an initial radius between 1.5nm and 3 nm. Contact parameter, sticking coefficient as well as charge effects on vapor pressure of small particles at mesospheric conditions are presented. These parameters are essential for the microphysical understanding and further global model calculations of PMC formation.

  6. Heterogeneous Nucleation of n-Butanol Vapor on Submicrometer Particles of SiO2 and TiO2.

    PubMed

    Chen; Huang; Tao

    1999-03-15

    Condensation of a supersaturated vapor of n-butanol on monodisperse submicrometer particles is investigated in a flow cloud chamber (FCC). The size dependence of critical supersaturation in the range of 20 to 90 nm is experimentally determined. Two types of aerosol, SiO2 and TiO2, are tested. The results show that both aerosols induce heterogeneous nucleation better than perfectly wetted particles. The experimental critical supersaturation is smaller than that predicted by the Fletcher version of Volmer theory of heterogeneous nucleation even with the line tension and surface diffusion taken into account and has a size dependence in qualitative agreement with that theoretically predicted but to a lesser degree. The discrepancy can not be fully accounted for by the effects of line tension and surface diffusion and the existing theory concerning the curvature-dependent physical properties. The law of corresponding states was extended to the heterogeneous nucleation, and a simple correlation was observed. We conclude that the macroscopic theory of heterogeneous nucleation leads to a prediction of critical supersaturation higher than that experimentally measured. Copyright 1999 Academic Press. PMID:10049535

  7. Heterogeneous Nucleation and Growth of Barium Sulfate at Organic-Water Interfaces: Interplay between Surface Hydrophobicity and Ba(2+) Adsorption.

    PubMed

    Dai, Chong; Stack, Andrew G; Koishi, Ayumi; Fernandez-Martinez, Alejandro; Lee, Sang Soo; Hu, Yandi

    2016-05-31

    Barium sulfate (BaSO4) is a common scale-forming mineral in natural and engineered systems, yet the rates and mechanisms of heterogeneous BaSO4 nucleation are not understood. To address these, we created idealized interfaces on which to study heterogeneous nucleation rates and mechanisms, which also are good models for organic-water interfaces: self-assembled thin films terminated with different functional groups (i.e., -COOH, -SH, or mixed -SH & COOH) coated on glass slides. BaSO4 precipitation on coatings from Barite-supersaturated solutions (saturation index, SI, = 1.1) was investigated using grazing-incidence small-angle X-ray scattering. After reaction for 1 h, a little amount of BaSO4 formed on hydrophilic bare and -COOH coated glasses. Meanwhile, BaSO4 nucleation was significantly promoted on hydrophobic -SH and mixed -SH & COOH coatings. This is because substrate hydrophobicity likely affected the interfacial energy and hence thermodynamic favorability of heterogeneous nucleation. The heterogeneous BaSO4 nucleation and growth kinetics were found to be affected by the amount of Ba(2+) adsorption onto the substrate and incipient BaSO4 nuclei. The importance of Ba(2+) adsorption was further corroborated by the finding that precipitation rate increased under [Ba(2+)]/[SO4(2-)] concentration ratios >1. These observations suggest that thermodynamic favorability for nucleation is governed by substrate-water interfacial energy, while given favorable thermodynamics, the rate is governed by ion attachment to substrates and incipient nuclei. PMID:27163157

  8. Aluminum affects heterogeneous Fe(III) (Hydr)oxide nucleation, growth, and ostwald ripening.

    PubMed

    Hu, Yandi; Li, Qingyun; Lee, Byeongdu; Jun, Young-Shin

    2014-01-01

    Heterogeneous coprecipitation of iron and aluminum oxides is an important process for pollutant immobilization and removal in natural and engineered aqueous environments. Here, using a synchrotron-based small-angle X-ray scattering technique, we studied heterogeneous nucleation and growth of Fe(III) (hydr)oxide on quartz under conditions found in acid mine drainage (at pH = 3.7 ± 0.2, [Fe(3+)] = 10(-4) M) with different initial aqueous Al/Fe ratios (0:1, 1:1, and 5:1). Interestingly, although the atomic ratios of Al/Fe in the newly formed Fe(III) (hydr)oxide precipitates were less than 1%, the in situ particle size and volume evolutions of the precipitates on quartz were significantly influenced by aqueous Al/Fe ratios. At the end of the 3 h experiments, with aqueous Al/Fe ratios of 0:1, 1:1, and 5:1, the average radii of gyration of particles on quartz were 5.7 ± 0.3, 4.6 ± 0.1, and 3.7 ± 0.3 nm, respectively, and the ratio of total particle volumes on quartz was 1.7:3.4:1.0. The Fe(III) (hydr)oxide precipitates were poorly crystallized, and were positively charged in all solutions. In the presence of Al(3+), Al(3+) adsorption onto quartz changed the surface charge of quartz from negative to positive, which caused the slower heterogeneous growth of Fe(III) (hydr)oxide on quartz. Furthermore, Al affected the amount of water included in the Fe(III) (hydr)oxides, which can influence their adsorption capacity. This study yielded important information usable for pollutant removal not only in natural environments, but also in engineered water treatment processes. PMID:24289329

  9. Heterogeneous chemistry of atmospheric mineral dust particles and their resulting cloud-nucleation properties

    NASA Astrophysics Data System (ADS)

    Sullivan, Ryan Christopher

    Mineral dust particles are a major component of tropospheric aerosol mass and affect regional and global atmospheric chemistry and climate. Dust particles experience heterogeneous reactions with atmospheric gases that alter the gas and particle-phase chemistry. These in turn influence the warm and cold cloud nucleation ability and optical properties of the dust particles. This dissertation investigates the atmospheric chemistry of mineral dust particles and their role in warm cloud nucleation through a combination of synergistic field measurements, laboratory experiments, and theoretical modeling. In-situ measurements made with a single-particle mass spectrometer during the ACE-Asia field campaign in 2001 provide the motivation for this work. The observed mixing state of the individual ambient particles with secondary organic and inorganic components is described in Chapter 2. A large Asian dust storm occurred during the campaign and produced dramatic changes in the aerosol's composition and mixing state. The effect of particle size and mineralogy on the atmospheric processing of individual dust particles is explored in Chapters 3 & 4. Sulfate was found to accumulate preferentially in submicron iron and aluminosilicate-rich dust particles, while nitrate and chloride were enriched in supermicron calcite-rich dust. The mineral dust (and sea salt particles) were also enriched in oxalic acid, the dominant component of water soluble organic carbon. Chapter 5 explores the roles of gas-phase photochemistry and partitioning of the diacids to the alkaline particles in producing this unique behavior. The effect of the dust's mixing state with secondary organic and inorganic components on the dust particles' solubility, hygroscopicity, and thus warm cloud nucleation properties is explored experimentally and theoretically in Chapter 6. Cloud condensation nucleation (CCN) activation curves revealed that while calcium nitrate and calcium chloride particles were very hygroscopic

  10. Laboratory measurements of heterogeneous CO2 ice nucleation on nanoparticles under conditions relevant to the Martian mesosphere

    NASA Astrophysics Data System (ADS)

    Nachbar, Mario; Duft, Denis; Mangan, Thomas Peter; Martin, Juan Carlos Gomez; Plane, John M. C.; Leisner, Thomas

    2016-05-01

    Clouds of CO2 ice particles have been observed in the Martian mesosphere. These clouds are believed to be formed through heterogeneous nucleation of CO2 on nanometer-sized meteoric smoke particles (MSPs) or upward propagated Martian dust particles (MDPs). Large uncertainties still exist in parameterizing the microphysical formation process of these clouds as key physicochemical parameters are not well known. We present measurements on the nucleation and growth of CO2 ice on sub-4 nm radius iron oxide and silica particles representing MSPs at conditions close to the mesosphere of Mars. For both particle materials we determine the desorption energy of CO2 to be ΔFdes = (18.5 ± 0.2) kJ mol-1 corresponding to ΔFdes = (0.192 ± 0.002) eV and obtain m = 0.78 ± 0.02 for the contact parameter that governs heterogeneous nucleation by analyzing the measurements using classical heterogeneous nucleation theory. We did not find any temperature dependence for the contact parameter in the temperature range examined (64 K to 73 K). By applying these values for MSPs in the Martian mesosphere, we derive characteristic temperatures for the onset of CO2 ice nucleation, which are 8-18 K below the CO2 frost point temperature, depending on particle size. This is in line with the occurrence of highly supersaturated conditions extending to 20 K below frost point temperature without the observation of clouds. Moreover, the sticking coefficient of CO2 on solid CO2 was determined to be near unity. We further argue that the same parameters can be applied to CO2 nucleation on upward propagated MDPs.

  11. Laboratory Experiments on Heterogeneous CO2 Ice Nucleation and Growth Rates on Meteor Smoke Particle Analogues in the Martian Mesosphere

    NASA Astrophysics Data System (ADS)

    Nachbar, M.; Duft, D.; Mangan, T.; Gomez Martin, J. C.; Plane, J. M. C.; Leisner, T.

    2014-12-01

    CO2 ice particles with radii of about 100 nm have been detected in the Martian mesosphere region at heights between 80 km and 100 km. Gravity waves propagating upward cause a cooling of this region leading to temporary supersaturated conditions during which heterogeneous nucleation of CO2 can take place. Large uncertainties in describing the nucleation processes at the extreme conditions of the Martian mesopause region state the need of laboratory measurements. Sub-3 nanometer radius meteor smoke particle (MSP) analogues are created in a microwave plasma and stored in an electrodynamic trap for examining CO2 ice nucleation as well as growth rates at low particle temperatures between 60 K and 75 K and CO2 concentrations up to 1017 m-3 which are reasonably close to conditions present in the Martian mesosphere. Ice nucleation and growth processes of the particles are examined by analyzing the mass distribution of the particles with a time of flight spectrometer as a function of the residence time under supersaturated conditions. In this paper, first measurements of CO2 ice nucleation and growth on iron oxide and silicate particles will be presented. These results are extrapolated to realistic Martian conditions reducing the large uncertainty in dealing with CO2 ice nucleation on MSPs.

  12. In Situ Determination of Interfacial Energies between Heterogeneously Nucleated CaCO 3 and Quartz Substrates: Thermodynamics of CO 2 Mineral Trapping

    SciTech Connect

    Fernandez-Martinez, Alejandro; Hu, Yandi; Lee, Byeongdu; Jun, Young-Shin; Waychunas, Glenn A.

    2013-01-02

    The precipitation of carbonate minerals—mineral trapping—is considered one of the safest sequestration mechanisms ensuring long-term geologic storage of CO{sub 2}. However, little is known about the thermodynamic factors controlling the extent of heterogeneous nucleation at mineral surfaces exposed to the fluids in porous reservoirs. The goal of this study is to determine the thermodynamic factors controlling heterogeneous nucleation of carbonate minerals on pristine quartz (100) surfaces, which are assumed representative of sandstone reservoirs. To probe CaCO{sub 3} nucleation on quartz (100) in solution and with nanoscale resolution, an in situ grazing incidence small-angle X-ray scattering technique has been utilized. With this method, a value of α = 36 ± 5 mJ/m{sup 2} for the effective interfacial free energy governing heterogeneous nucleation of CaCO{sub 3} has been obtained by measuring nucleation rates at different solution supersaturations. This value is lower than the interfacial energy governing calcite homogeneous nucleation (α ≈ 120 mJ/m{sup 2}), suggesting that heterogeneous nucleation of calcium carbonate is favored on quartz (100) at ambient pressure and temperature conditions, with nucleation barriers between 2.5% and 15% lower than those expected for homogeneous nucleation. These observations yield important quantitative parameters readily usable in reactive transport models of nucleation at the reservoir scale.

  13. Heterogeneous nucleation of the primary phase in the rapid solidification of Al-4.5wt%Cu alloy droplet

    NASA Astrophysics Data System (ADS)

    Maitre, A.; Bogno, A.-A.; Bedel, M.; Reinhart, G.; Henein, H.

    2015-06-01

    This paper reports on rapid solidification of Al-Cu alloys. A heterogeneous nucleation/growth model coupled with a thermal model of a falling droplet through a stagnant gas was developed. The primary undercooling as well as the number of nucleation points was compared with Al-Cu alloy droplets produced by Impulse Atomization (IA). Based on experimental results from Neutron Diffraction, secondary (eutectic) phases were obtained. Then, primary and secondary undercoolings were estimated using the metastable extensions of solidus and liquidus lines calculated by Thermo-Calc. Moreover, Synchrotron X-ray microtomography has been performed on Al-4.5wt%Cu droplets. The undercoolings are in good agreement. Results also evidence the presence of one nucleation point and are in agreement with the experimental observations.

  14. Parameterization of heterogeneous ice nucleation on mineral dust particles: An application in a regional scale model

    NASA Astrophysics Data System (ADS)

    Niemand, M.; Vogel, B.; Vogel, H.; Connolly, P.; Klein, H.; Bingemer, H.; Hoose, C.; Moehler, O.; Leisner, T.

    2010-12-01

    In climate and weather models, the quantitative description of aerosol and cloud processes relies on simplified assumptions. This contributes major uncertainties to the prediction of global and regional climate change. The parameterization of heterogeneous ice nucleation is a step towards improving our current knowledge of the importance of the cloud ice phase in weather and climate models and can aid in the theoretical understanding of such processes. This contribution presents a new parameterization derived from a large number of experiments carried out at the aerosol and cloud chamber facility AIDA [1] of Karlsruhe Institute of Technology. AIDA is especially suitable to study ice nucleation processes at tropospheric and stratospheric cloud conditions covering a wide range of temperature and pressure. During pumping expansion, cooling rates between -0.3 and -5.0 K/min, equating to vertical wind velocities of 0.5 to 8 m/s, and a relative humidity range of up to more than 200% with respect to ice can be reached. The parameterization is valid for the temperature range -35°C to -15°C. In order to derive and test the parameterization a parameter called the ice-active surface site density was calculated for a number of different experiments with mineral dust acting as ice nuclei in the immersion and/or deposition mode. An exponential function was fitted to this data of ice-active surface site density vs. temperature. The curve fit was then used within the bin microphysical model ACPIM [2] to simulate the ice formation rates from the experiments. The major dust outbreak over the Sahara in May 2008 which was followed by a dust transport over the Mediterranean and Western Europe was simulated using the regional scale online coupled model system COSMO-ART (Vogel et al., 2009). Based on the model results the exponential curve fit was used to calculate the ice nuclei number concentration at Kleiner Feldberg (Germany). The results will be compared to measurements from

  15. A theory-based parameterization for heterogeneous ice nucleation and implications for the simulation of ice processes in atmospheric models

    NASA Astrophysics Data System (ADS)

    Savre, J.; Ekman, A. M. L.

    2015-05-01

    A new parameterization for heterogeneous ice nucleation constrained by laboratory data and based on classical nucleation theory is introduced. Key features of the parameterization include the following: a consistent and modular modeling framework for treating condensation/immersion and deposition freezing, the possibility to consider various potential ice nucleating particle types (e.g., dust, black carbon, and bacteria), and the possibility to account for an aerosol size distribution. The ice nucleating ability of each aerosol type is described using a contact angle (θ) probability density function (PDF). A new modeling strategy is described to allow the θ PDF to evolve in time so that the most efficient ice nuclei (associated with the lowest θ values) are progressively removed as they nucleate ice. A computationally efficient quasi Monte Carlo method is used to integrate the computed ice nucleation rates over both size and contact angle distributions. The parameterization is employed in a parcel model, forced by an ensemble of Lagrangian trajectories extracted from a three-dimensional simulation of a springtime low-level Arctic mixed-phase cloud, in order to evaluate the accuracy and convergence of the method using different settings. The same model setup is then employed to examine the importance of various parameters for the simulated ice production. Modeling the time evolution of the θ PDF is found to be particularly crucial; assuming a time-independent θ PDF significantly overestimates the ice nucleation rates. It is stressed that the capacity of black carbon (BC) to form ice in the condensation/immersion freezing mode is highly uncertain, in particular at temperatures warmer than -20°C. In its current version, the parameterization most likely overestimates ice initiation by BC.

  16. Heterogeneous nucleation of supercooled water, and the effect of an added catalyst

    PubMed Central

    Heneghan, A. F.; Wilson, P. W.; Haymet, A. D. J.

    2002-01-01

    The statistics of liquid-to-crystal nucleation are measured rigorously by using a recently developed automated lag-time apparatus (ALTA). A single sample, in this case a sample of pure water both with and without an (insoluble) AgI crystal, is repeatedly cooled, nucleated, and thawed. Analysis of the data, coupled with a second kind of experiment, shows that the statistics of nucleation are consistent with a first-order kinetic mechanism over a wide range of supercooling temperatures. The limitations of classical nucleation theory are exhibited. Our analysis unifies many related experiments in biology, physics, chemistry, and chemical engineering. PMID:12114536

  17. Heterogeneous Ice Nucleation on Kaolinite Particles, Particle Surrogates of HUmic-Like Substances (HULIS), and Organics-Containing Urban Aerosols

    NASA Astrophysics Data System (ADS)

    Wang, B.; Knopf, D. A.

    2009-12-01

    Aerosol particles can affect the global radiation budget through aerosol-cloud interactions by acting as cloud condensation nuclei and ice nuclei (IN) thereby inducing new clouds and/or modifying the radiative properties of existing clouds. This study presents heterogeneous ice nucleation data as a function of particle temperature and relative humidity with respect to ice (RHice) for laboratory generated kaolinite particles, leonardite and fulvic acid particles serving as surrogates for aerosols composed of HULIS, and organics-containing urban aerosols collected during the MILAGRO (Mexico City) campaign. These experiments are conducted using an improved version of a previously developed ice nucleation cell coupled to an optical microscope which allows to control particle temperatures between 200-300 K and corresponding atmospherically relevant RHice. Micrometer-sized particles are deposited onto a hydrophobic substrate and are placed in the nucleation cell. To validate the experimental approach and quality of substrates, ice nucleation experiments were performed 1. on plain sample substrates and 2. using a well studied IN: kaolinite particles. The results corroborate that kaolinite particles are efficient IN inducing ice nucleation at 102-120% RHice via deposition mode at temperatures between 200 and 245 K, in agreement with previous studies. The ice nucleation efficiency of leonardite and fulvic acid particles with median diameters of 2-3 µm is determined. Leonardite particles nucleate ice via deposition mode at 120-140% RHice for temperatures between 200 and 240 K with the minimum RHice threshold observed at 220 K. Fulvic acid particles nucleate ice via deposition mode at 135-150% RHice for temperatures between 200 and 230 K with the minimum RHice threshold determined at 216 K. The fulvic acid particles take up water at RH>95% for temperatures between 235 and 250 K. The contact angle derived from experimentally determined heterogeneous ice nucleation rate

  18. Unprecedented Evidence for Large Scale Heterogeneous Nucleation of Polar Stratospheric Clouds, Likely by Nanometer-Sized Meteoritic Particles

    NASA Astrophysics Data System (ADS)

    Engel, I.; Pitts, M. C.; Luo, B.; Hoyle, C. R.; Zobrist, B.; Jacot, L.; Poole, L. R.; Grooss, J.; Weigel, R.; Borrmann, S.; Ebert, M.; Duprat, J.; Peter, T.

    2012-12-01

    Recent observations cast serious doubts on our understanding of the processes responsible for polar stratospheric cloud (PSC) formation. PSCs play crucial roles in polar ozone chemistry by hosting heterogeneous reactions and by removal of reactive nitrogen through sedimenting nitric acid trihydrate (NAT) particles. An extensive field campaign took place in the Arctic during the winter 2009/2010 within the European Union project RECONCILE, complemented by measurements from the spaceborne CALIOP (Cloud-Aerosol LIdar with Orthogonal Polarization) instrument. Through trajectory and microphysical box model calculations, we analyzed CALIOP data from the RECONCILE winter to investigate the nucleation of PSC particles in detail. One significant finding was that liquid/NAT mixture PSCs were prevalent in late December 2009, a period during which no ice PSCs were observed, and temperatures were higher by 6 K than required for homogeneous ice freezing at the onset of PSC formation. These NAT particles must have formed through some non-ice nucleation mechanism, which runs counter to the widely held view that the only efficient NAT nuclei were ice crystals formed by homogeneous freezing of STS droplets. Furthermore, in mid-January 2010, a large region of the Arctic vortex cooled below the frost point, leading to widespread synoptic-scale ice PSCs, unusual for the Arctic. Our modeling studies indicate that a match with the CALIOP data calls for new heterogeneous nucleation mechanisms for both NAT and ice particles, namely freezing on nanometer-sized, solid nuclei immersed in the liquid stratospheric aerosols. Number concentrations of non-volatile particles were measured in situ during RECONCILE by means of the heated channel of the condensation nuclei (CN) counter COPAS on board of the high-flying aircraft Geophysica. 60-80 % of all CN survived heating to 250 °C. Offline Environmental Scanning Electron Microscopy and Energy Dispersive X-Ray Analysis of RECONCILE impactor samples

  19. A first test of the hypothesis of biogenic magnetite-based heterogeneous ice-crystal nucleation in cryopreservation.

    PubMed

    Kobayashi, Atsuko; Golash, Harry N; Kirschvink, Joseph L

    2016-06-01

    An outstanding biophysical puzzle is focused on the apparent ability of weak, extremely low-frequency oscillating magnetic fields to enhance cryopreservation of many biological tissues. A recent theory holds that these weak magnetic fields could be inhibiting ice-crystal nucleation on the nanocrystals of biological magnetite (Fe3O4, an inverse cubic spinel) that are present in many plant and animal tissues by causing them to oscillate. In this theory, magnetically-induced mechanical oscillations disrupt the ability of water molecules to nucleate on the surface of the magnetite nanocrystals. However, the ability of the magnetite crystal lattice to serve as a template for heterogeneous ice crystal nucleation is as yet unknown, particularly for particles in the 10-100 nm size range. Here we report that the addition of trace-amounts of finely-dispersed magnetite into ultrapure water samples reduces strongly the incidence of supercooling, as measured in experiments conducted using a controlled freezing apparatus with multiple thermocouples. SQUID magnetometry was used to quantify nanogram levels of magnetite in the water samples. We also report a relationship between the volume change of ice, and the degree of supercooling, that may indicate lower degassing during the crystallization of supercooled water. In addition to supporting the role of ice-crystal nucleation by biogenic magnetite in many tissues, magnetite nanocrystals could provide inexpensive, non-toxic, and non-pathogenic ice nucleating agents needed in a variety of industrial processes, as well as influencing the dynamics of ice crystal nucleation in many natural environments. PMID:27087604

  20. Importance of aerosol composition, mixing state, and morphology for heterogeneous ice nucleation: A combined field and laboratory approach

    SciTech Connect

    Baustian, Kelly J.; Cziczo, Daniel J.; Wise, M. A.; Pratt, Kerri; Kulkarni, Gourihar R.; Hallar, Anna G.; Tolbert, Margaret A.

    2012-03-30

    In this study chemical compositions of background aerosol and ice nuclei were examined through laboratory investigations using Raman spectroscopy and field measurements by single-particle mass spectrometry. Aerosol sampling took place at Storm Peak Laboratory in Steamboat Springs, Colorado (elevation of 3210 m). A cascade impactor was used to collect coarse-mode aerosol particles for laboratory analysis by Raman spectroscopy; the composition, mixing state, and heterogeneous ice nucleation activity of individual particles were examined. For in situ analysis of fine-mode aerosol, ice nucleation on ambient particles was observed using a compact ice nucleation chamber. Ice crystals were separated from unactivated aerosol using a pumped counterflow virtual impactor, and ice nuclei were analyzed using particle analysis by laser mass spectrometry. For both fine and coarse modes, the ice nucleating particle fractions were enriched in minerals and depleted in sulfates and nitrates, compared to the background aerosol sampled. The vast majority of particles in both the ambient and ice active aerosol fractions contained a detectable amount of organic material. Raman spectroscopy showed that organic material is sometimes present in the form of a coating on the surface of inorganic particles. We find that some organic-containing particles serve as efficient ice nuclei while others do not. For coarse-mode aerosol, organic particles were only observed to initiate ice formation when oxygen signatures were also present in their spectra.

  1. Importance of aerosol composition, mixing state, and morphology for heterogeneous ice nucleation: A combined field and laboratory approach

    NASA Astrophysics Data System (ADS)

    Baustian, Kelly J.; Cziczo, Daniel J.; Wise, Matthew E.; Pratt, Kerri A.; Kulkarni, Gourihar; Hallar, A. Gannet; Tolbert, Margaret A.

    2012-03-01

    In this study chemical compositions of background aerosol and ice nuclei were examined through laboratory investigations using Raman spectroscopy and field measurements by single-particle mass spectrometry. Aerosol sampling took place at Storm Peak Laboratory in Steamboat Springs, Colorado (elevation of 3210 m). A cascade impactor was used to collect coarse-mode aerosol particles for laboratory analysis by Raman spectroscopy; the composition, mixing state, and heterogeneous ice nucleation activity of individual particles were examined. For in situ analysis of fine-mode aerosol, ice nucleation on ambient particles was observed using a compact ice nucleation chamber. Ice crystals were separated from unactivated aerosol using a pumped counterflow virtual impactor, and ice nuclei were analyzed using particle analysis by laser mass spectrometry. For both fine and coarse modes, the ice nucleating particle fractions were enriched in minerals and depleted in sulfates and nitrates, compared to the background aerosol sampled. The vast majority of particles in both the ambient and ice active aerosol fractions contained a detectable amount of organic material. Raman spectroscopy showed that organic material is sometimes present in the form of a coating on the surface of inorganic particles. We find that some organic-containing particles serve as efficient ice nuclei while others do not. For coarse-mode aerosol, organic particles were only observed to initiate ice formation when oxygen signatures were also present in their spectra.

  2. Heterogeneous Nucleation of n-Butanol Vapor on Submicrometer Charged and Neutral Particles of Lactose and Monosodium Glutamate.

    PubMed

    Chen; Tao; Shu

    2000-04-01

    Condensation of a supersaturated vapor of n-butanol on monodisperse submicrometer particles of lactose and monosodium glutamate is investigated in a flow cloud chamber (FCC). The dependence of critical supersaturation S(cr) on the particle size in the range 30 to 90 nm is experimentally examined. The results show that the size dependence of S(cr) qualitatively agrees with that predicted by the Fletcher version of the Volmer theory of heterogeneous nucleation, but to a lesser degree. The experimental S(cr) is smaller than the theoretical prediction even with the line tension and surface diffusion taken into account, and they induce heterogeneous nucleation better than perfectly wetted particles. The discrepancy can not be fully accounted for by the effects of line tension and surface diffusion and the existing theory concerning the curvature-dependent surface tension. The condensation on single positive-charged particles of diameter 30, 60, and 90 nm is also examined. A lowering of S(cr) at an efficiency much larger than the prediction by Volmer's theory for ion-induced nucleation is observed, and the charge effect fades away as particle size increases. Copyright 2000 Academic Press. PMID:10708489

  3. Effect of surface free energies on the heterogeneous nucleation of water droplet: a molecular dynamics simulation approach.

    PubMed

    Xu, W; Lan, Z; Peng, B L; Wen, R F; Ma, X H

    2015-02-01

    Heterogeneous nucleation of water droplet on surfaces with different solid-liquid interaction intensities is investigated by molecular dynamics simulation. The interaction potentials between surface atoms and vapor molecules are adjusted to obtain various surface free energies, and the nucleation process and wetting state of nuclei on surfaces are investigated. The results indicate that near-constant contact angles are already established for nano-scale nuclei on various surfaces, with the contact angle decreasing with solid-liquid interaction intensities linearly. Meanwhile, noticeable fluctuation of vapor-liquid interfaces can be observed for the nuclei that deposited on surfaces, which is caused by the asymmetric forces from vapor molecules. The formation and growth rate of nuclei are increasing with the solid-liquid interaction intensities. For low energy surface, the attraction of surface atoms to water molecules is comparably weak, and the pre-existing clusters can depart from the surface and enter into the bulk vapor phase. The distribution of clusters within the bulk vapor phase becomes competitive as compared with that absorbed on surface. For moderate energy surfaces, heterogeneous nucleation predominates and the formation of clusters within bulk vapor phase is suppressed. The effect of high energy particles that embedded in low energy surface is also discussed under the same simulation system. The nucleation preferably initiates on the high energy particles, and the clusters that formed on the heterogeneous particles are trapped around their original positions instead of migrating around as that observed on smooth surfaces. This feature makes it possible for the heterogeneous particles to act as fixed nucleation sites, and simulation results also suggest that the number of nuclei increases monotonously with the number of high energy particles. The growth of nuclei on high energy particles can be divided into three sub-stages, beginning with the formation

  4. Effect of surface free energies on the heterogeneous nucleation of water droplet: A molecular dynamics simulation approach

    NASA Astrophysics Data System (ADS)

    Xu, W.; Lan, Z.; Peng, B. L.; Wen, R. F.; Ma, X. H.

    2015-02-01

    Heterogeneous nucleation of water droplet on surfaces with different solid-liquid interaction intensities is investigated by molecular dynamics simulation. The interaction potentials between surface atoms and vapor molecules are adjusted to obtain various surface free energies, and the nucleation process and wetting state of nuclei on surfaces are investigated. The results indicate that near-constant contact angles are already established for nano-scale nuclei on various surfaces, with the contact angle decreasing with solid-liquid interaction intensities linearly. Meanwhile, noticeable fluctuation of vapor-liquid interfaces can be observed for the nuclei that deposited on surfaces, which is caused by the asymmetric forces from vapor molecules. The formation and growth rate of nuclei are increasing with the solid-liquid interaction intensities. For low energy surface, the attraction of surface atoms to water molecules is comparably weak, and the pre-existing clusters can depart from the surface and enter into the bulk vapor phase. The distribution of clusters within the bulk vapor phase becomes competitive as compared with that absorbed on surface. For moderate energy surfaces, heterogeneous nucleation predominates and the formation of clusters within bulk vapor phase is suppressed. The effect of high energy particles that embedded in low energy surface is also discussed under the same simulation system. The nucleation preferably initiates on the high energy particles, and the clusters that formed on the heterogeneous particles are trapped around their original positions instead of migrating around as that observed on smooth surfaces. This feature makes it possible for the heterogeneous particles to act as fixed nucleation sites, and simulation results also suggest that the number of nuclei increases monotonously with the number of high energy particles. The growth of nuclei on high energy particles can be divided into three sub-stages, beginning with the formation

  5. Effect of surface free energies on the heterogeneous nucleation of water droplet: A molecular dynamics simulation approach

    SciTech Connect

    Xu, W.; Lan, Z.; Peng, B. L.; Wen, R. F.; Ma, X. H.

    2015-02-07

    Heterogeneous nucleation of water droplet on surfaces with different solid-liquid interaction intensities is investigated by molecular dynamics simulation. The interaction potentials between surface atoms and vapor molecules are adjusted to obtain various surface free energies, and the nucleation process and wetting state of nuclei on surfaces are investigated. The results indicate that near-constant contact angles are already established for nano-scale nuclei on various surfaces, with the contact angle decreasing with solid-liquid interaction intensities linearly. Meanwhile, noticeable fluctuation of vapor-liquid interfaces can be observed for the nuclei that deposited on surfaces, which is caused by the asymmetric forces from vapor molecules. The formation and growth rate of nuclei are increasing with the solid-liquid interaction intensities. For low energy surface, the attraction of surface atoms to water molecules is comparably weak, and the pre-existing clusters can depart from the surface and enter into the bulk vapor phase. The distribution of clusters within the bulk vapor phase becomes competitive as compared with that absorbed on surface. For moderate energy surfaces, heterogeneous nucleation predominates and the formation of clusters within bulk vapor phase is suppressed. The effect of high energy particles that embedded in low energy surface is also discussed under the same simulation system. The nucleation preferably initiates on the high energy particles, and the clusters that formed on the heterogeneous particles are trapped around their original positions instead of migrating around as that observed on smooth surfaces. This feature makes it possible for the heterogeneous particles to act as fixed nucleation sites, and simulation results also suggest that the number of nuclei increases monotonously with the number of high energy particles. The growth of nuclei on high energy particles can be divided into three sub-stages, beginning with the formation

  6. New cloud chamber experiments on the heterogeneous ice nucleation ability of oxalic acid in the deposition nucleation and immersion freezing modes

    NASA Astrophysics Data System (ADS)

    Moehler, O.; Wagner, R.; Saathoff, H.; Schnaiter, M.; Leisner, T.

    2010-12-01

    crystallised from less supersaturated solution droplets and exposed to slow growth conditions in a supersaturated environment in the AIDA camber over a time period of several hours, were found to be much poorer heterogeneous ice nuclei. We speculate that under these conditions a crystal surface structure with less-active sites for the initiation of ice nucleation was generated. Such particles were found to be almost ice-inactive in both the deposition and condensation mode. At times, the heterogeneous ice nucleation ability of oxalic acid dihydrate significantly changed when the particles had been processed in preceding cloud droplet activation steps. Experimental methods, results, and atmospheric implications will be presented and discussed at the conference. [1] Kerminen et al., Atmos. Env., 33, 2089-2100, 1999. [2] Kerminen et al., J. Aerosol Sci., 31, 349-362, 2000. [3] Kawamura et al., Atmos. Env., 30, 1709-1722, 1996. [4] Marcolli et al., J. Phys. Chem. A, 108, 2216-2224, 2004. [5] Zobrist et al., Atmos. Chem. Phys., 6, 3115-3129, 2006. [6] Wagner et al., Atmos. Chem. Phys., 10, 7617-7641, 2010.

  7. Understanding cirrus ice crystal number variability for different heterogeneous ice nucleation spectra

    DOE PAGESBeta

    Sullivan, Sylvia C.; Morales Betancourt, Ricardo; Barahona, Donifan; Nenes, Athanasios

    2016-03-03

    Along with minimizing parameter uncertainty, understanding the cause of temporal and spatial variability of the nucleated ice crystal number, Ni, is key to improving the representation of cirrus clouds in climate models. To this end, sensitivities of Ni to input variables like aerosol number and diameter provide valuable information about nucleation regime and efficiency for a given model formulation. Here we use the adjoint model of the adjoint of a cirrus formation parameterization (Barahona and Nenes, 2009b) to understand Ni variability for various ice-nucleating particle (INP) spectra. Inputs are generated with the Community Atmosphere Model version 5, and simulations are donemore » with a theoretically derived spectrum, an empirical lab-based spectrum and two field-based empirical spectra that differ in the nucleation threshold for black carbon particles and in the active site density for dust. The magnitude and sign of Ni sensitivity to insoluble aerosol number can be directly linked to nucleation regime and efficiency of various INP. The lab-based spectrum calculates much higher INP efficiencies than field-based ones, which reveals a disparity in aerosol surface properties. Ni sensitivity to temperature tends to be low, due to the compensating effects of temperature on INP spectrum parameters; this low temperature sensitivity regime has been experimentally reported before but never deconstructed as done here.« less

  8. Understanding cirrus ice crystal number variability for different heterogeneous ice nucleation spectra

    DOE PAGESBeta

    Sullivan, Sylvia C.; Morales Betancourt, Ricardo; Barahona, Donifan; Nenes, Athanasios

    2016-03-03

    Along with minimizing parameter uncertainty, understanding the cause of temporal and spatial variability of the nucleated ice crystal number, Ni, is key to improving the representation of cirrus clouds in climate models. To this end, sensitivities of Ni to input variables like aerosol number and diameter provide valuable information about nucleation regime and efficiency for a given model formulation. Here we use the adjoint model of the adjoint of a cirrus formation parameterization (Barahona and Nenes, 2009b) to understand Ni variability for various ice-nucleating particle (INP) spectra. Inputs are generated with the Community Atmosphere Model version 5, and simulations are donemore » with a theoretically derived spectrum, an empirical lab-based spectrum and two field-based empirical spectra that differ in the nucleation threshold for black carbon particles and in the active site density for dust. The magnitude and sign of Ni sensitivity to insoluble aerosol number can be directly linked to nucleation regime and efficiency of various INP. The lab-based spectrum calculates much higher INP efficiencies than field-based ones, which reveals a disparity in aerosol surface properties. In conclusion, Ni sensitivity to temperature tends to be low, due to the compensating effects of temperature on INP spectrum parameters; this low temperature sensitivity regime has been experimentally reported before but never deconstructed as done here.« less

  9. Understanding cirrus ice crystal number variability for different heterogeneous ice nucleation spectra

    NASA Astrophysics Data System (ADS)

    Sullivan, Sylvia C.; Morales Betancourt, Ricardo; Barahona, Donifan; Nenes, Athanasios

    2016-03-01

    Along with minimizing parameter uncertainty, understanding the cause of temporal and spatial variability of the nucleated ice crystal number, Ni, is key to improving the representation of cirrus clouds in climate models. To this end, sensitivities of Ni to input variables like aerosol number and diameter provide valuable information about nucleation regime and efficiency for a given model formulation. Here we use the adjoint model of the adjoint of a cirrus formation parameterization (Barahona and Nenes, 2009b) to understand Ni variability for various ice-nucleating particle (INP) spectra. Inputs are generated with the Community Atmosphere Model version 5, and simulations are done with a theoretically derived spectrum, an empirical lab-based spectrum and two field-based empirical spectra that differ in the nucleation threshold for black carbon particles and in the active site density for dust. The magnitude and sign of Ni sensitivity to insoluble aerosol number can be directly linked to nucleation regime and efficiency of various INP. The lab-based spectrum calculates much higher INP efficiencies than field-based ones, which reveals a disparity in aerosol surface properties. Ni sensitivity to temperature tends to be low, due to the compensating effects of temperature on INP spectrum parameters; this low temperature sensitivity regime has been experimentally reported before but never deconstructed as done here.

  10. Heterogeneous nucleation and growth of water vapor on meteoric smoke particle analogues at mesospheric conditions

    NASA Astrophysics Data System (ADS)

    Nachbar, Mario; Duft, Denis; Leisner, Thomas

    2016-04-01

    Sub 2 nm meteoric smoke particles (MSP) produced from the ablation and recondensation of meteoric material are believed to be the major kind of nuclei causing the formation of water ice particles in the mesopause of Earth at heights of 80-90 km. These so called noctiLucent clouds (NLC) are frequently detected during polar summer, whereas the microphysical nucleation process and subsequent growth on such small particles are understood only poorly. Parameterizing these processes results in large uncertainties especially due to a lack of experimental data on desorption energies and critical saturation for the activation of nucleation under realistic mesospheric conditions, which states the need of laboratory measurements. We produce charged nanometer sized (2-3 nm) MSP analogues in a microwave plasma particle source and transfer them to a novel linear ion trap which allows us to trap the particles under typical mesospheric temperatures and H2O concentrations. The adsorption of H2O molecules on the particles surface followed by nucleation and growth can be examined by analyzing the mass distribution of the particles with a time-of-flight mass spectrometer as function of the residence time under supersaturated conditions. In this contribution we present such measurements for single positively as well as negatively charged particles which allow us to determine the desorption energy of water vapor on the investigated nanoparticles as well as the critical saturation needed to activate nucleation and subsequent growth.

  11. Producing Solar Cells By Surface Preparation For Accelerated Nucleation Of Microcrystalline Silicon On Heterogeneous Substrates.

    DOEpatents

    Yang, Liyou; Chen, Liangfan

    1998-03-24

    Attractive multi-junction solar cells and single junction solar cells with excellent conversion efficiency can be produced with a microcrystalline tunnel junction, microcrystalline recombination junction or one or more microcrystalline doped layers by special plasma deposition processes which includes plasma etching with only hydrogen or other specified etchants to enhance microcrystalline growth followed by microcrystalline. nucleation with a doped hydrogen-diluted feedstock.

  12. On the feasibility of cirrus cloud thinning: Dependence of homo- and heterogeneous ice nucleation on latitude and season

    NASA Astrophysics Data System (ADS)

    Mitchell, David; Garnier, Anne; Avery, Melody

    2015-04-01

    While GCM testing of cirrus cloud climate engineering (CE) reveals some advantages over stratospheric aerosol injection, cirrus CE will not work when ice is primarily formed through heterogeneous nucleation for T < -38°C. Field campaigns have shown that ice in cold cirrus is generally produced heterogeneously, but these campaigns have not addressed the cirrus at high latitudes that would determine the effectiveness of cirrus CE. This presentation introduces a new understanding of the satellite retrieved "effective absorption optical depth ratio", or βeff, based on the 12.05 and 10.60 μm channels of the imaging infrared radiometer (IIR) aboard the CALIPSO satellite. Using βeff calculations from in situ data, it is found that βeff is tightly related to the N/IWC ratio, where N = ice particle number concentration and IWC = ice water content. This is because N is primarily determined by the smallest ice particles, and βeff is primarily due to differences in wave resonance (i.e. photon tunneling) absorption, a process that is only significant when ice particle maximum dimension D < ~ 60 μm (i.e. when wavelength and effective particle size are comparable). Thus βeff is a measure of the concentration of small (D < 60 μm) ice crystals relative to the concentration of larger ice particles. Since homogeneous ice nucleation generally results in N > 500 liter-1, with a relatively high concentration of small ice crystals, βeff may be used to determine when homogeneous nucleation dominates in a region for T < -38°C. Satellite retrievals of βeff from anvil cirrus having N > 500 liter-1 (based on co-located/coincident in situ measurements) suggest that homogeneous nucleation dominates when βeff > 1.15 ± 0.05. A global analysis of βeff was conducted for the boreal summer (July-Aug.) and winter (Jan.-Feb.) of 2007 and 2008, respectively. Using βeff to discriminate between regions of homo- and heterogeneous ice nucleation for cirrus clouds having emissivities between

  13. Heterogeneous nucleation of entrained eutectic Si in high purity melt spun Al-Si alloys investigated by entrained droplet technique and DSC

    NASA Astrophysics Data System (ADS)

    Li, J. H.; Albu, M.; Ludwig, T. H.; Hofer, F.; Arnberg, L.; Schumacher, P.

    2016-03-01

    Entrained droplet technique and DSC analyses were employed to investigate the influence of trace elements of Sr, Eu and P on the heterogeneous nucleation of entrained eutectic Si in high purity melt spun Al-5wt.% Si alloys. Sr and Eu addition was found to exert negative effects on the nucleation process, while an increased undercooling was observed. This can be attributed to the formation of phosphide compounds having a lower free energy and hence may preferentially form compared to AlP. Only a trace P addition was found to have a profound effect on the nucleation process. The nucleation kinetics is discussed on the basis of the classical nucleation theory and the free growth model, respectively. The estimated AlP patch size was found to be sufficient for the free growth of Si to occur within the droplets, which strongly indicates that the nucleation of Si on an AlP patch or AlP particle is a limiting step for free growth. The maximum nucleation site density within one droplet is directly related to the size distribution of AlP particles or AlP patches for Si nucleation, but is independent of the cooling rates. Although the nucleation conditions were optimized in entrained droplet experiments, the observed mechanisms are also valid at moderate cooling conditions, such as in shape casting.

  14. Can we define an asymptotic value for the ice active surface site density for heterogeneous ice nucleation?

    NASA Astrophysics Data System (ADS)

    Niedermeier, Dennis; Augustin-Bauditz, Stefanie; Hartmann, Susan; Wex, Heike; Ignatius, Karoliina; Stratmann, Frank

    2015-04-01

    The formation of ice in atmospheric clouds has a substantial influence on the radiative properties of clouds as well as on the formation of precipitation. Therefore much effort has been made to understand and quantify the major ice formation processes in clouds. Immersion freezing has been suggested to be a dominant primary ice formation process in low and mid-level clouds (mixed-phase cloud conditions). It also has been shown that mineral dust particles are the most abundant ice nucleating particles in the atmosphere and thus may play an important role for atmospheric ice nucleation (Murray et al., 2012). Additionally, biological particles like bacteria and pollen are suggested to be potentially involved in atmospheric ice formation, at least on a regional scale (Murray et al., 2012). In recent studies for biological particles (SNOMAX and birch pollen), it has been demonstrated that freezing is induced by ice nucleating macromolecules and that an asymptotic value for the mass density of these ice nucleating macromolecules can be determined (Hartmann et al., 2013; Augustin et al., 2013, Wex et al., 2014). The question arises whether such an asymptotic value can also be determined for the ice active surface site density ns, a parameter which is commonly used to describe the ice nucleation activity of e.g., mineral dust. Such an asymptotic value for ns could be an important input parameter for atmospheric modeling applications. In the presented study, we therefore investigated the immersion freezing behavior of droplets containing size-segregated, monodisperse feldspar particles utilizing the Leipzig Aerosol Cloud Interaction Simulator (LACIS). For all particle sizes considered in the experiments, we observed a leveling off of the frozen droplet fraction reaching a plateau within the heterogeneous freezing temperature regime (T > -38°C) which was proportional to the particle surface area. Based on these findings, we could determine an asymptotic value for the ice

  15. A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets.

    PubMed

    Knopf, Daniel A; Alpert, Peter A

    2013-01-01

    Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T, and solution water activity, a(w), which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humidity (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, J(het), to be uniquely expressed by T and a(w), a result we term the a(w) based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, J(het), frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A, and cooling rates, r, of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log10(J(het)) values for the various IN types derived exclusively by Tand a(w), provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T, RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Lastly, we demonstrate that ABIFM can

  16. Heterogeneous nucleation and growth dynamics in the light-induced phase transition in vanadium dioxide.

    PubMed

    Brady, Nathaniel F; Appavoo, Kannatassen; Seo, Minah; Nag, Joyeeta; Prasankumar, Rohit P; Haglund, Richard F; Hilton, David J

    2016-03-31

    We report on ultrafast optical investigations of the light-induced insulator-to-metal phase transition in vanadium dioxide with controlled disorder generated by substrate mismatch. These results reveal common dynamics of this optically-induced phase transition that are independent of this disorder. Above the fluence threshold for completing the transition to the rutile crystalline phase, we find a common time scale, independent of sample morphology, of [Formula: see text] ps that is consistent with nucleation and growth dynamics of the R phase from the parent M1 ground state. PMID:26932975

  17. Heterogeneous nucleation and growth dynamics in the light-induced phase transition in vanadium dioxide

    NASA Astrophysics Data System (ADS)

    Brady, Nathaniel F.; Appavoo, Kannatassen; Seo, Minah; Nag, Joyeeta; Prasankumar, Rohit P.; Haglund, Richard F., Jr.; Hilton, David J.

    2016-03-01

    We report on ultrafast optical investigations of the light-induced insulator-to-metal phase transition in vanadium dioxide with controlled disorder generated by substrate mismatch. These results reveal common dynamics of this optically-induced phase transition that are independent of this disorder. Above the fluence threshold for completing the transition to the rutile crystalline phase, we find a common time scale, independent of sample morphology, of 40.5+/- 2 ps that is consistent with nucleation and growth dynamics of the R phase from the parent M1 ground state.

  18. Heterogeneous nucleation and growth dynamics in the light-induced phase transition in vanadium dioxide

    DOE PAGESBeta

    Brady, Nathaniel F.; Appavoo, Kannatassen; Seo, Minah; Nag, Joyeeta; Prasankumar, Rohit P.; Haglund, Richard F.; Hilton, David J.

    2016-03-02

    Here we report on ultrafast optical investigations of the light-induced insulator-to-metal phase transition in vanadium dioxide with controlled disorder generated by substrate mismatch. These results reveal common dynamics of this optically-induced phase transition that are independent of this disorder. Lastly, above the fluence threshold for completing the transition to the rutile crystalline phase, we find a common time scale, independent of sample morphology, of 40.5 ± 2 ps that is consistent with nucleation and growth dynamics of the R phase from the parent M1 ground state.

  19. Heterogeneous ice nucleation activity of bacteria: new laboratory experiments at simulated cloud conditions

    NASA Astrophysics Data System (ADS)

    Möhler, O.; Georgakopoulos, D. G.; Morris, C. E.; Benz, S.; Ebert, V.; Hunsmann, S.; Saathoff, H.; Schnaiter, M.; Wagner, R.

    2008-04-01

    The ice nucleation activities of five different Pseudomonas syringae, Pseudomonas viridiflava and Erwinia herbicola bacterial species and of SnomaxTM were investigated in the temperature range between -5 and -15°C. Water suspensions of these bacteria were directly spray into the cloud chamber of the AIDA facility of Forschungszentrum Karlsruhe at a temperature of -5.7°. At this temperature, about 1% of the SnomaxTM cells induced freezing of the spray droplets before they evaporated in the cloud chamber. The other suspensions of living cells didn't induce any measurable ice concentration during spray formation at -5.7°. The remaining aerosol was exposed to typical cloud activation conditions in subsequent experiments with expansion cooling to about -11°C. During these experiments, the bacterial cells first acted as cloud condensation nuclei to form cloud droplets and then eventually acted as ice nuclei to freeze the droplets. The results indicate that the bacteria investigated in the present study are mainly ice active in the temperature range between -7 and -11°C with an INA fraction of the order of 10-4. The ice nucleation efficiency of SnomaxTM cells was much larger with an INA fraction of 0.2 at temperatures around -8°C.

  20. Capturing heterogeneous nucleation of nanoscale pits and subsequent crystal shrinkage during Ostwald ripening of a metal phosphate.

    PubMed

    Chung, Sung-Yoon; Kim, Young-Min; Choi, Si-Young; Kim, Jin-Gyu

    2015-01-27

    It has been generally accepted that crystal shrinkage during Ostwald ripening can be understood simply as a reverse process of crystal growth, and as a result, little attention has been paid to shrinkage behavior. The entire microstructure of polycrystalline materials, however, forms as a consequence of both growing and shrinking crystals. Thus, scrutiny of shrinking characteristics in addition to growth aspects is essential for a complete understanding of the evolution of microstructure during Ostwald ripening. By capturing real-time in situ high-resolution electron micrographs at high temperature, we herein demonstrate the shrinkage behavior of nanocrystals embedded in a solid crystalline matrix during the ripening process of a metal phosphate. Unlike typical crystal growth behavior based on two-dimensional homogeneous nucleation, heterogeneous types of nucleation with nanoscale pits at solid-solid interfaces (or crystal edges) are observed to dominantly occur during shrinkage of the crystals. The findings of this study suggest that crystal shrinkage proceeds with a lower activation energy barrier than that of crystal growth, although both crystal growth and shrinkage take place at the same time during Ostwald ripening. PMID:25588182

  1. Inversion of multicomponent seismic data and rock-physics intepretation for evaluating lithology, fracture and fluid distribution in heterogeneous anisotropic reservoirs

    SciTech Connect

    Ilya Tsvankin; Kenneth L. Larner

    2004-11-17

    Within the framework of this collaborative project with the Lawrence Livermore National Laboratory (LLNL) and Stanford University, the Colorado School of Mines (CSM) group developed and implemented a new efficient approach to the inversion and processing of multicomponent, multiazimuth seismic data in anisotropic media. To avoid serious difficulties in the processing of mode-converted (PS) waves, we devised a methodology for transforming recorded PP- and PS-wavefields into the corresponding SS-wave reflection data that can be processed by velocity-analysis algorithms designed for pure (unconverted) modes. It should be emphasized that this procedure does not require knowledge of the velocity model and can be applied to data from arbitrarily anisotropic, heterogeneous media. The azimuthally varying reflection moveouts of the PP-waves and constructed SS-waves are then combined in anisotropic stacking-velocity tomography to estimate the velocity field in the depth domain. As illustrated by the case studies discussed in the report, migration of the multicomponent data with the obtained anisotropic velocity model yields a crisp image of the reservoir that is vastly superior to that produced by conventional methods. The scope of this research essentially amounts to building the foundation of 3D multicomponent, anisotropic seismology. We have also worked with the LLNL and Stanford groups on relating the anisotropic parameters obtained from seismic data to stress, lithology, and fluid distribution using a generalized theoretical treatment of fractured, poroelastic rocks.

  2. Nonclassical nucleation and growth of inorganic nanoparticles

    NASA Astrophysics Data System (ADS)

    Lee, Jisoo; Yang, Jiwoong; Kwon, Soon Gu; Hyeon, Taeghwan

    2016-08-01

    The synthesis of nanoparticles with particular compositions and structures can lead to nanoparticles with notable physicochemical properties, thus promoting their use in various applications. In this area of nanoscience, the focus is shifting from size- and shape-uniform single-component nanoparticles to multicomponent nanoparticles with enhanced performance and/or multifunctionality. With the increasing complexity of synthetic reactions, an understanding of the formation mechanisms of the nanoparticles is needed to enable a systematic synthetic approach. This Review highlights mechanistic studies underlying the synthesis of nanoparticles, with an emphasis on nucleation and growth behaviours that are not expected from classical theories. We discuss the structural properties of nanoclusters that are of a size that bridges molecules and solids. We then describe the role of nanoclusters in the prenucleation process as well as in nonclassical nucleation models. The growth of nanoparticles via the assembly and merging of primary particles is also overviewed. Finally, we present the heterogeneous nucleation mechanisms behind the synthesis of multicomponent nanoparticles.

  3. A Comprehensive Parameterization of Heterogeneous Ice Nucleation of Dust Surrogate: Laboratory Study with Hematite Particles and Its Application to Atmospheric Models

    SciTech Connect

    Hiranuma, Naruki; Paukert, Marco; Steinke, Isabelle; Zhang, Kai; Kulkarni, Gourihar R.; Hoose, Corinna; Schnaiter, Martin; Saathoff, Harald; Mohler, Ottmar

    2014-12-10

    A new heterogeneous ice nucleation parameterization that covers a wide temperature range (-36 °C to -78 °C) is presented. Developing and testing such an ice nucleation parameterization, which is constrained through identical experimental conditions, is critical in order to accurately simulate the ice nucleation processes in cirrus clouds. The surface-scaled ice nucleation efficiencies of hematite particles, inferred by ns, were derived from AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber measurements under water subsaturated conditions that were realized by continuously changing temperature (T) and relative humidity with respect to ice (RHice) in the chamber. Our measurements showed several different pathways to nucleate ice depending on T and RHice conditions. For instance, almost independent freezing was observed at -60 °C < T < -50 °C, where RHice explicitly controlled ice nucleation efficiency, while both T and RHice played roles in other two T regimes: -78 °C < T < -60 °C and -50 °C < T < -36 °C. More specifically, observations at T colder than -60 °C revealed that higher RHice was necessary to maintain constant ns, whereas T may have played a significant role in ice nucleation at T warmer than -50 °C. We implemented new ns parameterizations into two cloud models to investigate its sensitivity and compare with the existing ice nucleation schemes towards simulating cirrus cloud properties. Our results show that the new AIDA-based parameterizations lead to an order of magnitude higher ice crystal concentrations and inhibition of homogeneous nucleation in colder temperature regions. Our cloud simulation results suggest that atmospheric dust particles that form ice nuclei at lower temperatures, below -36 °C, can potentially have stronger influence on cloud properties such as cloud longevity and initiation when compared to previous parameterizations.

  4. A comprehensive parameterization of heterogeneous ice nucleation of dust surrogate: laboratory study with hematite particles and its application to atmospheric models

    NASA Astrophysics Data System (ADS)

    Hiranuma, N.; Paukert, M.; Steinke, I.; Zhang, K.; Kulkarni, G.; Hoose, C.; Schnaiter, M.; Saathoff, H.; Möhler, O.

    2014-12-01

    A new heterogeneous ice nucleation parameterization that covers a wide temperature range (-36 to -78 °C) is presented. Developing and testing such an ice nucleation parameterization, which is constrained through identical experimental conditions, is important to accurately simulate the ice nucleation processes in cirrus clouds. The ice nucleation active surface-site density (ns) of hematite particles, used as a proxy for atmospheric dust particles, were derived from AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber measurements under water subsaturated conditions. These conditions were achieved by continuously changing the temperature (T) and relative humidity with respect to ice (RHice) in the chamber. Our measurements showed several different pathways to nucleate ice depending on T and RHice conditions. For instance, almost T-independent freezing was observed at -60 °C < T < -50 °C, where RHice explicitly controlled ice nucleation efficiency, while both T and RHice played roles in other two T regimes: -78 °C < T < -60 °C and -50 °C < T < -36 °C. More specifically, observations at T lower than -60 °C revealed that higher RHice was necessary to maintain a constant ns, whereas T may have played a significant role in ice nucleation at T higher than -50 °C. We implemented the new hematite-derived ns parameterization, which agrees well with previous AIDA measurements of desert dust, into two conceptual cloud models to investigate their sensitivity to the new parameterization in comparison to existing ice nucleation schemes for simulating cirrus cloud properties. Our results show that the new AIDA-based parameterization leads to an order of magnitude higher ice crystal concentrations and to an inhibition of homogeneous nucleation in lower-temperature regions. Our cloud simulation results suggest that atmospheric dust particles that form ice nuclei at lower temperatures, below -36 °C, can potentially have a stronger influence on cloud

  5. Application of an online-coupled regional climate model, WRF-CAM5, over East Asia for examination of ice nucleation schemes. Part II. Sensitivity to heterogeneous ice nucleation parameterizations and dust emissions

    SciTech Connect

    Zhang, Yang; Chen, Ying; Fan, Jiwen; Leung, Lai -Yung

    2015-09-14

    Aerosol particles can affect cloud microphysical properties by serving as ice nuclei (IN). Large uncertainties exist in the ice nucleation parameterizations (INPs) used in current climate models. In this Part II paper, to examine the sensitivity of the model predictions to different heterogeneous INPs, WRF-CAM5 simulation using the INP of Niemand et al. (N12) [1] is conducted over East Asia for two full years, 2006 and 2011, and compared with simulation using the INP of Meyers et al. (M92) [2], which is the original INP used in CAM5. M92 calculates the nucleated ice particle concentration as a function of ice supersaturation, while N12 represents the nucleated ice particle concentration as a function of temperature and the number concentrations and surface areas of dust particles. Compared to M92, the WRF-CAM5 simulation with N12 produces significantly higher nucleated ice crystal number concentrations (ICNCs) in the northern domain where dust sources are located, leading to significantly higher cloud ice number and mass concentrations and ice water path, but the opposite is true in the southern domain where temperatures and moistures play a more important role in ice formation. Overall, the simulation with N12 gives lower downward shortwave radiation but higher downward longwave radiation, cloud liquid water path, cloud droplet number concentrations, and cloud optical depth. The increase in cloud optical depth and the decrease in downward solar flux result in a stronger shortwave and longwave cloud forcing, and decreases temperature at 2-m and precipitation. Changes in temperature and radiation lower surface concentrations of OH, O₃, SO₄²⁻, and PM2.5, but increase surface concentrations of CO, NO₂, and SO₂ over most of the domain. By acting as cloud condensation nuclei (CCN) and IN, dust particles have different impacts on cloud water and ice number concentrations, radiation, and temperature at 2-m and precipitation depending on

  6. Application of an online-coupled regional climate model, WRF-CAM5, over East Asia for examination of ice nucleation schemes. Part II. Sensitivity to heterogeneous ice nucleation parameterizations and dust emissions

    DOE PAGESBeta

    Zhang, Yang; Chen, Ying; Fan, Jiwen; Leung, Lai -Yung

    2015-09-14

    Aerosol particles can affect cloud microphysical properties by serving as ice nuclei (IN). Large uncertainties exist in the ice nucleation parameterizations (INPs) used in current climate models. In this Part II paper, to examine the sensitivity of the model predictions to different heterogeneous INPs, WRF-CAM5 simulation using the INP of Niemand et al. (N12) [1] is conducted over East Asia for two full years, 2006 and 2011, and compared with simulation using the INP of Meyers et al. (M92) [2], which is the original INP used in CAM5. M92 calculates the nucleated ice particle concentration as a function of icemore » supersaturation, while N12 represents the nucleated ice particle concentration as a function of temperature and the number concentrations and surface areas of dust particles. Compared to M92, the WRF-CAM5 simulation with N12 produces significantly higher nucleated ice crystal number concentrations (ICNCs) in the northern domain where dust sources are located, leading to significantly higher cloud ice number and mass concentrations and ice water path, but the opposite is true in the southern domain where temperatures and moistures play a more important role in ice formation. Overall, the simulation with N12 gives lower downward shortwave radiation but higher downward longwave radiation, cloud liquid water path, cloud droplet number concentrations, and cloud optical depth. The increase in cloud optical depth and the decrease in downward solar flux result in a stronger shortwave and longwave cloud forcing, and decreases temperature at 2-m and precipitation. Changes in temperature and radiation lower surface concentrations of OH, O₃, SO₄²⁻, and PM2.5, but increase surface concentrations of CO, NO₂, and SO₂ over most of the domain. By acting as cloud condensation nuclei (CCN) and IN, dust particles have different impacts on cloud water and ice number concentrations, radiation, and temperature at 2-m and precipitation depending on whether the

  7. Characterizing protein crystal nucleation

    NASA Astrophysics Data System (ADS)

    Akella, Sathish V.

    We developed an experimental microfluidic based technique to measure the nucleation rates and successfully applied the technique to measure nucleation rates of lysozyme crystals. The technique involves counting the number of samples which do not have crystals as a function of time. Under the assumption that nucleation is a Poisson process, the fraction of samples with no crystals decays exponentially with the decay constant proportional to nucleation rate and volume of the sample. Since nucleation is a random and rare event, one needs to perform measurements on large number of samples to obtain good statistics. Microfluidics offers the solution of producing large number of samples at minimal material consumption. Hence, we developed a microfluidic method and measured nucleation rates of lysozyme crystals in supersaturated protein drops, each with volume of ˜ 1 nL. Classical Nucleation Theory (CNT) describes the kinetics of nucleation and predicts the functional form of nucleation rate in terms of the thermodynamic quantities involved, such as supersaturation, temperature, etc. We analyzed the measured nucleation rates in the context of CNT and obtained the activation energy and the kinetic pre-factor characterizing the nucleation process. One conclusion is that heterogeneous nucleation dominates crystallization. We report preliminary studies on selective enhancement of nucleation in one of the crystal polymorprhs of lysozyme (spherulite) using amorphous mesoporous bioactive gel-glass te{naomi06, naomi08}, CaO.P 2O5.SiO2 (known as bio-glass) with 2-10 nm pore-size diameter distribution. The pores act as heterogeneous nucleation centers and claimed to enhance the nucleation rates by molecular confinement. The measured kinetic profiles of crystal fraction of spherulites indicate that the crystallization of spherulites may be proceeding via secondary nucleation pathways.

  8. Crystallization and immersion freezing ability of oxalic and succinic acid in multicomponent aqueous organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Wagner, Robert; Höhler, Kristina; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin

    2015-04-01

    This study reports on heterogeneous ice nucleation efficiency of immersed oxalic and succinic acid crystals in the temperature range from 245 to 215 K, as investigated with expansion cooling experiments using suspended particles. In contrast to previous laboratory work with emulsified solution droplets where the precipitation of solid inclusions required a preceding freezing/evaporation cycle, we show that immersed solids readily form by homogeneous crystallization within aqueous solution droplets of multicomponent organic mixtures, which have noneutonic compositions with an excess of oxalic or succinic acid. Whereas succinic acid crystals did not act as heterogeneous ice nuclei, immersion freezing by oxalic acid dihydrate crystals led to a reduction of the ice saturation ratio at freezing onset by 0.066-0.072 compared to homogeneous freezing, which is by a factor of 2 higher than previously reported laboratory data. These observations emphasize the importance of oxalic acid in heterogeneous ice nucleation.

  9. Gas-dynamic signs of explosive eruptions of volcanoes. 2. Model of homogeneous-heterogeneous nucleation. Specific features of destruction of the cavitating magma

    NASA Astrophysics Data System (ADS)

    Kedrinskii, V. K.

    2009-03-01

    The dynamics of state of the crystallite-containing magma is studied within the framework of the gas-dynamic model of bubble cavitation. The effect of crystallites on flow evolution is considered for two cases: where the crystallites are cavitation nuclei (homogeneous-heterogeneous nucleation model) and where large clusters of crystallites are formed in the magma in the period between eruptions. In the first case, decompression jumps are demonstrated to arise as early as in the wave precursor; the intensity of these jumps turns out to be sufficient to form a series of discrete zones of nucleation ahead of the front of the main decompression wave. Results of experimental modeling of an explosive eruption with ejection of crystallite clusters (magmatic “bombs”) suggest that a cocurrent flow of the cavitating magma with dynamically varying properties (mean density and viscosity) transforms to an independent unsteady flow whose velocity is greater than the magma flow velocity. Experimental results on modeling the flow structure during the eruption show that coalescence of bubbles in the flow leads to the formation of spatial “slugs” consisting of the gas and particles. This process is analyzed within a combined nucleation model including the two-phase Iordansky-Kogarko-van Wijngaarden model and the model of the “frozen” field of mass velocities in the cavitation zone.

  10. Heterogeneous nucleation at a wall near a wetting transition: a Monte Carlo test of the classical theory.

    PubMed

    Winter, David; Virnau, Peter; Binder, Kurt

    2009-11-18

    While for a slightly supersaturated vapor the free energy barrier ΔF(hom)(*), which needs to be overcome in a homogeneous nucleation event, may be extremely large, nucleation is typically much easier at the walls of the container in which the vapor is located. While no nucleation barrier exists if the walls are wet, for incomplete wetting of the walls, described via a nonzero contact angle Θ, classical theory predicts that nucleation happens through sphere-cap-shaped droplets attracted to the wall, and their formation energy is ΔF(het)(*) = ΔF(hom)(*)f(Θ), with f(Θ) = (1-cosΘ)(2)(2+cosΘ)/4. This prediction is tested through simulations for the simple cubic lattice gas model with nearest-neighbor interactions. The attractive wall is described in terms of a local 'surface field', leading to a critical wetting transition. The variation of the contact angle with the strength of the surface field is determined by using thermodynamic integration methods to obtain the wall free energies which enter Young's equation. Obtaining the chemical potential as a function of the density for a system with periodic boundary conditions (and no walls), the droplet free energy of a spherical droplet in the bulk is obtained for a wide range of droplet radii. Similarly, ΔF(het)(*) is obtained for a system with two parallel walls. We find that the classical theory is fairly accurate if a line tension correction for the contact angle is taken into account. PMID:21715882

  11. CRYSTALLIZATION IN MULTICOMPONENT GLASSES

    SciTech Connect

    KRUGER AA; HRMA PR

    2009-10-08

    In glass processing situations involving glass crystallization, various crystalline forms nucleate, grow, and dissolve, typically in a nonuniform temperature field of molten glass subjected to convection. Nuclear waste glasses are remarkable examples of multicomponent vitrified mixtures involving partial crystallization. In the glass melter, crystals form and dissolve during batch-to-glass conversion, melter processing, and product cooling. Crystals often agglomerate and sink, and they may settle at the melter bottom. Within the body of cooling glass, multiple phases crystallize in a non-uniform time-dependent temperature field. Self-organizing periodic distribution (the Liesegnang effect) is common. Various crystallization phenomena that occur in glass making are reviewed.

  12. Preferential earthquake-nucleating locations on faults determined by heterogeneous direct- and evolution-effect parameters of rate- and state-dependent friction

    NASA Astrophysics Data System (ADS)

    Viesca, R. C.; Ray, S.

    2015-12-01

    Rock friction experiments show that low-velocity fault friction may have a direct and subsequent evolutionary response to changes in slip velocity; the magnitude of which are respectively proportional to parameters a and b in constitutive relations of such rate- and state-dependent friction [e.g., Dieterich 1979; Ruina, 1983]. When a and b are uniform on a fault, translational invariance implies any location is a potential nucleation site, the choice determined by pre-instability conditions and external forcing. With heterogeneous parameters, symmetry is broken, which can create preferred nucleation sites. Recent work showed such heterogeneity does create favorable sites (Ray and Viesca, AGU '14). Here we study how distributions of (i) relative (0nucleation occurs at the local minimum and maximum of (ii) for nonlocal and local interactions, respectively

  13. Kinetics of heterogeneous bubble nucleation in rhyolitic melts: implications for the number density of bubbles in volcanic conduits and for pumice textures

    NASA Astrophysics Data System (ADS)

    Cluzel, N.; Laporte, D.; Provost, A.; Kannewischer, I.

    2008-12-01

    We performed decompression experiments to simulate the ascent of a phenocryst-bearing rhyolitic magma in a volcanic conduit. The starting materials were bubble-free rhyolites water-saturated at 200 MPa 800°C under oxidizing conditions: they contained 6.0 wt% dissolved H2O and a dense population of hematite crystals (8.7 ± 2 × 105 mm-3). Pressure was decreased from the saturation value to a final value ranging from 99 to 20 MPa, at constant temperature (800°C); the rate of decompression was either 1,000 or 27.8 kPa/s. In all experiments, we observed a single event of heterogeneous bubble nucleation beginning at a pressure P N equal to 63 ± 3 MPa in the 1,000 kPa/s series, and to 69 ± 1 MPa in the 27.8 kPa/s series. Below P N, the degree of water supersaturation in the liquid rapidly decreased to a few 0.1 wt%, the nucleation rate dropped, and the bubble number density (BND) stabilized to a value strongly sensitive to decompression rate: 80 mm-3 at 27.8 kPa/s vs. 5,900 mm-3 at 1,000 kPa/s. This behaviour is like the behavior formerly described in the case of homogeneous bubble nucleation in the rhyolite-H2O system and in numerical simulations of vesiculation in ascending magmas. Similar degrees of water supersaturation were measured at 27.8 and 1,000 kPa/s, implying that a faster decompression rate does not result in a larger departure from equilibrium. Our experimental results imply that BNDs in acid to intermediate magmas ascending in volcanic conduits will depend on both the decompression rate left| {left. {{text{d}}P/{text{d}}t} right|} right. and the number density of phenocrysts, especially the number density of magnetite microphenocrysts (1 100 mm-3), which is the only mineral species able to reduce significantly the degree of water supersaturation required for bubble nucleation. Very low BNDs (≈1 mm-3) are predicted in the case of effusive eruptions ( left| {left. {{text{d}}P/{text{d}}t} right|} right. ≈ 0.1 kPa/s). High BNDs (up to 107 mm-3) and

  14. An Atomistic View of Amyloidogenic Self-assembly: Structure and Dynamics of Heterogeneous Conformational States in the Pre-nucleation Phase.

    PubMed

    Matthes, Dirk; Gapsys, Vytautas; Brennecke, Julian T; de Groot, Bert L

    2016-01-01

    The formation of well-defined filamentous amyloid structures involves a polydisperse collection of oligomeric states for which relatively little is known in terms of structural organization. Here we use extensive, unbiased explicit solvent molecular dynamics (MD) simulations to investigate the structural and dynamical features of oligomeric aggregates formed by a number of highly amyloidogenic peptides at atomistic resolution on the μs time scale. A consensus approach has been adopted to analyse the simulations in multiple force fields, yielding an in-depth characterization of pre-fibrillar oligomers and their global and local structure properties. A collision cross section analysis revealed structurally heterogeneous aggregate ensembles for the individual oligomeric states that lack a single defined quaternary structure during the pre-nucleation phase. To gain insight into the conformational space sampled in early aggregates, we probed their substructure and found emerging β-sheet subunit layers and a multitude of ordered intermolecular β-structure motifs with growing aggregate size. Among those, anti-parallel out-of-register β-strands compatible with toxic β-barrel oligomers were particularly prevalent already in smaller aggregates and formed prior to ordered fibrillar structure elements. Notably, also distinct fibril-like conformations emerged in the oligomeric state and underscore the notion that pre-nucleated oligomers serve as a critical intermediate step on-pathway to fibrils. PMID:27616019

  15. A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

    NASA Technical Reports Server (NTRS)

    Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

    1992-01-01

    Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

  16. Nucleation in Synoptically Forced Cirrostratus

    NASA Technical Reports Server (NTRS)

    Lin, R.-F.; Starr, D. OC.; Reichardt, J.; DeMott, P. J.

    2004-01-01

    Formation and evolution of cirrostratus in response to weak, uniform and constant synoptic forcing is simulated using a one-dimensional numerical model with explicit microphysics, in which the particle size distribution in each grid box is fully resolved. A series of tests of the model response to nucleation modes (homogeneous-freezing-only/heterogeneous nucleation) and heterogeneous nucleation parameters are performed. In the case studied here, nucleation is first activated in the prescribed moist layer. A continuous cloud-top nucleation zone with a depth depending on the vertical humidity gradient and one of the nucleation parameters is developed afterward. For the heterogeneous nucleation cases, intermittent nucleation zones in the mid-upper portion of the cloud form where the relative humidity is on the rise, because existent ice crystals do not uptake excess water vapor efficiently, and ice nuclei (IN) are available. Vertical resolution as fine as 1 m is required for realistic simulation of the homogeneous-freezing-only scenario, while the model resolution requirement is more relaxed in the cases where heterogeneous nucleation dominates. Bulk microphysical and optical properties are evaluated and compared. Ice particle number flux divergence, which is due to the vertical gradient of the gravity-induced particle sedimentation, is constantly and rapidly changing the local ice number concentration, even in the nucleation zone. When the depth of the nucleation zone is shallow, particle number concentration decreases rapidly as ice particles grow and sediment away from the nucleation zone. When the depth of the nucleation zone is large, a region of high ice number concentration can be sustained. The depth of nucleation zone is an important parameter to be considered in parametric treatments of ice cloud generation.

  17. Hybrid Au-CdSe and Ag-CdSe nanoflowers and core-shell nanocrystals via one-pot heterogeneous nucleation and growth.

    PubMed

    AbouZeid, Khaled M; Mohamed, Mona B; El-Shall, M Samy

    2011-12-01

    A general approach, based on heterogeneous nucleation and growth of CdSe nanostructures on Au or Ag nanocrystals, for the synthesis of Au-CdSe and Ag-CdSe hybrid nanostructures is developed. The new approach provides a versatile one-pot route for the synthesis of hybrid nanoflowers consisting of a gold or silver core and multipod CdSe rods or an intact CdSe shell with controlled thickness, depending on the nucleation and growth parameters. At lower growth temperatures such as 150 °C, the CdSe clusters are adsorbed on the surface of the metal cores in their surface defects, then multiple arms and branches form, resulting in nanoflower-shaped hybrid structures. Increasing the size of the metal core through the choice of the reducing and capping agents results in an improvement of the interface between the metal and CdSe domains, producing core-shell structures. The growth temperature appears to be the most important factor determining the nature of the interface between the metal and CdSe domains. At relatively high temperatures such as 300 °C, the formation of large, faceted Au cores creates preferential growth sites for the CdSe nanocrystalline shell, thus resulting in well-defined Au-CdSe core-shell structures with large interfaces between the Au and CdSe domains. The present approach is expected to foster systematic studies of the electronic structures and optical properties of the metal-semiconductor hybrid materials for potential applications in photovoltaic and nanoelectronic devices. PMID:21994186

  18. Can we define an asymptotic value for the ice active surface site density for heterogeneous ice nucleation?

    NASA Astrophysics Data System (ADS)

    Niedermeier, Dennis; Augustin-Bauditz, Stefanie; Hartmann, Susan; Wex, Heike; Ignatius, Karoliina; Stratmann, Frank

    2015-05-01

    The immersion freezing behavior of droplets containing size-segregated, monodisperse feldspar particles was investigated. For all particle sizes investigated, a leveling off of the frozen droplet fraction was observed reaching a plateau within the heterogeneous freezing temperature regime (T >- 38°C). The frozen fraction in the plateau region was proportional to the particle surface area. Based on these findings, an asymptotic value for ice active surface site density ns, which we named ns⋆, could be determined for the investigated feldspar sample. The comparison of these results with those of other studies not only elucidates the general feasibility of determining such an asymptotic value but also shows that the value of ns⋆ strongly depends on the method of the particle surface area determination. However, such an asymptotic value might be an important input parameter for atmospheric modeling applications. At least it shows that care should be taken when ns is extrapolated to lower or higher temperature.

  19. Multicomponent membranes

    DOEpatents

    Kulprathipanja, Santi; Kulkarni, Sudhir S.; Funk, Edward W.

    1988-01-01

    A multicomponent membrane which may be used for separating various components which are present in a fluid feed mixture comprises a mixture of a plasticizer such as a glycol and an organic polymer cast upon a porous organic polymer support. The membrane may be prepared by casting an emulsion or a solution of the plasticizer and polymer on the porous support, evaporating the solvent and recovering the membrane after curing.

  20. On the Ice Nucleation Spectrum

    NASA Technical Reports Server (NTRS)

    Barahona, D.

    2012-01-01

    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

  1. Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: Nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors

    SciTech Connect

    Abdelsayed, Victor; Samy El-Shall, M.

    2014-08-07

    This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicates that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong

  2. The influence of heterogeneous nucleation on the surface crystallization of guaifenesin from melt extrudates containing Eudragit L10055 or Acryl-EZE.

    PubMed

    Bruce, Caroline D; Fegely, Kurt A; Rajabi-Siahboomi, Ali R; McGinity, James W

    2010-05-01

    The objective of this study was to investigate the influence of talc and humidity conditions during storage on the crystal growth of guaifenesin on the surface of melt-extruded matrix tablets. Tablets consisted of the model drug guaifenesin in a matrix of either Acryl-EZE(R) or Eudragit(R) L10055 and either no talc, 25% or 50% talc. After processing, the hot-melt-extruded matrix tablets were supersaturated with amorphous guaifenesin, which resulted in the development of guaifenesin drug crystals on exposed surfaces of the tablet during storage (all tablets were stored at 24 degrees C). A previously developed, quantitative test was used to assay for surface guaifenesin. In tablets with a drug-to-polymer ratio of 19:81, talc-containing tablets exhibited an earlier onset of crystal growth (storage at 17% relative humidity). The presence of talc also increased the amount of surface crystallization and was independent of the talc concentration, since the talc levels used in this study exceeded the critical nucleant concentration. Additional non-melting components did not have an additive effect on surface crystal growth. High humidity during storage (78%) increased guaifenesin crystallization, but moisture uptake of tablets did not correlate with increased drug recrystallization. When storage at 17% relative humidity was interrupted for 3days by storage at 78% relative humidity before the tablets were returned to their previous low RH storage conditions, crystal growth quickly increased during the high RH interval and remained at an elevated level throughout the remaining storage period. A similar intermediate period of low, 17% relative humidity in tablets stored before and after that time at 78% RH did not affect surface crystallization levels. The effects of humidity and talc on the crystallization of guaifenesin from melt-extruded dosage forms supersaturated with amorphous drug were ascribed to heterogeneous nucleation. PMID:19995604

  3. Nucleation dynamics of water nanodroplets.

    PubMed

    Bhattacharya, Dipanjan; Bosman, Michel; Mokkapati, Venkata R S S; Leong, Fong Yew; Mirsaidov, Utkur

    2014-04-01

    The origin of the condensation of water begins at the nanoscale, a length-scale that is challenging to probe for liquids. In this work we directly image heterogeneous nucleation of water nanodroplets by in situ transmission electron microscopy. Using gold nanoparticles bound to a flat surface as heterogeneous nucleation sites, we observe nucleation and growth of water nanodroplets. The growth of nanodroplet radii follows the power law: R(t)~(t-t 0) β , where β~0.2-0.3. PMID:24667092

  4. Theoretical study of production of unique glasses in space. [kinetic relationships describing nucleation and crystallization phenomena

    NASA Technical Reports Server (NTRS)

    Larsen, D. C.; Sievert, J. L.

    1975-01-01

    The potential of producing the glassy form of selected materials in the weightless, containerless nature of space processing is examined through the development of kinetic relationships describing nucleation and crystallization phenomena. Transformation kinetics are applied to a well-characterized system (SiO2), an excellent glass former (B2O3), and a poor glass former (Al2O3) by conventional earth processing methods. Viscosity and entropy of fusion are shown to be the primary materials parameters controlling the glass forming tendency. For multicomponent systems diffusion-controlled kinetics and heterogeneous nucleation effects are considered. An analytical empirical approach is used to analyze the mullite system. Results are consistent with experimentally observed data and indicate the promise of mullite as a future space processing candidate.

  5. Absorption cross sections of surface-adsorbed H2O in the 295-370 nm region and heterogeneous nucleation of H2O on fused silica surfaces.

    PubMed

    Du, Juan; Huang, Li; Zhu, Lei

    2013-09-12

    We have determined absorption cross sections of a monolayer of H2O adsorbed on the fused silica surfaces in the 295-370 nm region at 293 ± 1 K by using Brewster angle cavity ring-down spectroscopy. Absorption cross sections of surface-adsorbed H2O vary between (4.66 ± 0.83) × 10(-20) and (1.73 ± 0.52) × 10(-21) cm(2)/molecule over this wavelength range, where errors quoted represent experimental scatter (1σ). Our experimental study provides direct evidence that surface-adsorbed H2O is an absorber of the near UV solar radiation. We also varied the H2O pressure in the surface study cell over the 0.01-17 Torr range and obtained probe laser absorptions at 295, 340, and 350 nm by multilayer of adsorbed H2O molecules until the heterogeneous nucleation of water occurred on fused silica surfaces. The average absorption cross sections of multilayer adsorbed H2O are (2.17 ± 0.53) × 10(-20), (2.48 ± 0.67) × 10(-21), and (2.34 ± 0.59) × 10(-21) cm(2)/molecule at 295, 340, and 350 nm. The average absorption cross sections of transitional H2O layer are (6.06 ± 2.73) × 10(-20), (6.48 ± 3.85) × 10(-21), and (8.04 ± 4.92) × 10(-21) cm(2)/molecule at 295, 340, and 350 nm. The average thin water film absorption cross sections are (2.39 ± 0.50) × 10(-19), (3.21 ± 0.81) × 10(-20), and (3.37 ± 0.94) × 10(-20) cm(2)/molecule at 295 nm, 340 nm, and 350 nm. Atmospheric implications of the results are discussed. PMID:23947798

  6. The C-protein tetramer binds 230 to 240 nucleotides of pre-mRNA and nucleates the assembly of 40S heterogeneous nuclear ribonucleoprotein particles.

    PubMed Central

    Huang, M; Rech, J E; Northington, S J; Flicker, P F; Mayeda, A; Krainer, A R; LeStourgeon, W M

    1994-01-01

    A series of in vitro protein-RNA binding studies using purified native (C1)3C2 and (A2)3B1 tetramers, total soluble heterogeneous nuclear ribonucleoprotein (hnRNP), and pre-mRNA molecules differing in length and sequence have revealed that a single C-protein tetramer has an RNA site size of 230 to 240 nucleotides (nt). Two tetramers bind twice this RNA length, and three tetramers fold monoparticle lengths of RNA (700 nt) into a unique 19S triangular complex. In the absence of this unique structure, the basic A- and B-group proteins bind RNA to form several different artifactual structures which are not present in preparations of native hnRNP and which do not function in hnRNP assembly. Three (A2)3B1 tetramers bind the 19S complex to form a 35S assembly intermediate. Following UV irradiation to immobilize the C proteins on the packaged RNA, the 19S triangular complex is recovered as a remnant structure from both native and reconstituted hnRNP particles. C protein-RNA complexes composed of three, six, or nine tetramers (one, two, or three triangular complexes) nucleate the stoichiometric assembly of monomer, dimer, and trimer hnRNP particles. The binding of C-protein tetramers to RNAs longer than 230 nt is through a self-cooperative combinatorial mode. RNA packaged in the 19S complex and in 40S hnRNP particles is efficiently spliced in vitro. These findings demonstrate that formation of the triangular C protein-RNA complex is an obligate first event in the in vitro and probably the in vivo assembly the 40S hnRNP core particle, and they provide insight into the mechanism through which the core proteins package 700-nt increments of RNA. These findings also demonstrate that unless excluded by other factors, the C proteins are likely to be located along the length of nascent transcripts. Images PMID:8264621

  7. Climate Impacts of Ice Nucleation

    NASA Technical Reports Server (NTRS)

    Gettelman, Andrew; Liu, Xiaohong; Barahona, Donifan; Lohmann, Ulrike; Chen, Celia

    2012-01-01

    Several different ice nucleation parameterizations in two different General Circulation Models (GCMs) are used to understand the effects of ice nucleation on the mean climate state, and the Aerosol Indirect Effects (AIE) of cirrus clouds on climate. Simulations have a range of ice microphysical states that are consistent with the spread of observations, but many simulations have higher present-day ice crystal number concentrations than in-situ observations. These different states result from different parameterizations of ice cloud nucleation processes, and feature different balances of homogeneous and heterogeneous nucleation. Black carbon aerosols have a small (0.06 Wm(exp-2) and not statistically significant AIE when included as ice nuclei, for nucleation efficiencies within the range of laboratory measurements. Indirect effects of anthropogenic aerosols on cirrus clouds occur as a consequence of increasing anthropogenic sulfur emissions with different mechanisms important in different models. In one model this is due to increases in homogeneous nucleation fraction, and in the other due to increases in heterogeneous nucleation with coated dust. The magnitude of the effect is the same however. The resulting ice AIE does not seem strongly dependent on the balance between homogeneous and heterogeneous ice nucleation. Regional effects can reach several Wm2. Indirect effects are slightly larger for those states with less homogeneous nucleation and lower ice number concentration in the base state. The total ice AIE is estimated at 0.27 +/- 0.10 Wm(exp-2) (1 sigma uncertainty). This represents a 20% offset of the simulated total shortwave AIE for ice and liquid clouds of 1.6 Wm(sup-2).

  8. Climate Impacts of Ice Nucleation

    SciTech Connect

    Gettelman, A.; Liu, Xiaohong; Barahona, Donifan; Lohmann, U.; Chen, Chih-Chieh

    2012-10-19

    [1] Several different ice nucleation parameterizations in two different General Circulation Models (GCMs) are used to understand the effects of ice nucleation on the mean climate state, and the Aerosol Indirect Effects (AIE) of cirrus clouds on climate. Simulations have a range of ice microphysical states that are consistent with the spread of observations, but many simulations have higher present-day ice crystal number concentrations than in-situ observations. These different states result from different parameterizations of ice cloud nucleation processes, and feature different balances of homogeneous and heterogeneous nucleation. Black carbon aerosols have a small (-0.06 Wm-2) and not statistically significant AIE when included as ice nuclei, for nucleation efficiencies within the range of laboratory measurements. Indirect effects of anthropogenic aerosols on cirrus clouds occur as a consequence of increasing anthropogenic sulfur emissions with different mechanisms important in different models. In one model this is due to increases in homogeneous nucleation fraction, and in the other due to increases in heterogeneous nucleation with coated dust. The magnitude of the effect is the same however. The resulting ice AIE does not seem strongly dependent on the balance between homogeneous and heterogeneous ice nucleation. Regional effects can reach several Wm-2. Indirect effects are slightly larger for those states with less homogeneous nucleation and lower ice number concentration in the base state. The total ice AIE is estimated at 0.27 ± 0.10 Wm-2 (1σ uncertainty). Finally, this represents a 20% offset of the simulated total shortwave AIE for ice and liquid clouds of -1.6 Wm-2.

  9. Ice Nucleation Properties of Oxidized Carbon Nanomaterials.

    PubMed

    Whale, Thomas F; Rosillo-Lopez, Martin; Murray, Benjamin J; Salzmann, Christoph G

    2015-08-01

    Heterogeneous ice nucleation is an important process in many fields, particularly atmospheric science, but is still poorly understood. All known inorganic ice nucleating particles are relatively large in size and tend to be hydrophilic. Hence it is not obvious that carbon nanomaterials should nucleate ice. However, in this paper we show that four different readily water-dispersible carbon nanomaterials are capable of nucleating ice. The tested materials were carboxylated graphene nanoflakes, graphene oxide, oxidized single walled carbon nanotubes and oxidized multiwalled carbon nanotubes. The carboxylated graphene nanoflakes have a diameter of ∼30 nm and are among the smallest entities observed so far to nucleate ice. Overall, carbon nanotubes were found to nucleate ice more efficiently than flat graphene species, and less oxidized materials nucleated ice more efficiently than more oxidized species. These well-defined carbon nanomaterials may pave the way to bridging the gap between experimental and computational studies of ice nucleation. PMID:26267196

  10. Ice Nucleation Properties of Oxidized Carbon Nanomaterials

    PubMed Central

    2015-01-01

    Heterogeneous ice nucleation is an important process in many fields, particularly atmospheric science, but is still poorly understood. All known inorganic ice nucleating particles are relatively large in size and tend to be hydrophilic. Hence it is not obvious that carbon nanomaterials should nucleate ice. However, in this paper we show that four different readily water-dispersible carbon nanomaterials are capable of nucleating ice. The tested materials were carboxylated graphene nanoflakes, graphene oxide, oxidized single walled carbon nanotubes and oxidized multiwalled carbon nanotubes. The carboxylated graphene nanoflakes have a diameter of ∼30 nm and are among the smallest entities observed so far to nucleate ice. Overall, carbon nanotubes were found to nucleate ice more efficiently than flat graphene species, and less oxidized materials nucleated ice more efficiently than more oxidized species. These well-defined carbon nanomaterials may pave the way to bridging the gap between experimental and computational studies of ice nucleation. PMID:26267196

  11. Communication. Kinetics of scavenging of small, nucleating clusters. First nucleation theorem and sum rules

    DOE PAGESBeta

    Malila, Jussi; McGraw, Robert; Laaksonen, Ari; Lehtinen, Kari E. J.

    2015-01-07

    Despite recent advances in monitoring nucleation from a vapor at close-to-molecular resolution, the identity of the critical cluster, forming the bottleneck for the nucleation process, remains elusive. During past twenty years, the first nucleation theorem has been often used to extract the size of the critical cluster from nucleation rate measurements. However, derivations of the first nucleation theorem invoke certain questionable assumptions that may fail, e.g., in the case of atmospheric new particle formation, including absence of subcritical cluster losses and heterogeneous nucleation on pre-existing nanoparticles. Here we extend the kinetic derivation of the first nucleation theorem to give amore » general framework to include such processes, yielding sum rules connecting the size dependent particle formation and loss rates to the corresponding loss-free nucleation rate and the apparent critical size from a naïve application of the first nucleation theorem that neglects them.« less

  12. Communication. Kinetics of scavenging of small, nucleating clusters. First nucleation theorem and sum rules

    SciTech Connect

    Malila, Jussi; McGraw, Robert; Laaksonen, Ari; Lehtinen, Kari E. J.

    2015-01-07

    Despite recent advances in monitoring nucleation from a vapor at close-to-molecular resolution, the identity of the critical cluster, forming the bottleneck for the nucleation process, remains elusive. During past twenty years, the first nucleation theorem has been often used to extract the size of the critical cluster from nucleation rate measurements. However, derivations of the first nucleation theorem invoke certain questionable assumptions that may fail, e.g., in the case of atmospheric new particle formation, including absence of subcritical cluster losses and heterogeneous nucleation on pre-existing nanoparticles. Here we extend the kinetic derivation of the first nucleation theorem to give a general framework to include such processes, yielding sum rules connecting the size dependent particle formation and loss rates to the corresponding loss-free nucleation rate and the apparent critical size from a naïve application of the first nucleation theorem that neglects them.

  13. Influence of local structural disorders on spectroscopic properties of multi-component CaF2-Bi2O3-P2O5-B2O3 glass ceramics with Cr2O3 as nucleating agent

    NASA Astrophysics Data System (ADS)

    Suresh, S.; Narendrudu, T.; Yusub, S.; Suneel Kumar, A.; Ravi Kumar, V.; Veeraiah, N.; Krishna Rao, D.

    2016-01-01

    Multi-component CaF2-Bi2O3-P2O5-B2O3 glasses doped with different concentrations of Cr2O3 were crystallized through heat treatment. The prepared glass ceramic samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and differential thermal analysis (DTA). Spectroscopic studies viz., optical absorption, Fourier transform infrared (FTIR), Raman and electron paramagnetic resonance (EPR) were carried out. The XRD, SEM and DTA studies indicated that the samples contain different crystalline phases. Results of optical absorption and EPR studies pointed out the gradual conversion of chromium ions from Cr3 + state to Cr6 + state with an increase of Cr2O3 content from 0.1 to 0.5 mol%. The results of FTIR, Raman and EPR studies revealed that Cr6 + ions participate in the glass network in tetrahedral positions and seemed to increase the polymerization of the glass ceramics. The quantitative analysis of results of the spectroscopic studies further indicated that the glasses crystallized with low concentration of Cr2O3 are favourable for solid state laser devices.

  14. Influence of local structural disorders on spectroscopic properties of multi-component CaF₂-Bi₂O₃-P₂O₅-B₂O₃ glass ceramics with Cr₂O₃ as nucleating agent.

    PubMed

    Suresh, S; Narendrudu, T; Yusub, S; Kumar, A Suneel; Kumar, V Ravi; Veeraiah, N; Rao, D Krishna

    2016-01-15

    Multi-component CaF2-Bi2O3-P2O5-B2O3 glasses doped with different concentrations of Cr2O3 were crystallized through heat treatment. The prepared glass ceramic samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and differential thermal analysis (DTA). Spectroscopic studies viz., optical absorption, Fourier transform infrared (FTIR), Raman and electron paramagnetic resonance (EPR) were carried out. The XRD, SEM and DTA studies indicated that the samples contain different crystalline phases. Results of optical absorption and EPR studies pointed out the gradual conversion of chromium ions from Cr(3+) state to Cr(6+) state with an increase of Cr2O3 content from 0.1 to 0.5 mol%. The results of FTIR, Raman and EPR studies revealed that Cr(6+) ions participate in the glass network in tetrahedral positions and seemed to increase the polymerization of the glass ceramics. The quantitative analysis of results of the spectroscopic studies further indicated that the glasses crystallized with low concentration of Cr2O3 are favourable for solid state laser devices. PMID:26318703

  15. Truncated Dual-Cap Nucleation Site Development

    NASA Technical Reports Server (NTRS)

    Matson, Douglas M.; Sander, Paul J.

    2012-01-01

    During heterogeneous nucleation within a metastable mushy-zone, several geometries for nucleation site development must be considered. Traditional spherical dual cap and crevice models are compared to a truncated dual cap to determine the activation energy and critical cluster growth kinetics in ternary Fe-Cr-Ni steel alloys. Results of activation energy results indicate that nucleation is more probable at grain boundaries within the solid than at the solid-liquid interface.

  16. Particle Formation (Nucleation) in the Martian Atmosphere

    NASA Astrophysics Data System (ADS)

    Määttänen, A.; Vehkamäki, H.; Lauri, A.; Napari, I.; Merikallio, S.; Kauhanen, J.; Savijärvi, H.; Kulmala, M.

    2006-10-01

    We have studied ice particle formation via heterogeneous nucleation in the present atmospheric conditions of Mars for both one-component (water OR carbon dioxide) and two-component (water AND carbon dioxide) cases.

  17. Pb, Nd, and Sr isotopic evidence for a multicomponent source for rocks of Cook-Austral Islands and heterogeneities of mantle plumes

    USGS Publications Warehouse

    Nakamura, Y.; Tatsumoto, M.

    1988-01-01

    Sr, Nd, and Pb isotopic compositions were measured in alkaline volcanic rocks (alkali basalt, ankaramite, nephelinite, phonolite, and trachyte) from the South Cook Islands (Aitutaki, Mauke, Rarotonga, Atiu, and Mangaia) and the Austral Islands (Rimatara and Rurutu). The results show that the Cook-Austral rocks have an extremely wide range in isotopic compositions of Pb: 206Pb 204Pb from 18.25 to 21.76, 207pb 204pb from 15.48 to 15.83, and sol208pb 204Pb from 38.37 to 40.62, whereas isotopic compositions of Sr and Nd are less variable. Isotopically, Mangaia, Rimatara, and Rurutu form one group (Mangaia group), which shows extremely radiogenic Pb isotopic compositions but near-MORB (mid-oceanic ridge basalts) values for Sr and Nd isotopic ratios. In contrast, samples from Aitutaki, Rarotonga, Mauke, and Atiu (Aitutaki group) have high 207Pb 204Pb and 208Pb 204Pb and moderately high 87Sr 86Sr (Dupal anomaly). The Aitutaki group could have been derived from heterogeneous mantle plumes, which rose from the enriched deep mantle (the almost primitive lower mantle or recycled continental and oceanic slabs). On the other hand, the Mangaia component could have been derived from the depleted upper mantle which may have been metasomatized with a CO2-rich fluid, as indicated by the near-MORB values of Sr and Nd isotopes. Although Pb isotopic data of the two groups cannot be distinguished from each other statistically, the end components of the Pb-Pb system do not match with those of the Nd-Sr system. Thus, the data must be explained by a multi-, at least three, component mixing model: the mantle plumes (Dupal component and a recycled oceanic slab), metasomatized upper mantle, and lithosphere. The K-Ar ages and isotopic characteristics of the Cook-Austral rocks indicate that if one mantle plume rises from the deep mantle in this region, it has separated into at least two segments on the way to the surface. ?? 1988.

  18. Atmospheric Aerosol Nucleation: Formation of Sub-3 nm Particles and Their Subsequent Growth

    NASA Astrophysics Data System (ADS)

    Lee, S.

    2012-12-01

    Aerosol nucleation is an important step in the chain reaction that lead to cloud formation but the nucleation mechanisms are poorly understand. Most of the previous aerosol nucleation studies were based on measurements of particles, typically larger than 3 nm, so it was unclear how gas phase molecules nucleate to form clusters and how they further grow to become aerosol particles. In this presentation, we will show recent results of aerosol nucleation based on direct measurements of sub-3 nm particles. We will show laboratory studies of multicomponent nucleation involving sulfuric acid, ammonia, and organic amines and atmospheric observations made in various atmospheric conditions (biogenic, marine, and less polluted continental atmosphere).

  19. Physical and spectroscopic properties of multi-component Na2O-PbO-Bi2O3-SiO2 glass ceramics with Cr2O3 as nucleating agent

    NASA Astrophysics Data System (ADS)

    Sambasiva Rao, M. V.; Rajyasree, Ch.; Narendrudu, T.; Suresh, S.; Suneel Kumar, A.; Veeraiah, N.; Krishna Rao, D.

    2015-09-01

    Transparent glass ceramics, synthesized from melt quenching followed by heat treatment, of the composition 10Na2O-30PbO-10Bi2O3-(50 - x)SiO2:xCr2O3 (mol%), where 0 ⩽ x ⩽ 0.5, were characterized with XRD, DTA, SEM and EDS. Physical and spectroscopic studies, viz., optical absorption, electron paramagnetic resonance (EPR), FTIR and Raman were investigated. The characterization of the host glass ceramic has revealed that the formation of a major phase of sodium silicate along with two minor phases such as lead silicate and bismuth oxide. By integrating Cr2O3 to the host glass additional crystal phases viz., NaCrO2, Na2Cr2O7 and Pb(CrO4) which are the complexes of Cr3+ and Cr6+ ions were also developed. As the concentration of nucleating agent is increased, a part of the Cr6+ ions is found to reduce in to Cr3+ ions. Spectroscopic studies have revealed that with an increase in the concentration of Cr2O3 from 0.1 to 0.5 mol%, there is a gradual increase in the intensity of vibrational modes of various asymmetric structural units of silicate, bismuthate and chromate in the glass ceramic network at the expense of symmetrical structural units. The analysis of the results of these studies has indicated that in the samples containing higher concentration of Cr2O3, chromium ions exists predominantly in Cr3+ state and occupy the octahedral positions in glass ceramic matrix and such glass ceramic samples are suitable for lasing action.

  20. Enhancing Nucleation rates using Porous Silica

    NASA Astrophysics Data System (ADS)

    Akella, Sathish; Fraden, Seth

    2013-03-01

    The role of nucleants in promoting protein crystal nucleation is an on-going field of research. Porous silica acts as heterogeneous nucleation centers and enhances nucleation rates. For the protein lysozyme there are multiple polymorphs and we demonstrate that porous silica preferentially increases one of the polymorphs. Preliminary studies are presented in which accurate nucleation rates for the different polymorphs as a function of nucleant concentration are obtained through optical microscopy studies of thousands of crystallization trials in identical water-in-oil emulsion drops produced using microfluidics. NSF-IDBR

  1. Heterogeneous nucleation of CdS to enhance visible-light photocatalytic hydrogen evolution of SiC/CdS composite

    NASA Astrophysics Data System (ADS)

    Peng, Yuan; Guo, Zhongnan; Wang, Da; Pan, Nanyan; Yuan, Wenxia

    2015-07-01

    Synthesis of composite photocatalyst is one of the most important strategies to enhance the yield of hydrogen produced by water splitting. However, one photocatalyst usually tends to randomly aggregate on the other's surface, which weakens the electron transport of the heterogeneous interface. Herein, we developed a hydrothermal reaction to synthesize the SiC/CdS composite with a feasible Z-scheme and well-controlled dispersion of CdS on SiC surface. Heterogeneous structure on the catalyst interface is obtained, leading to more light-absorption and effective electron-hole separation between the well-contacted components, which contribute to the doubly enhanced photocatalytic performance of the composite. This work provides a simple and practical route to improve the catalytic activity by optimizing the intrinsic contact of Z-scheme composite semiconductors.

  2. Heterogeneous nucleation of CdS to enhance visible-light photocatalytic hydrogen evolution of SiC/CdS composite

    SciTech Connect

    Peng, Yuan; Guo, Zhongnan E-mail: wxyuanwz@163.com; Wang, Da; Pan, Nanyan; Yuan, Wenxia E-mail: wxyuanwz@163.com

    2015-07-06

    Synthesis of composite photocatalyst is one of the most important strategies to enhance the yield of hydrogen produced by water splitting. However, one photocatalyst usually tends to randomly aggregate on the other's surface, which weakens the electron transport of the heterogeneous interface. Herein, we developed a hydrothermal reaction to synthesize the SiC/CdS composite with a feasible Z-scheme and well-controlled dispersion of CdS on SiC surface. Heterogeneous structure on the catalyst interface is obtained, leading to more light-absorption and effective electron-hole separation between the well-contacted components, which contribute to the doubly enhanced photocatalytic performance of the composite. This work provides a simple and practical route to improve the catalytic activity by optimizing the intrinsic contact of Z-scheme composite semiconductors.

  3. Hydrophobic hydration driven self-assembly of curcumin in water: Similarities to nucleation and growth under large metastability, and an analysis of water dynamics at heterogeneous surfaces

    NASA Astrophysics Data System (ADS)

    Hazra, Milan Kumar; Roy, Susmita; Bagchi, Biman

    2014-11-01

    As the beneficial effects of curcumin have often been reported to be limited to its small concentrations, we have undertaken a study to find the aggregation properties of curcumin in water by varying the number of monomers. Our molecular dynamics simulation results show that the equilibrated structure is always an aggregated state with remarkable structural rearrangements as we vary the number of curcumin monomers from 4 to 16 monomers. We find that the curcumin monomers form clusters in a very definite pattern where they tend to aggregate both in parallel and anti-parallel orientation of the phenyl rings, often seen in the formation of β-sheet in proteins. A considerable enhancement in the population of parallel alignments is observed with increasing the system size from 12 to 16 curcumin monomers. Due to the prevalence of such parallel alignment for large system size, a more closely packed cluster is formed with maximum number of hydrophobic contacts. We also follow the pathway of cluster growth, in particular the transition from the initial segregated to the final aggregated state. We find the existence of a metastable structural intermediate involving a number of intermediate-sized clusters dispersed in the solution. We have constructed a free energy landscape of aggregation where the metatsable state has been identified. The course of aggregation bears similarity to nucleation and growth in highly metastable state. The final aggregated form remains stable with the total exclusion of water from its sequestered hydrophobic core. We also investigate water structure near the cluster surface along with their orientation. We find that water molecules form a distorted tetrahedral geometry in the 1st solvation layer of the cluster, interacting rather strongly with the hydrophilic groups at the surface of the curcumin. The dynamics of such quasi-bound water molecules near the surface of curcumin cluster is considerably slower than the bulk signifying a restricted

  4. Multicomponent mass transfer

    SciTech Connect

    Taylor, R.; Krishna, R.

    1993-01-01

    This is an important book on multicomponent mass transfer, meant for readers already acquainted with the theory of mass transfer and the fundamentals of transport phenomena. Part 1, entitled Molecular Diffusion, contains the following chapters: Preliminary Concepts; The Maxwell-Stefan Relations; Fick's Law; Estimation of Diffusion Coefficients; Solution of multicomponent Diffusion Problems: The Linearized Theory; and Solution of Multicomponent Diffusion Problems: Effective Diffusivity Methods. Part 2, entitled Interphase Transfer, contains the following chapters: Mass-Transfer Coefficients; Film Theory; Unsteady-State Mass-Transfer Models; Mass Transfer in Turbulent Flow; and Simultaneous Mass and Energy Transfer. Part 3, entitled Design, contains the following chapters: Multicomponent Distillation: Mass-Transfer Models; Multicomponent Distillation: Efficiency Models; Multicomponent Distillation: A Nonequilibrium Stage Model; and Condensation of Vapor Mixtures. Appendices are provided on matrix algebra, equation-solving and estimation of a thermodynamic derivative matrix. A computer diskette is provided with the book; the examples in Chapters 1--13 are solvable using this diskette and the commercial package Mathcad which the user must obtain. A separate software package, Chemsep, is needed for some of the exercises in Chapter 14.

  5. Experiments on Nucleation in Different Flow Regimes

    NASA Technical Reports Server (NTRS)

    Bayuzick, R. J.; Hofmeister, W. H.; Morton, C. M.; Robinson, M. B.

    1999-01-01

    The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods. Dilatometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov. The advantage of these experiments is that the samples are directly observable. The nucleation temperature

  6. Ice nucleation activity of polysaccharides

    NASA Astrophysics Data System (ADS)

    Bichler, Magdalena; Felgitsch, Laura; Haeusler, Thomas; Seidl-Seiboth, Verena; Grothe, Hinrich

    2015-04-01

    Heterogeneous ice nucleation is an important process in the atmosphere. It shows direct impact on our climate by triggering ice cloud formation and therefore it has much influence on the radiation balance of our planet (Lohmann et al. 2002; Mishchenko et al. 1996). The process itself is not completely understood so far and many questions remain open. Different substances have been found to exhibit ice nucleation activity (INA). Due to their vast differences in chemistry and morphology it is difficult to predict what substance will make good ice nuclei and which will not. Hence simple model substances must be found and be tested regarding INA. Our work aims at gaining to a deeper understanding of heterogeneous ice nucleation. We intend to find some reference standards with defined chemistry, which may explain the mechanisms of heterogeneous ice nucleation. A particular focus lies on biological carbohydrates in regards to their INA. Biological carbohydrates are widely distributed in all kingdoms of life. Mostly they are specific for certain organisms and have well defined purposes, e.g. structural polysaccharides like chitin (in fungi and insects) and pectin (in plants), which has also water-binding properties. Since they are widely distributed throughout our biosphere and mostly safe to use for nutrition purposes, they are well studied and easily accessible, rendering them ideal candidates as proxies. In our experiments we examined various carbohydrates, like the already mentioned chitin and pectin, as well as their chemical modifications. Lohmann U.; A Glaciation Indirect Aerosol Effect Caused by Soot Aerosols; J. Geoph. Res.; Vol. 24 No.4; pp 11-1 - 11-4; 2002 Mishchenko M.I., Rossow W.B., Macke A., Lacis A. A.; Sensitivity of Cirrus Cloud Albedo, Bidirectional Reflectance and Optical Thickness Retrieval Accuracy to Ice Particle Shape, J. Geoph. Res.; Vol. 101, No D12; pp. 16,973 - 16,985; 1996

  7. Efficient multicomponent fuel algorithm

    NASA Astrophysics Data System (ADS)

    Torres, D. J.; O'Rourke, P. J.; Amsden, A. A.

    2003-03-01

    We derive equations for multicomponent fuel evaporation in airborne fuel droplets and wall films, and implement the model into KIVA-3V. Temporal and spatial variations in liquid droplet composition and temperature are not modelled but solved for by discretizing the interior of the droplet in an implicit and computationally efficient way. We find that an interior discretization is necessary to correctly compute the evolution of the droplet composition. The details of the one-dimensional numerical algorithm are described. Numerical simulations of multicomponent evaporation are performed for single droplets and compared to experimental data.

  8. Ice Nucleation in Deep Convection

    NASA Technical Reports Server (NTRS)

    Jensen, Eric; Ackerman, Andrew; Stevens, David; Gore, Warren J. (Technical Monitor)

    2001-01-01

    The processes controlling production of ice crystals in deep, rapidly ascending convective columns are poorly understood due to the difficulties involved with either modeling or in situ sampling of these violent clouds. A large number of ice crystals are no doubt generated when droplets freeze at about -40 C. However, at higher levels, these crystals are likely depleted due to precipitation and detrainment. As the ice surface area decreases, the relative humidity can increase well above ice saturation, resulting in bursts of ice nucleation. We will present simulations of these processes using a large-eddy simulation model with detailed microphysics. Size bins are included for aerosols, liquid droplets, ice crystals, and mixed-phase (ice/liquid) hydrometers. Microphysical processes simulated include droplet activation, freezing, melting, homogeneous freezing of sulfate aerosols, and heterogeneous ice nucleation. We are focusing on the importance of ice nucleation events in the upper part of the cloud at temperatures below -40 C. We will show that the ultimate evolution of the cloud in this region (and the anvil produced by the convection) is sensitive to these ice nucleation events, and hence to the composition of upper tropospheric aerosols that get entrained into the convective column.

  9. Multicomponent Implant Releasing Dexamethasone

    NASA Astrophysics Data System (ADS)

    Nikkola, L.; Vapalahti, K.; Ashammakhi, N.

    2008-02-01

    Several inflammatory conditions are usually treated with corticosteroids. There are various problems like side effects with traditional applications of steroids, e.g. topical, or systemic routes. Local drug delivery systems have been studied and developed to gain more efficient administration with fewer side effects. Earlier, we reported on developing Dexamethasone (DX) releasing biodegradable fibers. However, their drug release properties were not satisfactory in terms of onset of drug release. Thus, we assessed the development of multicomponent (MC) implant to enhance earlier drug release from such biodegradable fibers. Poly (lactide-co-glycolide) (PLGA) and 2 wt-% and 8 wt-% DX were compounded and extruded with twin-screw extruder to form of fibers. Some of the fibers were sterilized to obtain a change in drug release properties. Four different fiber classes were studied: 2 wt-%, 8 wt-%, sterilized 2 wt-%, and sterilized 8 wt-%. 3×4 different DX-releasing fibers were then heat-pressed to form one multicomponent rod. Half of the rods where sterilized. Drug release was measured from initial fibers and multicomponent rods using a UV/VIS spectrometer. Shear strength and changes in viscosity were also measured. Drug release studies showed that drug release commenced earlier from multicomponent rods than from component fibers. Drug release from multicomponent rods lasted from day 30 to day 70. The release period of sterilized rods extended from day 23 to day 57. When compared to the original component fibers, the drug release from MC rods commenced earlier. The initial shear strength of MC rods was 135 MPa and decreased to 105 MPa during four weeks of immersion in phosphate buffer solution. Accordingly, heat pressing has a positive effect on drug release. After four weeks in hydrolysis, no disintegration was observed.

  10. [Effect of nucleation modes on the induced crystallization process for copper contained wastewater treatment].

    PubMed

    Xiong, Ya; Yan, Zhong; Zhang, Guo-Chen; Zheng, Ming-Xia; Wang, Kai-Jun

    2011-10-01

    The effect of nucleation modes on the induced crystallization process for copper contained wastewater treatment was studied. Tests were undertaken to observe the difference of copper removal efficiency and the crystal growth with homogeneous and heterogeneous nucleation. When the influent copper concentration was 50 mg x L(-1), copper removal efficiency could achieve 98.0% with the heterogeneous and 26.3% with homogeneous nucleation. And the SEM-EDS showed that the growth of crystals with heterogeneous nucleation was better and the purity of the crystals was higher than that with homogeneous nucleation. It is obvious that the homogeneous nucleation was an unfavorable condition on the induced crystallization process. Then the research devoted to discuss the process of induced crystallization with the two different nucleation mode and analysis the influencing mechanism of the homogeneous nucleation on the induced crystallization. PMID:22279909

  11. Crystal nucleation in Pd-Si alloys. [in containerless environment

    NASA Technical Reports Server (NTRS)

    Drehman, A. J.; Turnbull, D.

    1982-01-01

    A study of the crystal phase nucleation in undercooled droplets of Pd-Si alloys with composition near the Pd(84.5)Si(15.5) eutectic composition is reported. Molten droplets are released at the top of a drop tube and solidify (to either a crystalline or glassy state) during descent. This provides a containerless (and nearly gravity free) environment so that nucleation due to container walls or vibrations is eliminated. It is found that crystallization, due to homogeneous nucleation, is bypassed in droplets of 1 mm diameter when cooled at 760 K/sec. From this an upper limit of the homogeneous nucleation rate is estimated. Results are compared with a previously published study of nucleation in 0.06 mm to 0.33 mm diameter droplets, which indicated that nucleation results from heterogeneous surface nucleation and that the number of these nuclei is dependent on the atmosphere in the drop tube.

  12. Hybrid Multicomponent Hydrogels for Tissue Engineering

    PubMed Central

    Jia, Xinqiao; Kiick, Kristi L.

    2009-01-01

    Artificial ECMs that not only closely mimic the hybrid nature of the natural ECM but also provide tunable material properties and enhanced biological functions are attractive candidates for tissue engineering applications. This review summarizes recent advances in developing multicomponent hybrid hydrogels by integrating modular and heterogeneous building blocks into well-defined, multifunctional hydrogel composites. The individual building blocks can be chemically, morphologically, and functionally diverse, and the hybridization can occur at molecular level or microscopic scale. The modular nature of the designs, combined with the potential synergistic effects of the hybrid systems, has resulted in novel hydrogel matrices with robust structure and defined functions. PMID:19107720

  13. Nucleation of shear bands in amorphous alloys

    PubMed Central

    Perepezko, John H.; Imhoff, Seth D.; Chen, Ming-Wei; Wang, Jun-Qiang; Gonzalez, Sergio

    2014-01-01

    The initiation and propagation of shear bands is an important mode of localized inhomogeneous deformation that occurs in a wide range of materials. In metallic glasses, shear band development is considered to center on a structural heterogeneity, a shear transformation zone that evolves into a rapidly propagating shear band under a shear stress above a threshold. Deformation by shear bands is a nucleation-controlled process, but the initiation process is unclear. Here we use nanoindentation to probe shear band nucleation during loading by measuring the first pop-in event in the load–depth curve which is demonstrated to be associated with shear band formation. We analyze a large number of independent measurements on four different bulk metallic glasses (BMGs) alloys and reveal the operation of a bimodal distribution of the first pop-in loads that are associated with different shear band nucleation sites that operate at different stress levels below the glass transition temperature, Tg. The nucleation kinetics, the nucleation barriers, and the density for each site type have been determined. The discovery of multiple shear band nucleation sites challenges the current view of nucleation at a single type of site and offers opportunities for controlling the ductility of BMG alloys. PMID:24594599

  14. Transient nucleation in glasses

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.

    1991-01-01

    Nucleation rates in condensed systems are frequently not at their steady state values. Such time dependent (or transient) nucleation is most clearly observed in devitrification studies of metallic and silicate glasses. The origin of transient nucleation and its role in the formation and stability of desired phases and microstructures are discussed. Numerical models of nucleation in isothermal and nonisothermal situations, based on the coupled differential equations describing cluster evolution within the classical theory, are presented. The importance of transient nucleation in glass formation and crystallization is discussed.

  15. Dew nucleation and growth

    NASA Astrophysics Data System (ADS)

    Beysens, Daniel

    2006-11-01

    Dew is the condensation of water vapor into liquid droplets on a substrate. It is characterized by an initial heterogeneous nucleation on a substrate and a further growth of droplets. The presence of a substrate that geometrically constrains the growth is the origin of the peculiarities and richness of the phenomenon. A key point is the drop interaction through drop fusion or coalescence, which leads to scaling in the growth and gives universality to the process. As a matter of fact, growth dynamics are only dependent on substrate and drop dimensionality. Coalescence events lead to temporal and spatio-temporal fluctuations in the substrate coverage, drop configuration, etc., which give rise to a very peculiar dynamics. When the substrate is a liquid or a liquid crystal, the drop pattern can exhibit special spatial order, such as crystalline, hexatic phases and fractal contours. Condensation on a solid substrate near its melting point can make the drop jump. The applications of monitoring dew formation are manifold. Examples can be found in medicine (sterilization process), agriculture (green houses) and hydrology (production of drinkable water). To cite this article: D. Beysens, C. R. Physique 7 (2006).

  16. New Understandings for Three-Dimensional Nucleation (I)

    NASA Astrophysics Data System (ADS)

    Liu, X. Y.

    The generic heterogeneous effect of foreign particles on 3D nucleation was examined both theoretically and experimentally. It shows that the nucleation observed under normal conditions includes a sequence of progressive heterogeneous processes, characterized by different interfacial correlation function f(m, x)s. At low supersaturations, nucleation will be controlled by the process with a small interfacial correlation function f(m, x), which results from a strong interaction and good structural match between the foreign bodies and the crystallizing phase. At high supersaturations, nucleation on foreign particles having a weak interaction and poor structural match with the crystallizing phase (f(m, x)-->1) will govern the kinetics. This frequently leads to the false identification of homogeneous nucleation. Genuine homogeneous nucleation, which is the up-limit of heterogeneous nucleation, may not be easily achievable under gravity. In order to check these results, the prediction is confronted with nucleation experiments of some crystals. The results are in excellent agreement with the theory. Apart from this, the implications for epitaxial growth have also been discussed. In order to grow crystals epitaxially, the supersaturation should be kept at a low level, despite a good structural match between the crystal and substrate.

  17. Ice-Nucleating Bacteria

    NASA Astrophysics Data System (ADS)

    Obata, Hitoshi

    Since the discovery of ice-nucleating bacteria in 1974 by Maki et al., a large number of studies on the biological characteristics, ice-nucleating substance, ice nucleation gene and frost damage etc. of the bacteria have been carried out. Ice-nucleating bacteria can cause the freezing of water at relatively warm temperature (-2.3°C). Tween 20 was good substrates for ice-nucleating activity of Pseudomonas fluorescens KUIN-1. Major fatty acids of Isolate (Pseudomonas fluorescens) W-11 grown at 30°C were palmitic, cis-9-hexadecenoic and cis-11-octadecenoic which amounted to 90% of the total fatty acids. Sequence analysis shows that an ice nucleation gene from Pseudomonas fluorescens is related to the gene of Pseudomonas syringae.

  18. Magnetization of multicomponent ferrofluids.

    PubMed

    Szalai, I; Dietrich, S

    2011-08-17

    The solution of the mean spherical approximation (MSA) integral equation for isotropic multicomponent dipolar hard sphere fluids without external fields is used to construct a density functional theory (DFT), which includes external fields, in order to obtain an analytical expression for the external field dependence of the magnetization of ferrofluidic mixtures. This DFT is based on a second-order Taylor series expansion of the free energy density functional of the anisotropic system around the corresponding isotropic MSA reference system. The ensuing results for the magnetic properties are in quantitative agreement with our canonical ensemble Monte Carlo simulation data presented here. PMID:21795777

  19. Electrohydrodynamics Of Multicomponent Vesicles

    NASA Astrophysics Data System (ADS)

    Gera, Prerna; Salac, David

    2015-11-01

    The addition of cholesterol into a lipid membrane induces the formation of distinct domains. These domains try to minimize the overall energy of the system by coalescence and migration. The application of electric fields will induce flow of these membrane domains and influence the rate at which they coarsen. In this work the electrohydrodynamics of multicomponent vesicles is numerically modelled. The method uses a Cahn-Hilliard-Cook model of the lipid domains restricted to a deforming three-dimensional vesicle and will be briefly discussed. Sample results will be presented and compared to experimental observations. This work supported by NSF Grant #1253739.

  20. Experiments on Nucleation in Different Flow Regimes

    NASA Technical Reports Server (NTRS)

    Bayuzick, Robert J.

    1999-01-01

    The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods [1-6]. Dilitometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics [7]. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov [8]. The advantage of these experiments is that the samples are directly observable. The nucleation

  1. Effect of solute on the nucleation and propagation of ice.

    PubMed

    Charoenrein, S; Goddard, M; Reid, D S

    1991-01-01

    Using the emulsion technique, we have studied nucleation of ice in aqueous solutions containing silver iodide or Pseudomonas syringae. Using a Differential Scanning Calorimeter (DSC), we determined characteristic temperatures of nucleation, and also rates of nucleation at selected temperatures. The freezing point depression induced by added solute is linearly related to the lowering of both homogeneous and heterogeneous nucleation temperature. Nucleation kinetics depend on a fifth power function of the temperature. Solute is found to affect the parameters of this relationship in different ways, dependent upon the nature of the catalytic site for ice nucleation. We have also studied the effect of composition on the linear propagation velocity (LPV) of ice in undercooled solutions contained in a U-tube. We have determined velocities in a range of concentrations of sugar solution at the same undercooling, and also as a function of undercooling. The role of added polymer has also been investigated. It is affected by the sugar concentration. PMID:1746327

  2. Kinetic theory of diffusion-limited nucleation.

    PubMed

    Philippe, T; Bonvalet, M; Blavette, D

    2016-05-28

    We examine binary nucleation in the size and composition space {R,c} using the formalism of the multivariable theory [N. V. Alekseechkin, J. Chem. Phys. 124, 124512 (2006)]. We show that the variable c drops out of consideration for very large curvature of the new phase Gibbs energy with composition. Consequently nuclei around the critical size have the critical composition, which is derived from the condition of criticality for the canonical variables and is found not to depend on surface tension. In this case, nucleation kinetics can be investigated in the size space only. Using macroscopic kinetics, we determine the general expression for the condensation rate when growth is limited by bulk diffusion, which accounts for both diffusion and capillarity and exhibits a different dependence with the critical size, as compared with the interface-limited regime. This new expression of the condensation rate for bulk diffusion-limited nucleation is the counterpart of the classical interface-limited result. We then extend our analysis to multicomponent solutions. PMID:27250310

  3. Kinetic theory of diffusion-limited nucleation

    NASA Astrophysics Data System (ADS)

    Philippe, T.; Bonvalet, M.; Blavette, D.

    2016-05-01

    We examine binary nucleation in the size and composition space {R,c} using the formalism of the multivariable theory [N. V. Alekseechkin, J. Chem. Phys. 124, 124512 (2006)]. We show that the variable c drops out of consideration for very large curvature of the new phase Gibbs energy with composition. Consequently nuclei around the critical size have the critical composition, which is derived from the condition of criticality for the canonical variables and is found not to depend on surface tension. In this case, nucleation kinetics can be investigated in the size space only. Using macroscopic kinetics, we determine the general expression for the condensation rate when growth is limited by bulk diffusion, which accounts for both diffusion and capillarity and exhibits a different dependence with the critical size, as compared with the interface-limited regime. This new expression of the condensation rate for bulk diffusion-limited nucleation is the counterpart of the classical interface-limited result. We then extend our analysis to multicomponent solutions.

  4. Diamond nucleation using polyethene

    DOEpatents

    Morell, Gerardo; Makarov, Vladimir; Varshney, Deepak; Weiner, Brad

    2013-07-23

    The invention presents a simple, non-destructive and non-abrasive method of diamond nucleation using polyethene. It particularly describes the nucleation of diamond on an electrically viable substrate surface using polyethene via chemical vapor deposition (CVD) technique in a gaseous environment.

  5. Diamond Nucleation Using Polyethene

    NASA Technical Reports Server (NTRS)

    Morell, Gerardo (Inventor); Makarov, Vladimir (Inventor); Varshney, Deepak (Inventor); Weiner, Brad (Inventor)

    2013-01-01

    The invention presents a simple, non-destructive and non-abrasive method of diamond nucleation using polyethene. It particularly describes the nucleation of diamond on an electrically viable substrate surface using polyethene via chemical vapor deposition (CVD) technique in a gaseous environment.

  6. Nucleation of amyloid fibrils

    NASA Astrophysics Data System (ADS)

    Kashchiev, Dimo; Auer, Stefan

    2010-06-01

    We consider nucleation of amyloid fibrils in the case when the process occurs by the mechanism of direct polymerization of practically fully extended protein segments, i.e., β-strands, into β-sheets. Applying the classical nucleation theory, we derive a general expression for the work to form a nanosized amyloid fibril (protofilament) constituted of successively layered β-sheets. Analysis of this expression reveals that with increasing its size, the fibril transforms from one-dimensional to two-dimensional aggregate in order to preserve the equilibrium shape corresponding to minimal formation work. We determine the size of the fibril nucleus, the fibril nucleation work, and the fibril nucleation rate as explicit functions of the concentration and temperature of the protein solution. The results obtained are applicable to homogeneous nucleation, which occurs when the solution is sufficiently pure and/or strongly supersaturated.

  7. Liquid Nucleation at Superheated Grain Boundaries

    NASA Astrophysics Data System (ADS)

    Frolov, T.; Mishin, Y.

    2011-04-01

    Grain boundaries with relatively low energies can be superheated above the melting temperature and eventually melt by heterogeneous nucleation of liquid droplets. We propose a thermodynamic model of this process based on the sharp-interface approximation with a disjoining potential. The distinct feature of the model is its ability to predict the shape and size of the critical nucleus by using a variational approach. The model reduces to the classical nucleation theory in the limit of large nuclei but is more general and remains valid for small nuclei. Contrary to the classical nucleation theory, the model predicts the existence of a critical temperature of superheating and offers a simple formula for its calculation. The model is tested against molecular dynamic simulations in which liquid nuclei at a superheated boundary were obtained by an adiabatic trapping procedure. The simulation results demonstrate a reassuring consistency with the model.

  8. Homogeneous freezing nucleation of stratospheric solution droplets

    NASA Technical Reports Server (NTRS)

    Jensen, Eric J.; Toon, Owen B.; Hamill, Patrick

    1991-01-01

    The classical theory of homogeneous nucleation was used to calculate the freezing rate of sulfuric acid solution aerosols under stratospheric conditions. The freezing of stratospheric aerosols would be important for the nucleation of nitric acid trihydrate particles in the Arctic and Antarctic stratospheres. In addition, the rate of heterogeneous chemical reactions on stratospheric aerosols may be very sensitive to their state. The calculations indicate that homogeneous freezing nucleation of pure water ice in the stratospheric solution droplets would occur at temperatures below about 192 K. However, the physical properties of H2SO4 solution at such low temperatures are not well known, and it is possible that sulfuric acid aerosols will freeze out at temperatures ranging from about 180 to 195 K. It is also shown that the temperature at which the aerosols freeze is nearly independent of their size.

  9. Probing Individual Ice Nucleation Events with Environmental Scanning Electron Microscopy

    NASA Astrophysics Data System (ADS)

    Wang, Bingbing; China, Swarup; Knopf, Daniel; Gilles, Mary; Laskin, Alexander

    2016-04-01

    Heterogeneous ice nucleation is one of the processes of critical relevance to a range of topics in the fundamental and the applied science and technologies. Heterogeneous ice nucleation initiated by particles proceeds where microscopic properties of particle surfaces essentially control nucleation mechanisms. Ice nucleation in the atmosphere on particles governs the formation of ice and mixed phase clouds, which in turn influence the Earth's radiative budget and climate. Heterogeneous ice nucleation is still insufficiently understood and poses significant challenges in predictive understanding of climate change. We present a novel microscopy platform allowing observation of individual ice nucleation events at temperature range of 193-273 K and relative humidity relevant for ice formation in the atmospheric clouds. The approach utilizes a home built novel ice nucleation cell interfaced with Environmental Scanning Electron Microscope (IN-ESEM system). The IN-ESEM system is applied for direct observation of individual ice formation events, determining ice nucleation mechanisms, freezing temperatures, and relative humidity onsets. Reported microanalysis of the ice nucleating particles (INP) include elemental composition detected by the energy dispersed analysis of X-rays (EDX), and advanced speciation of the organic content in particles using scanning transmission x-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). The performance of the IN-ESEM system is validated through a set of experiments with kaolinite particles with known ice nucleation propensity. We demonstrate an application of the IN-ESEM system to identify and characterize individual INP within a complex mixture of ambient particles.

  10. Homogeneous ice nucleation from aqueous inorganic/organic particles representative of biomass burning: water activity, freezing temperatures, nucleation rates.

    PubMed

    Knopf, Daniel A; Rigg, Yannick J

    2011-02-10

    Homogeneous ice nucleation plays an important role in the formation of cirrus clouds with subsequent effects on the global radiative budget. Here we report on homogeneous ice nucleation temperatures and corresponding nucleation rate coefficients of aqueous droplets serving as surrogates of biomass burning aerosol. Micrometer-sized (NH(4))(2)SO(4)/levoglucosan droplets with mass ratios of 10:1, 1:1, 1:5, and 1:10 and aqueous multicomponent organic droplets with and without (NH(4))(2)SO(4) under typical tropospheric temperatures and relative humidities are investigated experimentally using a droplet conditioning and ice nucleation apparatus coupled to an optical microscope with image analysis. Homogeneous freezing was determined as a function of temperature and water activity, a(w), which was set at droplet preparation conditions. The ice nucleation data indicate that minor addition of (NH(4))(2)SO(4) to the aqueous organic droplets renders the temperature dependency of water activity negligible in contrast to the case of aqueous organic solution droplets. The mean homogeneous ice nucleation rate coefficient derived from 8 different aqueous droplet compositions with average diameters of ∼60 μm for temperatures as low as 195 K and a(w) of 0.82-1 is 2.18 × 10(6) cm(-3) s(-1). The experimentally derived freezing temperatures and homogeneous ice nucleation rate coefficients are in agreement with predictions of the water activity-based homogeneous ice nucleation theory when taking predictive uncertainties into account. However, the presented ice nucleation data indicate that the water activity-based homogeneous ice nucleation theory overpredicts the freezing temperatures by up to 3 K and corresponding ice nucleation rate coefficients by up to ∼2 orders of magnitude. A shift of 0.01 in a(w), which is well within the uncertainty of typical field and laboratory relative humidity measurements, brings experimental and predicted freezing temperatures and homogeneous ice

  11. Dynamics of ice nucleation on water repellent surfaces.

    PubMed

    Alizadeh, Azar; Yamada, Masako; Li, Ri; Shang, Wen; Otta, Shourya; Zhong, Sheng; Ge, Liehui; Dhinojwala, Ali; Conway, Ken R; Bahadur, Vaibhav; Vinciquerra, A Joseph; Stephens, Brian; Blohm, Margaret L

    2012-02-14

    Prevention of ice accretion and adhesion on surfaces is relevant to many applications, leading to improved operation safety, increased energy efficiency, and cost reduction. Development of passive nonicing coatings is highly desirable, since current antiicing strategies are energy and cost intensive. Superhydrophobicity has been proposed as a lead passive nonicing strategy, yet the exact mechanism of delayed icing on these surfaces is not clearly understood. In this work, we present an in-depth analysis of ice formation dynamics upon water droplet impact on surfaces with different wettabilities. We experimentally demonstrate that ice nucleation under low-humidity conditions can be delayed through control of surface chemistry and texture. Combining infrared (IR) thermometry and high-speed photography, we observe that the reduction of water-surface contact area on superhydrophobic surfaces plays a dual role in delaying nucleation: first by reducing heat transfer and second by reducing the probability of heterogeneous nucleation at the water-substrate interface. This work also includes an analysis (based on classical nucleation theory) to estimate various homogeneous and heterogeneous nucleation rates in icing situations. The key finding is that ice nucleation delay on superhydrophobic surfaces is more prominent at moderate degrees of supercooling, while closer to the homogeneous nucleation temperature, bulk and air-water interface nucleation effects become equally important. The study presented here offers a comprehensive perspective on the efficacy of textured surfaces for nonicing applications. PMID:22235939

  12. Hydrocarbon nucleation and aerosol formation in Neptune's atmosphere.

    PubMed

    Moses, J I; Allen, M; Yung, Y L

    1992-10-01

    Photodissociation of methane at high altitude levels in Neptune's atmosphere leads to the production of complex hydrocarbon species such as acetylene (C2H2), ethane (C2H6), methylacetylene (CH3C2H), propane (C3H8), diacetylene (C4H2), and butane (C4H8). These gases diffuse to the lower stratosphere where temperatures are low enough to initiate condensation. Particle formation may not occur readily, however, as the vapor species become supersaturated. We present a theoretical analysis of particle formation mechanisms at conditions relevant to Neptune's troposphere and stratosphere and show that hydrocarbon nucleation is very inefficient under Neptunian conditions: saturation ratios much greater than unity are required for aerosol formation by either homogeneous, heterogeneous, or ion-induced nucleation. Homogeneous nucleation will not be important for any of the hydrocarbon species considered; however, both heterogeneous and ion-induced nucleation should be possible on Neptune for most of the above species. The relative effectiveness of heterogeneous and ion-induced nucleation depends on the physical and thermodynamic properties of the particular species, the abundance of the condensable species, the temperature at which the vapor becomes supersaturated, and the number and type of condensation nuclei or ions available. Typical saturation ratios required for observable particle formation rates on Neptune range from approximately 3 for heterogeneous nucleation of methane in the upper troposphere to greater than 1000 for heterogeneous nucleation of methylacetylene, diacetylene, and butane in the lower stratosphere. Thus, methane clouds may form slightly above, and stratospheric hazes far below, their saturation levels. When used in conjunction with the results of detailed models of atmospheric photochemistry, our nucleation models place realistic constraints on the altitude levels at which we expect hydrocarbon hazes or clouds to form on Neptune. PMID:11538166

  13. Molecular Ice Nucleation Activity of Birch Pollen

    NASA Astrophysics Data System (ADS)

    Felgitsch, Laura; Bichler, Magdalena; Häusler, Thomas; Weiss, Victor U.; Marchetti-Deschmann, Martina; Allmaier, Günter; Grothe, Hinrich

    2015-04-01

    Heterogeneous ice nucleation plays a major part in ecosystem and climate. Due to the triggering of ice cloud formation it influences the radiation balance of the earth, but also on the ground it can be found to be important in many processes of nature. So far the process of heterogeneous ice nucleation is not fully understood and many questions remain to be answered. Biological ice nucleation is hereby from great interest, because it shows the highest freezing temperatures. Several bacteria and fungi act as ice nuclei. A famous example is Pseudomonas syringae, a bacterium in commercial use (Snomax®), which increases the freezing from homogeneous freezing temperatures of approx. -40° C (for small volumes as in cloud droplets) to temperatures up to -2° C. In 2001 it was found that birch pollen can trigger ice nucleation (Diehl et al. 2001; Diehl et al. 2002). For a long time it was believed that this is due to macroscopic features of the pollen surface. Recent findings of Bernhard Pummer (2012) show a different picture. The ice nuclei are not attached on the pollen surface directly, but on surface material which can be easily washed off. This shows that not only the surface morphology, but also specific molecules or molecular structures are responsible for the ice nucleation activity of birch pollen. With various analytic methods we work on elucidating the structure of these molecules as well as the mechanism with which they trigger ice nucleation. To solve this we use various instrumental analytic techniques like Nuclear Magnetic Resonance spectroscopy (NMR), Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS), and Gas-phase Electrophoretic Mobility Molecular Analysis (GEMMA). Also standard techniques like various chromatographic separation techniques and solvent extraction are in use. We state here that this feature might be due to the aggregation of small molecules, with agglomerates showing a specific surface structure. Our results

  14. Nonequilibrium thermodynamics of nucleation.

    PubMed

    Schweizer, M; Sagis, L M C

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects. PMID:25494727

  15. Nonequilibrium thermodynamics of nucleation

    SciTech Connect

    Schweizer, M.; Sagis, L. M. C.

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  16. Ice nucleation terminology

    NASA Astrophysics Data System (ADS)

    Vali, G.; DeMott, P.; Möhler, O.; Whale, T. F.

    2014-08-01

    Progress in the understanding of ice nucleation is being hampered by the lack of uniformity in how some terms are used in the literature. This even extends to some ambiguity of meanings attached to some terms. Suggestions are put forward here for common use of terms. Some are already well established and clear of ambiguities. Others are less engrained and will need a conscious effort in adoption. Evolution in the range of systems where ice nucleation is being studied enhances the need for a clear nomenclature. The ultimate limit in the clarity of definitions is, of course, the limited degree to which ice nucleation processes are understood.

  17. Nonstationary homogeneous nucleation

    NASA Technical Reports Server (NTRS)

    Harstad, K. G.

    1974-01-01

    The theory of homogeneous condensation is reviewed and equations describing this process are presented. Numerical computer solutions to transient problems in nucleation (relaxation to steady state) are presented and compared to a prior computation.

  18. Critical dynamics in multicomponent lipid membranes.

    PubMed

    Haataja, Mikko

    2009-08-01

    The formation and dynamics of spatially extended compositional domains in multicomponent lipid membranes both in vivo and in vitro lie at the heart of many important biological and biophysical phenomena. While the thermodynamic basis for domain formation has been explored extensively in the past, the roles of membrane and exterior fluid hydrodynamics on domain formation kinetics have received less attention. A case in point is the impact of hydrodynamics on the dynamics of compositional heterogeneities in lipid membranes in the vicinity of a critical point. In this Rapid Communication it is argued that the asymptotic dynamic behavior of a lipid membrane system in the vicinity of a critical point is strongly influenced by hydrodynamic interactions. More specifically, a mode-coupling argument is developed which predicts a scaling behavior of lipid transport coefficients near the critical point for both symmetric and asymmetric bilayers immersed in a bulk fluid. PMID:19792068

  19. Direct imaging of quantum wires nucleated at diatomic steps

    SciTech Connect

    Molina, S. I.; Varela, M.; Sales, D. L.; Ben, T.; Pizarro, J.; Galindo, P. L.; Fuster, D.; Gonzalez, Y.; Gonzalez, L.; Pennycook, S. J.

    2007-10-01

    Atomic steps at growth surfaces are important heterogeneous sources for nucleation of epitaxial nano-objects. In the presence of misfit strain, we show that the nucleation process takes place preferentially at the upper terrace of the step as a result of the local stress relaxation. Evidence for strain-induced nucleation comes from the direct observation by postgrowth, atomic resolution, Z-contrast imaging of an InAs-rich region in a nanowire located on the upper terrace surface of an interfacial diatomic step.

  20. Multicomponent aerosol dynamics model UHMA: model development and validation

    NASA Astrophysics Data System (ADS)

    Korhonen, H.; Lehtinen, K. E. J.; Kulmala, M.

    2004-05-01

    A size-segregated aerosol dynamics model UHMA (University of Helsinki Multicomponent Aerosol model) was developed for studies of multicomponent tropospheric aerosol particles. The model includes major aerosol microphysical processes in the atmosphere with a focus on new particle formation and growth; thus it incorporates particle coagulation and multicomponent condensation, applying a revised treatment of condensation flux onto free molecular regime particles and the activation of nanosized clusters by organic vapours (Nano-Köhler theory), as well as recent parameterizations for binary H2SO4-H2O and ternary H2SO4-NH3-H2O homogeneous nucleation and dry deposition. The representation of particle size distribution can be chosen from three sectional methods: the hybrid method, the moving center method, and the retracking method in which moving sections are retracked to a fixed grid after a certain time interval. All these methods can treat particle emissions and atmospheric transport consistently, and are therefore suitable for use in large scale atmospheric models. In a test simulation against an accurate high resolution solution, all the methods showed reasonable treatment of new particle formation with 20 size sections although the hybrid and the retracking methods suffered from artificial widening of the distribution. The moving center approach, on the other hand, showed extra dents in the particle size distribution and failed to predict the onset of detectable particle formation. In a separate test simulation of an observed nucleation event, the model captured the key qualitative behaviour of the system well. Furthermore, its prediction of the organic volume fraction in newly formed particles, suggesting values as high as 0.5 for 3-4 nm particles and approximately 0.8 for 10 nm particles, agrees with recent indirect composition measurements.

  1. EVALUATING MULTICOMPONENT COMPETITIVE ADSORPTION IN FIXED BEDS

    EPA Science Inventory

    An equilibrium column model (ECM) was developed to evaluate multicomponent competition in fixed-bed adsorption columns. The model ignores mass transfer resistances and uses ideal adsorbed solution theory to predict the competitive effects in multicomponent mixtures. The bed capac...

  2. Heterogeneous Catalysis: On Bathroom Mirrors and Boiling Stones

    ERIC Educational Resources Information Center

    Philipse, Albert P.

    2011-01-01

    Though heterogeneous nucleation of liquid droplets on a smooth surface (such as a bathroom mirror) is a classical topic in nucleation theory, it is not well-known that this topic is actually a pedagogical example of heterogeneous catalysis: the one and only effect of the surface is to lower the activation Gibbs energy of droplet formation. In…

  3. Colloids and Nucleation

    NASA Technical Reports Server (NTRS)

    Ackerson, Bruce

    1997-01-01

    The objectives of the work funded under this grant were to develop a microphotographic technique and use it to monitor the nucleation and growth of crystals of hard colloidal spheres. Special attention is given to the possible need for microgravity studies in future experiments. A number of persons have been involved in this work. A masters student, Keith Davis, began the project and developed a sheet illumination apparatus and an image processing system for detection and analysis. His work on a segmentation program for image processing was sufficient for his master's research and has been published. A post doctoral student Bernie Olivier and a graduate student Yueming He, who originally suggested the sheet illumination, were funded by another source but along with Keith made photographic series of several samples (that had been made by Keith Davis). Data extraction has been done by Keith, Bernie, Yueming and two undergraduates employed on the grant. Results are published in Langmuir. These results describe the sheet lighting technique as one which illuminates not only the Bragg scattering crystal, but all the crystals. Thus, accurate crystal counts can be made for nucleation rate measurements. The strange crystal length scale reduction, observed in small angle light scattering (SALS) studies, following the initial nucleation and growth period, has been observed directly. The Bragg scattering (and dark) crystal size decreases in the crossover region. This could be an effect due to gravitational forces or due to over- compression of the crystal during growth. Direct observations indicate a complex morphology for the resulting hard sphere crystals. The crystal edges are fairly sharp but the crystals have a large degree of internal structure. This structure is a result of (unstable) growth and not aggregation. As yet unpublished work compares growth exponents data with data obtained by SALS. The nucleation rate density is determined over a broad volume fraction range

  4. Self-assembly protocol design for periodic multicomponent structures.

    PubMed

    Jacobs, William M; Frenkel, Daan

    2015-12-14

    Assembling molecular superstructures with many distinct components will allow unprecedented control over morphology at the nanoscale. Recently, this approach has been used to assemble periodic structures with precisely defined features, such as repeating arrays of pores and channels, using a large number of building blocks. Here we propose a predictive tool that allows us to optimize the nucleation and growth of unbounded, ordered structures. In what follows, we call these structures 'crystals', even though they may only be periodic in one or two dimensions. We find that the nucleation barriers and growth pathways for crystals consisting of many components exhibit generic features that are very different from those of simple crystals. To illustrate the very non-classical nature of the nucleation and growth of such structures, we study the formation of one and two-dimensional crystals with multicomponent unit cells. We find that, whilst the boundaries in the non-periodic dimensions significantly affect the stabilities of these crystals, the nucleation barriers are largely determined by the local connectivity of the associated bulk crystal and are independent of the number of distinct components in the unit cell. We predict that the self-assembly of crystals with complex morphologies can be made to follow specific pathways toward the target structure that successively incorporate key features of the three-dimensional target structure. In contrast with simple crystals, it is possible to tune the kinetics of nucleation and growth separately, thus minimizing defect formation. We show how control over self-assembly pathways can be used to optimize the kinetics of formation of extended structures with arbitrary nanoscale patterns. PMID:26404794

  5. A detailed study of ice nucleation by feldspar minerals

    NASA Astrophysics Data System (ADS)

    Whale, T. F.; Murray, B. J.; Wilson, T. W.; Carpenter, M. A.; Harrison, A.; Holden, M. A.; Vergara Temprado, J.; Morris, J.; O'Sullivan, D.

    2015-12-01

    Immersion mode heterogeneous ice nucleation plays a crucial role in controlling the composition of mixed phase clouds, which contain both supercooled liquid water and ice particles. The amount of ice in mixed phase clouds can affect cloud particle size, lifetime and extent and so affects radiative properties and precipitation. Feldspar minerals are probably the most important minerals for ice nucleation in mixed phase clouds because they nucleate ice more efficiently than other components of atmospheric mineral dust (Atkinson et al. 2013). The feldspar class of minerals is complex, containing numerous chemical compositions, several crystal polymorphs and wide variations in microscopic structure. Here we present the results of a study into ice nucleation by a wide range of different feldspars. We found that, in general, alkali feldspars nucleate ice more efficiently than plagioclase feldspars. However, we also found that particular alkali feldspars nucleate ice relatively inefficiently, suggesting that chemical composition is not the only important factor that dictates the ice nucleation efficiency of feldspar minerals. Ice nucleation by feldspar is described well by the singular model and is probably site specific in nature. The alkali feldspars that do not nucleate ice efficiently possess relatively homogenous structure on the micrometre scale suggesting that the important sites for nucleation are related to surface topography. Ice nucleation active site densities for the majority of tested alkali feldspars are similar to those found by Atkinson et al (2013), meaning that the validity of global aerosol modelling conducted in that study is not affected. Additionally, we have found that ice nucleation by feldspars is strongly influenced, both positively and negatively, by the solute content of droplets. Most other nucleants we have tested are unaffected by solutes. This provides insight into the mechanism of ice nucleation by feldspars and could be of importance

  6. Heterogeneous atmospheric chemistry

    NASA Technical Reports Server (NTRS)

    Schryer, D. R.

    1982-01-01

    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.

  7. Nucleation of Ice

    NASA Astrophysics Data System (ADS)

    Molinero, Valeria

    2009-03-01

    The freezing of water into ice is a ubiquitous transformation in nature, yet the microscopic mechanism of homogeneous nucleation of ice has not yet been elucidated. One of the reasons is that nucleation happens in time scales that are too fast for an experimental characterization and two slow for a systematic study with atomistic simulations. In this work we use coarse-grained molecular dynamics simulations with the monatomic model of water mW[1] to shed light into the mechanism of homogeneous nucleation of ice and its relationship to the thermodynamics of supercooled water. Cooling of bulk water produces either crystalline ice or low- density amorphous ice (LDA) depending on the quenching rate. We find that ice crystallization occurs faster at temperatures close to the liquid-liquid transition, defined as the point of maximum inflection of the density with respect to the temperature. At the liquid-liquid transition, the time scale of nucleation becomes comparable to the time scale of relaxation within the liquid phase, determining --effectively- the end of the metastable liquid state. Our results imply that no ultraviscous liquid water can exist at temperatures just above the much disputed glass transition of water. We discuss how the scenario is changed when water is in confinement, and the relationship of the mechanism of ice nucleation to that of other liquids that present the same phase behavior, silicon [2] and germanium [3]. [4pt] [1] Molinero, V. & Moore, E. B. Water modeled as an intermediate element between carbon and silicon. Journal of Physical Chemistry B (2008). Online at http://pubs.acs.org/cgi- bin/abstract.cgi/jpcbfk/asap/abs/jp805227c.html [0pt] [2] Molinero, V., Sastry, S. & Angell, C. A. Tuning of tetrahedrality in a silicon potential yields a series of monatomic (metal-like) glass formers of very high fragility. Physical Review Letters 97, 075701 (2006).

  8. Experimental Studies in Ice Nucleation

    NASA Astrophysics Data System (ADS)

    Wright, Timothy Peter

    Ice nuclei play a critical role in the formation of precipitation in mixed phase clouds. Modification of IN concentrations can lead to changes in cloud lifetimes and precipitation size. Presented in this study are experimental investigations into ice nuclei in an ongoing effort to reduce the uncertainties that ice nuclei have on cloud processes and climate. This research presents a new version of the cold stage drop freezing assay to investigate the time-dependence of heterogeneous nucleation. The temperature range for the instrument spans from the melting point of water to the homogeneous freezing limit of ˜-38 deg C. Temperature stability for the instrument allowed for experimental operation for up to four days while interrogating the same sample. Up to a one hundred fold increase in the number of analyzed drops was accomplished through an in-house written automated drop freezing detection software package. Combined instrument design improvements allow for the analysis of IN concentrations down to ˜10-8 ice nuclei per picoliter of sample water. A new variant of the multiple-component stochastic model for heterogeneous ice nucleation was used to investigate the time dependence of heterogeneous freezing processes. This was accomplished by analyzing how the changes in the cooling rate can impact the observed nucleation rate. The model employed four material-dependent parameters to accurately capture the observed freezing of water drops containing Arizona Test Dust. The parameters were then used to accurately predict the freezing behavior of the drops in time dependent experiments. The time dependence freezing of a wide range of materials was then investigated. These materials included the minerals montmorillonite and kaolinite, the biological proxy ice nuclei contained within the product Icemax, and flame soot generated from the incomplete combustion of ethylene gas. The time dependence for ice nuclei collected from rainwater samples was also investigated. The

  9. Effect of cloud-scale vertical velocity on the contribution of homogeneous nucleation to cirrus formation and radiative forcing

    NASA Astrophysics Data System (ADS)

    Shi, X.; Liu, X.

    2016-06-01

    Ice nucleation is a critical process for the ice crystal formation in cirrus clouds. The relative contribution of homogeneous nucleation versus heterogeneous nucleation to cirrus formation differs between measurements and predictions from general circulation models. Here we perform large-ensemble simulations of the ice nucleation process using a cloud parcel model driven by observed vertical motions and find that homogeneous nucleation occurs rather infrequently, in agreement with recent measurement findings. When the effect of observed vertical velocity fluctuations on ice nucleation is considered in the Community Atmosphere Model version 5, the relative contribution of homogeneous nucleation to cirrus cloud occurrences decreases to only a few percent. However, homogeneous nucleation still has strong impacts on the cloud radiative forcing. Hence, the importance of homogeneous nucleation for cirrus cloud formation should not be dismissed on the global scale.

  10. Parameterizations for ice nucleation in biological and atmospheric systems.

    PubMed

    Koop, Thomas; Zobrist, Bernhard

    2009-12-14

    Ice nucleation is an important process in numerous environmental systems such as atmospheric aerosol droplets or biological tissues. Here we analyze two widely used approaches for describing homogeneous ice nucleation in aqueous solutions with respect to their applicability to heterogeneous ice nucleation processes: the lambda approach and the water-activity-based approach. We study experimentally the heterogeneous ice nucleation behaviour of mineral dust particles and biological ice nuclei (Snomax; Pseudomonas syringae) in aqueous solutions as a function of solute concentration for various solutes (sulfuric acid, ammonium sulfate, glucose, and poly(ethylene glycol) with two different molar masses of 400 and 6000 g mol(-1)). We show that the ice nucleation temperature and the corresponding lambda values depend on both the type of ice nucleus and the type of solute, while the water-activity-based approach depends only on the type of ice nucleus when the solution water activity is known. Finally, we employ both approaches to the study of ice nucleation in biological systems such as the supercooling point of living larvae and insects. We show that the behaviour of freeze tolerant and freeze avoiding species can be described using the two approaches and we discuss how the analysis can be used to interpret experimental results of the freezing behaviour of living species. PMID:19924318

  11. Mediating conducting polymer growth within hydrogels by controlling nucleation

    NASA Astrophysics Data System (ADS)

    Patton, A. J.; Green, R. A.; Poole-Warren, L. A.

    2015-01-01

    This study examines the efficacy of primary and secondary nucleation for electrochemical polymerisation of conductive polymers within poly(vinyl alcohol) methacrylate hydrogels. The two methods of nucleation investigated were a primary heterogeneous mechanism via introduction of conductive bulk metallic glass (Mg64Zn30Ca5Na1) particles and a secondary mechanism via introduction of "pre-polymerised" conducting polymer within the hydrogel (PEDOT:PSS). Evidence of nucleation was not seen in the bulk metallic glass loaded gels, however, the PEDOT:PSS loaded gels produced charge storage capacities over 15 mC/cm2 when sufficient polymer was loaded. These studies support the hypothesis that secondary nucleation is an efficient approach to producing stand-alone conducting hydrogels.

  12. Biomaterials-Potential nucleation agents in blood and possible implications.

    PubMed

    Rohnke, Marcus; Henss, Anja

    2016-01-01

    Blood, simulated body fluids, and many cell culture media are supersaturated solutions with respect to several calcium phosphates. Therefore biomaterials can act as nucleation agents and evoke heterogeneous nucleation of salts on the surface of immersed biomaterials. Depending on the field of application, this can be either beneficial or disadvantageous. Although nucleation from supersaturated solutions is an old and well-known scientific phenomenon it is not standard to test new developed materials with surface analytical methods for their ability to initiate nucleation in vitro. Therefore, this communication aims to review the mineralization effect and to emphasize the possible negative implications, especially to functionalized bone implants. Surface coatings with proteins, growth factors, and, etc., can become ineffective due to deposition of a dense calcium phosphate layer. In the case of drug loaded implants, drug release might be inhibited. PMID:27316221

  13. Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

    PubMed Central

    Hamm, Laura M.; Giuffre, Anthony J.; Han, Nizhou; Tao, Jinhui; Wang, Debin; De Yoreo, James J.; Dove, Patricia M.

    2014-01-01

    The physical basis for how macromolecules regulate the onset of mineral formation in calcifying tissues is not well established. A popular conceptual model assumes the organic matrix provides a stereochemical match during cooperative organization of solute ions. In contrast, another uses simple binding assays to identify good promoters of nucleation. Here, we reconcile these two views and provide a mechanistic explanation for template-directed nucleation by correlating heterogeneous nucleation barriers with crystal–substrate-binding free energies. We first measure the kinetics of calcite nucleation onto model substrates that present different functional group chemistries (carboxyl, thiol, phosphate, and hydroxyl) and conformations (C11 and C16 chain lengths). We find rates are substrate-specific and obey predictions of classical nucleation theory at supersaturations that extend above the solubility of amorphous calcium carbonate. Analysis of the kinetic data shows the thermodynamic barrier to nucleation is reduced by minimizing the interfacial free energy of the system, γ. We then use dynamic force spectroscopy to independently measure calcite–substrate-binding free energies, ΔGb. Moreover, we show that within the classical theory of nucleation, γ and ΔGb should be linearly related. The results bear out this prediction and demonstrate that low-energy barriers to nucleation correlate with strong crystal–substrate binding. This relationship is general to all functional group chemistries and conformations. These findings provide a physical model that reconciles the long-standing concept of templated nucleation through stereochemical matching with the conventional wisdom that good binders are good nucleators. The alternative perspectives become internally consistent when viewed through the lens of crystal–substrate binding. PMID:24434555

  14. High-Precision Nucleation Rate Measurements for Higher Melting Metals

    NASA Astrophysics Data System (ADS)

    Bokeloh, Joachim; Wilde, Gerhard

    2014-08-01

    Nucleation of a crystal in undercooled melts of higher melting face-centered-cubic-metals has often been studied in the past. However, the data available were not of sufficient accuracy and only covered nucleation rates in too small of a range to allow precise conclusions concerning the nature of the underlying process as well as concerning important parameters such as the solid-liquid interface free energy that can in principle be deducted from such analyses. One way to circumvent ambiguities and analyze nucleation kinetics under well-defined conditions experimentally is given by performing statistically significant numbers of repeated single droplet experiments. Application of proper statistics analyses yields nucleation rates that are independent of a specific nucleation model. The first studies that were conducted in accordance with this approach on pure model materials revealed that the approach is valid. The results are comparable to those obtained by classic nucleation theory applied to experimental data, and it was shown that one might need to rethink the common assumption that heterogeneous nucleation is almost always responsible for solidification initiation. The current results also show that often-used models for the solid-liquid interface free energy might lead to overestimated values.

  15. Nucleation at the Contact Line Observed on Nanotextured Surfaces

    NASA Astrophysics Data System (ADS)

    Kostinski, A. B.; Gurganus, C.; Charnawskas, J. C.; Shaw, R. A.

    2015-12-01

    Surface nucleation, and contact nucleation in particular, are important for many physical processes, including pharmaceutical drug synthesis, metallurgy, and heterogeneous ice nucleation. It has been conjectured that roughness plays a role in surface nucleation, the tendency for freezing to begin preferentially at the liquid-gas interface. Using high speed imaging, we sought evidence for freezing at the contact line on catalyst substrates with imposed characteristic length scales (texture). It is found that nano-scale texture causes a shift in the nucleation of ice in super-cooled water to the three-phase contact line, while micro-scale texture does not. The reduction in the Gibbs barrier for nucleation at the droplet triple line suggests that a line tension, inversely proportional to the surface feature length scale, may be the relevant physical mechanism. A survey of line tension values in literature supports this hypothesis. This work suggests that the physical morphology of a particle, and not just its chemical composition, is important for characterizing a nucleation catalyst.

  16. Surface Bubble Nucleation Stability

    NASA Astrophysics Data System (ADS)

    Seddon, James R. T.; Kooij, E. Stefan; Poelsema, Bene; Zandvliet, Harold J. W.; Lohse, Detlef

    2011-02-01

    Recent research has revealed several different techniques for nanoscopic gas nucleation on submerged surfaces, with findings seemingly in contradiction with each other. In response to this, we have systematically investigated the occurrence of surface nanobubbles on a hydrophobized silicon substrate for various different liquid temperatures and gas concentrations, which we controlled independently. We found that nanobubbles occupy a distinct region of this parameter space, occurring for gas concentrations of approximately 100%-110%. Below the nanobubble region we did not detect any gaseous formations on the substrate, whereas micropancakes (micron wide, nanometer high gaseous domains) were found at higher temperatures and gas concentrations. We moreover find that supersaturation of dissolved gases is not a requirement for nucleation of bubbles.

  17. Scale Reliability Evaluation with Heterogeneous Populations

    ERIC Educational Resources Information Center

    Raykov, Tenko; Marcoulides, George A.

    2015-01-01

    A latent variable modeling approach for scale reliability evaluation in heterogeneous populations is discussed. The method can be used for point and interval estimation of reliability of multicomponent measuring instruments in populations representing mixtures of an unknown number of latent classes or subpopulations. The procedure is helpful also…

  18. Bleb Nucleation through Membrane Peeling

    NASA Astrophysics Data System (ADS)

    Alert, Ricard; Casademunt, Jaume

    2016-02-01

    We study the nucleation of blebs, i.e., protrusions arising from a local detachment of the membrane from the cortex of a cell. Based on a simple model of elastic linkers with force-dependent kinetics, we show that bleb nucleation is governed by membrane peeling. By this mechanism, the growth or shrinkage of a detached membrane patch is completely determined by the linker kinetics, regardless of the energetic cost of the detachment. We predict the critical nucleation radius for membrane peeling and the corresponding effective energy barrier. These may be typically smaller than those predicted by classical nucleation theory, implying a much faster nucleation. We also perform simulations of a continuum stochastic model of membrane-cortex adhesion to obtain the statistics of bleb nucleation times as a function of the stress on the membrane. The determinant role of membrane peeling changes our understanding of bleb nucleation and opens new directions in the study of blebs.

  19. Multi-Component Dark Matter

    SciTech Connect

    Zurek, Kathryn M.

    2008-11-01

    We explore multi-component dark matter models where the dark sector consists of multiple stable states with different mass scales, and dark forces coupling these states further enrich the dynamics. The multi-component nature of the dark matter naturally arises in supersymmetric models, where both R parity and an additional symmetry, such as a Z{sub 2}, is preserved. We focus on a particular model where the heavier component of dark matter carries lepton number and annihilates mostly to leptons. The heavier component, which is essentially a sterile neutrino, naturally explains the PAMELA, ATIC and synchrotron signals, without an excess in antiprotons which typically mars other models of weak scale dark matter. The lighter component, which may have a mass from a GeV to a TeV, may explain the DAMA signal, and may be visible in low threshold runs of CDMS and XENON, which search for light dark matter.

  20. Multicomponent reactions in nucleoside chemistry

    PubMed Central

    Buchowicz, Włodzimierz

    2014-01-01

    Summary This review covers sixty original publications dealing with the application of multicomponent reactions (MCRs) in the synthesis of novel nucleoside analogs. The reported approaches were employed for modifications of the parent nucleoside core or for de novo construction of a nucleoside scaffold from non-nucleoside substrates. The cited references are grouped according to the usually recognized types of the MCRs. Biochemical properties of the novel nucleoside analogs are also presented (if provided by the authors). PMID:25161730

  1. A Sustainable Multicomponent Pyrimidine Synthesis.

    PubMed

    Deibl, Nicklas; Ament, Kevin; Kempe, Rhett

    2015-10-14

    Since alcohols are accessible from indigestible biomass (lignocellulose), the development of novel preferentially catalytic reactions in which alcohols are converted into important classes of fine chemicals is a central topic of sustainable synthesis. Multicomponent reactions are especially attractive in organic chemistry as they allow the synthesis of large libraries of diversely functionalized products in a short time when run in a combinatorial fashion. Herein, we report a novel, regioselective, iridium-catalyzed multicomponent synthesis of pyrimidines from amidines and up to three (different) alcohols. This reaction proceeds via a sequence of condensation and dehydrogenation steps which give rise to selective C-C and C-N bond formations. While the condensation steps deoxygenate the alcohol components, the dehydrogenations lead to aromatization. Two equiv of hydrogen and water are liberated in the course of the reactions. PN5P-Ir-pincer complexes, recently developed in our laboratory, catalyze this sustainable multicomponent process most efficiently. A total of 38 different pyrimidines were synthesized in isolated yields of up to 93%. Strong points of the new protocol are its regioselectivity and thus the immediate access to pyrimidines that are highly and unsymmetrically decorated with alkyl or aryl substituents. The combination of this novel protocol with established methods for converting alcohols to nitriles now allows to selectively assemble pyrimidines from four alcohol building blocks and 2 equiv of ammonia. PMID:26414993

  2. Crystal nucleation and glass formation in metallic alloy melts

    NASA Technical Reports Server (NTRS)

    Spaepen, F.

    1984-01-01

    Homogeneous nucleation, containerless solidification, and bulk formation of metallic glasses are discussed. Homogeneous nucleation is not a limiting factor for metallic glass formation at slow cooling rates if the reduced glass transition temperature is high enough. Such glasses can be made in bulk if heterogeneous nucleants are removed. Containerless processing eleminates potential sources of nucleants, but as drop tube experiments on the Pd-Si alloys show, the free surface may still be a very effective heterogeneous nucleant. Combination of etching and heating in vacuum or fluxing can be effective for cleaning fairly large ingots of nucleants. Reduced gravity processing has a potentially useful role in the fluxing technique, for example to keep large metallic ingots surrounded by a low density, low fluidity flux if this proved difficult under ground conditions. For systems where heterogeneous nucleants in the bulk of the ingot need gravity to segregate to the flux-metal interface, reduced gravity processing may not be appropriate for bulk glass formation.

  3. Ice Nucleation by High Molecular Weight Organic Compounds

    NASA Astrophysics Data System (ADS)

    Cantrell, W.

    2003-12-01

    Deep convection in the tropics is frequently associated with biomass burning. Recent work has suggested that the size of ice crystals in the anvils of tropical cumulonimbus clouds may be affected by biomass burning, though the mechanism for such an effect is uncertain (Sherwood, 2002). We will present results of an investigation of the role that high molecular weight organic compounds, known to be produced in biomass burning (Elias et al., 1999), may play in tropical cirrus anvils through heterogeneous nucleation of ice. In particular, we examine the mechanisms underlying heterogeneous nucleation of ice by films of long chain alcohols by studying the interaction of the alcohols and water/ice using temperature controlled, Attenuated Total Reflection - Fourier Transform Infrared spectroscopy. The mechanisms are interpreted in the context of recent criticisms of some aspects of classical nucleation theory (Seeley and Seidler, 2001; Oxtoby, 1998). References V. Elias, B. Simoneit, A. Pereira, J. Cabral, and J. Cardoso, Detection of high molecular weight organic tracers in vegetation smoke samples by high-temperature gas chromatography-mass spectrometry. Environ. Sci. Tecnol., 33, 2369-2376, 1999. D. Oxtoby, Nucleation of first-order phase transitions. Acc. Chem. Res., 31, 91-97, 1998. L. Seeley and G. Seidler, Preactivation in the nucleation of ice by Langmuir films of aliphatic alcohols. J. Chem. Phys., 114, 10464-10470, 2001. S. Sherwood, Aerosols and ice particle size in tropical cumulonimbus. J. Climate, 15, 1051-1063, 2002.

  4. Surface Nanobubbles Nucleate Microdroplets

    NASA Astrophysics Data System (ADS)

    Zhang, Xuehua; Lhuissier, Henri; Sun, Chao; Lohse, Detlef

    2014-04-01

    When a hydrophobic solid is in contact with water, surface nanobubbles often form at the interface. They have a lifetime many orders of magnitude longer than expected. Here, we show that they even withstand a temperature increase to temperatures close to the boiling point of bulk water; i.e., they do not nucleate larger bubbles ("superstability"). On the contrary, when the vapor-liquid contact line passes a nanobubble, a liquid film remains around it, which, after pinch-off, results in a microdroplet in which the nanobubbles continue to exist. Finally, the microdroplet evaporates and the nanobubble consequently bursts. Our results support that pinning plays a crucial role for nanobubble stability.

  5. Transient nucleation in condensed systems

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Greer, A. L.; Thompson, C. V.

    1983-01-01

    Using classical nucleation theory we consider transient nucleation occurring in a one-component, condensed system under isothermal conditions. We obtain an exact closed-form expression for the time dependent cluster populations. In addition, a more versatile approach is developed: a numerical simulation technique which models directly the reactions by which clusters are produced. This simulation demonstrates the evolution of cluster populations and nucleation rate in the transient regime. Results from the simulation are verified by comparison with exact analytical solutions for the steady state. Experimental methods for measuring transient nucleation are assessed, and it is demonstrated that the observed behavior depends on the method used. The effect of preexisting cluster distributions is studied. Previous analytical and numerical treatments of transient nucleation are compared to the solutions obtained from the simulation. The simple expressions of Kashchiev are shown to give good descriptions of the nucleation behavior.

  6. Nucleation in a nickel-based superalloy utilizing computational thermodynamics and diffusion kinetics

    NASA Astrophysics Data System (ADS)

    Boutwell, Brett Allen Rohrer

    A model for predicting nucleation kinetics of coherent, homogeneous precipitates using thermodynamic and diffusion kinetic data calculated by computer modeling software was developed. The nucleation model incorporated classical nucleation theory along with derivations of the incubation time using the theory of time reversal symmetry. An atomic mobility database was developed for a seven-element nickel-based superalloy to allow for the calculation of multicomponent diffusivities to be used in the incubation time calculations. The seven elements modeled in the database were: nickel (Ni), iron (Fe), chromium (Cr), niobium (Nb), titanium (Ti), aluminum (Al), and carbon (C). The process of assessing an atomic mobility database is discussed, and the difficulties of assembling such a database are reviewed. The nucleation model and atomic mobility database were then applied to modeling the nucleation kinetics of gamma' in two nickel-aluminum binary alloys. The results of the nucleation model were in good agreement with one binary alloy but did not agree well with the results for the second alloy. Enhanced diffusion due to excess vacancy concentrations was identified as the most probable reason for the discrepancy with the second nickel-aluminum alloy. The nucleation model and atomic mobility database were then tested on an industrial, multicomponent nickel-based superalloy, Inconel alloy 706. The precipitation kinetics of two coherent precipitates, gamma' and gamma'', were modeled and compared to Time-Temperature-Transformation diagrams and Time-Temperature-Hardness diagrams for the alloy. The calculated incubation times for gamma ' and gamma'' were faster than the experimentally observed transformation start times. The results of the gamma' incubation time calculations were in close approximation to the experimental data at higher temperatures. The results of the gamma'' calculations did not agree well with the experimental data.

  7. The Ice Nucleation Ability of Selected Atmospherically Abundant Fungal Spores

    NASA Astrophysics Data System (ADS)

    Iannone, R.; Chernoff, D. I.; Bertram, A. K.

    2010-12-01

    Ice clouds are widely recognized for their roles in the earth’s radiation budget and climate systems. However, their formation mechanisms are poorly understood thus constituting an uncertainty in the evaluation of the global radiation budget. An important mechanism of ice cloud formation is heterogeneous nucleation on aerosol particles. The surface properties of these particles, called ice nuclei (IN), directly affect the temperature at which ice nucleation occurs. There is a growing emphasis on the study of bioaerosols (e.g., bacteria, fungi, pollen) as IN since they are ubiquitous in the atmosphere. The focus of the current study is to determine the ice nucleation properties of spores obtained from a variety of fungi. Aerosolized spores were impacted onto a hydrophobic glass substrate and immersed in ultrapure water. A technique involving an optical light microscope coupled to a flow cell was used to precisely control temperature and humidity within the cell. A digital camera captured high-resolution video of the particles undergoing ice nucleation, allowing for the analyses of freezing events and particle sizes. The first experimental results using spores obtained from the fungal genera Cladosporium and Penicillium reveal an average temperature increase of ~1-5 K in the ice nucleation temperature compared to homogeneous nucleation (i.e., freezing of pure liquid water). Furthermore, there appears to be a relationship between the amount of spores present per droplet and the freezing temperature of water. These results are presented and discussed, and the potential contribution of these data to further the understanding of heterogeneous nucleation in the atmosphere is provided. Box plot summarizing freezing data for homogeneous nucleation experiments (leftmost box) and binned data from heterogeneous nucleation experiments involving spores of Cladosporium. Freezing data are distributed into 200 µm2 bins that represent the total area of all observable inclusions

  8. Immersion freezing of ice nucleating active protein complexes

    NASA Astrophysics Data System (ADS)

    Hartmann, S.; Augustin, S.; Clauss, T.; Voigtländer, J.; Niedermeier, D.; Wex, H.; Stratmann, F.

    2012-08-01

    Biological particles, e.g. bacteria and their Ice Nucleating Active (INA) protein complexes, might play an important role for the ice formation in atmospheric mixed-phase clouds. Therefore, the immersion freezing behavior of INA protein complexes generated from a SnomaxTM solution/suspension was investigated as function of temperature in a range of -5 °C to -38 °C at the Leipzig Aerosol Cloud Interaction Simulator (LACIS). The immersion freezing of droplets containing small numbers of INA protein complexes occurs in a temperature range of -7 °C and -10 °C. The experiments performed in the lower temperature range, where all droplets freeze which contain at least one INA protein complex, are used to determine the average number of INA protein complexes present, assuming that the INA protein complexes are Poisson distributed over the droplet ensemble. Knowing the average number of INA protein complexes, the heterogeneous ice nucleation rate and rate coefficient of a single INA protein complex is determined by using the newly-developed CHESS model (stoCHastic model of idEntical poiSSon distributed ice nuclei). Therefore, we assume the ice nucleation process to be of stochastic nature, and a parameterization of the INA protein complex's nucleation rate. Analyzing the results of immersion freezing experiments from literature (SnomaxTM and Pseudomonas syringae bacteria), to results gained in this study, demonstrates that first, a similar temperature dependence of the heterogeneous ice nucleation rate for a single INA protein complex was found in all experiments, second, the shift of the ice fraction curves to higher temperatures can be explained consistently by a higher average number of INA protein complexes being present in the droplet ensemble, and finally the heterogeneous ice nucleation rate of one single INA protein complex might be also applicable for intact Pseudomonas syringae bacteria cells. The results obtained in this study allow a new perspective on the

  9. Parameterization of the Cloud Nucleating Activity of Fresh, Aged, and Internally-Mixed Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Kreidenweis, S.; Petters, M.; Demott, P.; Prenni, A.; Ziemann, P.

    2006-12-01

    Carbonaceous particle types affect global climate, visibility, and human health, but their primary and secondary sources, sinks, and tropospheric lifetimes are highly uncertain. The size and hygroscopicity of particles, and in particular their activity as cloud condensation nuclei (CCN), plays a large role in determining their atmospheric impacts and lifetimes. However, hygroscopicity is difficult to parameterize for many organic species for which no thermodynamic data exist, and for complex, multicomponent aerosols of undefined composition. We propose a simple method to describe the relationship between dry particle diameter and CCN activity using a single hygroscopicity parameter, κ. We derive values of κ from fitting of experimental CCN-activity data from the literature and from recent experiments, including oxidation-aged organic particles and secondary organic aerosols. Values of κ are between 0.5 and 2 for highly-CCN- active salts such as sodium chloride, between 0.01 and 0.5 for slightly to very hygroscopic organic aerosols such as those produced in biomass burning and as secondary organic aerosols, and 0 for nonhygroscopic components. The hygroscopicity of internal mixtures can be calculated as a volume fraction weighted average of the hygroscopicity parameters of the individual species comprising the mixture. Aging of aerosol, understood as changes in hygroscopicity due to condensation of hydrophilic species, coagulation of aerosol populations, or heterogeneous chemical reactions, are described conveniently by changes in κ. Our studies show that oxidative aging that proceeds by addition of functional groups to the CHx carbon backbone leads to only small changes in κ, and thus the process alone is inefficient at rendering small, initially- hydrophobic primary organic particles capable of being scavenged by cloud-drop nucleation. Other processes, such as coagulation and condensation, control the rate of hydrophobic-to-hydrophilic conversion of primary

  10. Nucleation of mesospheric cloud particles: Sensitivities and limits

    NASA Astrophysics Data System (ADS)

    Wilms, Henrike; Rapp, Markus; Kirsch, Annekatrin

    2016-03-01

    Nucleation of mesospheric ice particles is thought to occur via heterogeneous nucleation on meteor smoke particles. However, several factors determining the nucleation rate are poorly known. To study the effect of uncertainties in the nucleation rate on cloud properties, we use the Community Aerosol and Radiation Model for Atmospheres and systematically vary the nucleation rate over ±10 orders of magnitude. In one set of simulations, the background state of the atmosphere is described by climatological conditions. In a second set, gravity wave-perturbed profiles from the Kühlungsborn Mechanistic general Circulation Model (KMCM) are used with typical temperature (vertical wind) perturbations at the mesopause on the order of 9 K (0.45 m/s). The resulting noctilucent cloud (NLC) characteristics are compared to lidar and satellite measurements. Realistic NLCs compared to the lidar measurements can only be modeled if the nucleation rate is reduced by up to 3 orders of magnitude compared to standard assumptions. For the same cases, the simulated NLCs compare best to the satellite measurements if the nucleation rate is reduced by 2 orders of magnitude or more. Dynamical processes at the mesopause strongly influence the NLC development. In a gravity wave-perturbed atmosphere, the ice particles have only limited time for nucleation and growth. The growth time is limited by the vertical wind, because the vertical wind determines the residence time of the ice particles in the supersaturated region. Since the vertical wind amplitudes reach 1.5 m/s in KMCM (compared to a mean upwelling of ˜4 cm/s in the climatology), the ice particles remain significantly smaller in a gravity wave-perturbed atmosphere than in climatological background conditions.

  11. A Multicomponent Latent Trait Model for Diagnosis

    ERIC Educational Resources Information Center

    Embretson, Susan E.; Yang, Xiangdong

    2013-01-01

    This paper presents a noncompensatory latent trait model, the multicomponent latent trait model for diagnosis (MLTM-D), for cognitive diagnosis. In MLTM-D, a hierarchical relationship between components and attributes is specified to be applicable to permit diagnosis at two levels. MLTM-D is a generalization of the multicomponent latent trait…

  12. Dynamics of vortex nucleation in sup 3 He- A flow

    SciTech Connect

    Kopnin, N.B.; Soininen, P.I.; Salomaa, M.M. )

    1992-03-01

    Quantum phase slippage in superfluid {sup 3}He flow is simulated numerically in rectangular slab geometries. Assuming that the flow is confined to a channel having horizontal surfaces close to each other, the spatial problem reduces to the two transverse dimensions; we report time-dependent computer simulations of superfluid {sup 3}He flow in 2+1 dimensions using the time-dependent Ginzburg-Landau equations. The quantum-dynamic processes of phase slippage in {sup 3}He are demonstrated to be associated with superfluid vortex nucleation; we thus confirm Anderson's assumption for phase slippage through vortex motion in superfluids. We also find several other phase-slip scenarios involving vortices, phase-slip lines, and combinations thereof for the coupled multicomponent order-parameter amplitudes. We consider both diffuse and specular boundary conditions at the side walls and demonstrate that our results are essentially independent of the boundaries. We compute the critical current for vortex nucleation as a function of the channel width, and compare it with existing theories of vortex nucleation; we also discuss our calculations in connection with experiments on phase slippage in {sup 3}He flow. One of our most important results is that the superfluid order parameter for the vortices generated in the computer simulations does not vanish anywhere; i.e., the vortices possess superfluid core structures; hence the processes of phase slip for superfluid {sup 3}He are nonlocal in space-time.

  13. Surface nanobubbles nucleate microdroplets.

    PubMed

    Zhang, Xuehua; Lhuissier, Henri; Sun, Chao; Lohse, Detlef

    2014-04-11

    When a hydrophobic solid is in contact with water, surface nanobubbles often form at the interface. They have a lifetime many orders of magnitude longer than expected. Here, we show that they even withstand a temperature increase to temperatures close to the boiling point of bulk water; i.e., they do not nucleate larger bubbles ("superstability"). On the contrary, when the vapor-liquid contact line passes a nanobubble, a liquid film remains around it, which, after pinch-off, results in a microdroplet in which the nanobubbles continue to exist. Finally, the microdroplet evaporates and the nanobubble consequently bursts. Our results support that pinning plays a crucial role for nanobubble stability. PMID:24765973

  14. On Capillary Rise and Nucleation

    ERIC Educational Resources Information Center

    Prasad, R.

    2008-01-01

    A comparison of capillary rise and nucleation is presented. It is shown that both phenomena result from a balance between two competing energy factors: a volume energy and a surface energy. Such a comparison may help to introduce nucleation with a topic familiar to the students, capillary rise. (Contains 1 table and 3 figures.)

  15. Preferential Nucleation during Polymorphic Transformations

    PubMed Central

    Sharma, H.; Sietsma, J.; Offerman, S. E.

    2016-01-01

    Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR’s) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR’s with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller – and therefore nucleation more probable - with increasing number of special OR’s. These insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material. PMID:27484579

  16. Preferential Nucleation during Polymorphic Transformations

    NASA Astrophysics Data System (ADS)

    Sharma, H.; Sietsma, J.; Offerman, S. E.

    2016-08-01

    Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR’s) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR’s with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller – and therefore nucleation more probable - with increasing number of special OR’s. These insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material.

  17. Nucleation rate in monotectic alloys

    NASA Astrophysics Data System (ADS)

    Falk, F.

    Cooling a melt of a monotectic system into the miscibility gap results in nucleation of fluid droplets in a fluid matrix prior to solidification. For homogeneous nucleation the temperature dependence of the nucleation rate is calculated. As material parameters the chemical potential of the species involved, the diffusion constant of the fluid, and the surface tension between adjacent phases are important. Since their temperature dependence is not well known from experiments, different theoretical models are used and their influence is discussed. The surface tension turns out to be the most crucial parameter in determining the nucleation rate. For AlIn numerical results are presented. In this system the undercooling with respect to homogeneous nucleation increases from zero at the critical point to 100 K at a composition near the monotectic point.

  18. Phase nucleation in curved space

    NASA Astrophysics Data System (ADS)

    Gómez, Leopoldo; García, Nicolás; Vitelli, Vincenzo; Lorenzana, José; Daniel, Vega

    Nucleation and growth is the dominant relaxation mechanism driving first-order phase transitions. In two-dimensional flat systems, nucleation has been applied to a wide range of problems in physics, chemistry and biology. Here we study nucleation and growth of two-dimensional phases lying on curved surfaces and show that curvature modifies both critical sizes of nuclei and paths towards the equilibrium phase. In curved space, nucleation and growth becomes inherently inhomogeneous and critical nuclei form faster on regions of positive Gaussian curvature. Substrates of varying shape display complex energy landscapes with several geometry-induced local minima, where initially propagating nuclei become stabilized and trapped by the underlying curvature (Gómez, L. R. et al. Phase nucleation in curved space. Nat. Commun. 6:6856 doi: 10.1038/ncomms7856 (2015).).

  19. Preferential Nucleation during Polymorphic Transformations.

    PubMed

    Sharma, H; Sietsma, J; Offerman, S E

    2016-01-01

    Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR's) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR's with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller - and therefore nucleation more probable - with increasing number of special OR's. These insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material. PMID:27484579

  20. Immersion freezing of ice nucleation active protein complexes

    NASA Astrophysics Data System (ADS)

    Hartmann, S.; Augustin, S.; Clauss, T.; Wex, H.; Šantl-Temkiv, T.; Voigtländer, J.; Niedermeier, D.; Stratmann, F.

    2013-06-01

    Utilising the Leipzig Aerosol Cloud Interaction Simulator (LACIS), the immersion freezing behaviour of droplet ensembles containing monodisperse particles, generated from a Snomax™ solution/suspension, was investigated. Thereto ice fractions were measured in the temperature range between -5 °C to -38 °C. Snomax™ is an industrial product applied for artificial snow production and contains Pseudomonas syringae} bacteria which have long been used as model organism for atmospheric relevant ice nucleation active (INA) bacteria. The ice nucleation activity of such bacteria is controlled by INA protein complexes in their outer membrane. In our experiments, ice fractions increased steeply in the temperature range from about -6 °C to about -10 °C and then levelled off at ice fractions smaller than one. The plateau implies that not all examined droplets contained an INA protein complex. Assuming the INA protein complexes to be Poisson distributed over the investigated droplet populations, we developed the CHESS model (stoCHastic modEl of similar and poiSSon distributed ice nuclei) which allows for the calculation of ice fractions as function of temperature and time for a given nucleation rate. Matching calculated and measured ice fractions, we determined and parameterised the nucleation rate of INA protein complexes exhibiting class III ice nucleation behaviour. Utilising the CHESS model, together with the determined nucleation rate, we compared predictions from the model to experimental data from the literature and found good agreement. We found that (a) the heterogeneous ice nucleation rate expression quantifying the ice nucleation behaviour of the INA protein complex is capable of describing the ice nucleation behaviour observed in various experiments for both, Snomax™ and P. syringae bacteria, (b) the ice nucleation rate, and its temperature dependence, seem to be very similar regardless of whether the INA protein complexes inducing ice nucleation are attached

  1. Main features of nucleation in model solutions of oral cavity

    NASA Astrophysics Data System (ADS)

    Golovanova, O. A.; Chikanova, E. S.; Punin, Yu. O.

    2015-05-01

    The regularities of nucleation in model solutions of oral cavity have been investigated, and the induction order and constants have been determined for two systems: saliva and dental plaque fluid (DPF). It is shown that an increase in the initial supersaturation leads to a transition from the heterogeneous nucleation of crystallites to a homogeneous one. Some additives are found to enhance nucleation: HCO{3/-} > C6H12O6 > F-, while others hinder this process: protein (casein) > Mg2+. It is established that crystallization in DPF occurs more rapidly and the DPF composition is favorable for the growth of small (52.6-26.1 μm) crystallites. On the contrary, the conditions implemented in the model saliva solution facilitate the formation of larger (198.4-41.8 μm) crystals.

  2. Molecular theory of vapor phase nucleation

    NASA Astrophysics Data System (ADS)

    Kusaka, Isamu

    1998-06-01

    An attempt has been made to establish the foundation of molecular level theory of vapor phase nucleation. We have focused on evaluating the reversible work of cluster formation and followed two major trends in this direction, namely, statistical mechanical density functional theory and molecular level simulation. We applied density functional theory to heterogeneous nucleation onto an ion. Our prime interest is to predict a sign preference of nucleation rate, which has been experimentally observed yet remained inexplicable in the classical framework. The theory indicates that asymmetry in ion-molecule interaction is directly responsible for the sign preference. The predicted sign dependence decreases as the supersaturation is increased. Our results from density functional theory agree well with the existing experimental observations. Molecular simulation offers an alternative to molecular level approach. A long-standing issue of fundamental importance in cluster simulation is the precise definition of a cluster. Thus far, all attempts of defining a cluster had introduced ad hoc criteria to determine unambiguously whether a given molecule in the system belongs to vapor or to a cluster for any instantaneous configuration of molecules. From a careful examination of the context in which a cluster should be introduced into nucleation theory, we conclude that such a criterion is unnecessary. Then, we present a new approach to cluster simulation which is free of any arbitrariness involved in the definition of a cluster. Instead, it preferentially and automatically generates the physical clusters, defined as the density fluctuations that lead to nucleation, and determines their equilibrium distribution in a single simulation. The latter feature permits one to completely bypass the computationally demanding free energy evaluation that is necessary in a conventional simulation. The method is applied first to water using the SPC/E model. We then turn to H2SO4/H2O binary

  3. Ice Nucleation and Droplet Formation by Bare and Coated Soot Particles

    SciTech Connect

    Friedman, Beth J.; Kulkarni, Gourihar R.; Beranek, Josef; Zelenyuk, Alla; Thornton, Joel A.; Cziczo, Daniel J.

    2011-09-13

    We have studied ice formation at temperatures relevant to homogeneous and heterogeneous ice nucleation, as well as droplet activation and hygroscopicity, of soot particles of variable size and composition. Coatings of adipic, malic, and oleic acid were applied to span an atmospherically relevant range of solubility, and both uncoated and oleic acid coated soot particles were exposed to ozone to simulate atmospheric oxidation. The results are interpreted in terms of onset ice nucleation, with a comparison to a mineral dust particle that acts as an efficient ice nucleus, and particle hygroscopicity. At 253K and 243K, we found no evidence of heterogeneous ice nucleation occurring above the level of detection for our experimental conditions. Above water saturation, only droplet formation was observed. At 233K, we observe the occurrence of homogeneous ice nucleation for all particles studied. Coatings also did not significantly alter the ice nucleation behavior of soot particles, but aided in the uptake of water. Hygroscopicity studies confirmed that pure soot particles were hydrophobic, and coated soot particles activated as droplets at high water supersaturations. A small amount of heterogeneous ice nucleation either below the detection limit of our instrument or concurrent with droplet formation and/or homogeneous freezing cannot be precluded, but we are able to set limits for its frequency. We conclude that both uncoated and coated soot particles representative of those generated in our studies are unlikely to significantly contribute to the global budget of heterogeneous ice nuclei at temperatures between 233K and 253K.

  4. Metadynamics studies of crystal nucleation

    PubMed Central

    Giberti, Federico; Salvalaglio, Matteo; Parrinello, Michele

    2015-01-01

    Crystallization processes are characterized by activated events and long timescales. These characteristics prevent standard molecular dynamics techniques from being efficiently used for the direct investigation of processes such as nucleation. This short review provides an overview on the use of metadynamics, a state-of-the-art enhanced sampling technique, for the simulation of phase transitions involving the production of a crystalline solid. In particular the principles of metadynamics are outlined, several order parameters are described that have been or could be used in conjunction with metadynamics to sample nucleation events and then an overview is given of recent metadynamics results in the field of crystal nucleation. PMID:25866662

  5. Enthalpy Diffusion in Multicomponent Flows

    SciTech Connect

    Cook, A W

    2008-11-12

    The enthalpy diffusion flux in the multicomponent energy equation is a well known yet frequently neglected term. It accounts for energy changes, associated with compositional changes, resulting from species diffusion. Enthalpy diffusion is important in flows where significant mixing occurs between species of dissimilar molecular weight. The term plays a critical role in preventing local violations of the entropy condition. In simulations of nonpremixed combustion, omission of the enthalpy flux can lead to anomalous temperature gradients, which may cause mixing regions to exceed ignition conditions. The term can also play a role in generating acoustic noise in turbulent mixing layers. Euler solvers that rely on numerical diffusion to mix fluids cannot accurately predict the temperature in mixed regions. On the other hand, Navier-Stokes solvers that incorporate enthalpy diffusion can provide much more accurate results.

  6. Multi-component assembly casting

    SciTech Connect

    James, Allister W.

    2015-10-13

    Multi-component vane segment and method for forming the same. Assembly includes: positioning a pre-formed airfoil component (12) and a preformed shroud heat resistant material (18) in a mold, wherein the airfoil component (12) and the shroud heat resistant material (18) each comprises an interlocking feature (24); preheating the mold; introducing molten structural material (46) into the mold; and solidifying the molten structural material such that it interlocks the pre-formed airfoil component (12) with respect to the preformed shroud heat resistant material (18) and is effective to provide structural support for the shroud heat resistant material (18). Surfaces between the airfoil component (12) and the structural material (46), between the airfoil component (12) and the shroud heat resistant material (18), and between the shroud heat resistant material (18) and the structural material (46) are free of metallurgical bonds.

  7. Uphill diffusion in multicomponent mixtures.

    PubMed

    Krishna, Rajamani

    2015-05-21

    Molecular diffusion is an omnipresent phenomena that is important in a wide variety of contexts in chemical, physical, and biological processes. In the majority of cases, the diffusion process can be adequately described by Fick's law that postulates a linear relationship between the flux of any species and its own concentration gradient. Most commonly, a component diffuses down the concentration gradient. The major objective of this review is to highlight a very wide variety of situations that cause the uphill transport of one constituent in the mixture. Uphill diffusion may occur in multicomponent mixtures in which the diffusion flux of any species is strongly coupled to that of its partner species. Such coupling effects often arise from strong thermodynamic non-idealities. For a quantitative description we need to use chemical potential gradients as driving forces. The transport of ionic species in aqueous solutions is coupled with its partner ions because of the electro-neutrality constraints; such constraints may accelerate or decelerate a specific ion. When uphill diffusion occurs, we observe transient overshoots during equilibration; the equilibration process follows serpentine trajectories in composition space. For mixtures of liquids, alloys, ceramics and glasses the serpentine trajectories could cause entry into meta-stable composition zones; such entry could result in phenomena such as spinodal decomposition, spontaneous emulsification, and the Ouzo effect. For distillation of multicomponent mixtures that form azeotropes, uphill diffusion may allow crossing of distillation boundaries that are normally forbidden. For mixture separations with microporous adsorbents, uphill diffusion can cause supra-equilibrium loadings to be achieved during transient uptake within crystals; this allows the possibility of over-riding adsorption equilibrium for achieving difficult separations. PMID:25761383

  8. Biomineralization: Ion binding and nucleation

    NASA Astrophysics Data System (ADS)

    Kröger, Roland

    2015-04-01

    The visualization of organic-acid-induced crystal growth by means of liquid-cell transmission electron microscopy can provide key insights into the nucleation of calcium carbonate in an organic matrix.

  9. Bubble nucleation in stout beers

    NASA Astrophysics Data System (ADS)

    Lee, W. T.; McKechnie, J. S.; Devereux, M. G.

    2011-05-01

    Bubble nucleation in weakly supersaturated solutions of carbon dioxide—such as champagne, sparkling wines, and carbonated beers—is well understood. Bubbles grow and detach from nucleation sites: gas pockets trapped within hollow cellulose fibers. This mechanism appears not to be active in stout beers that are supersaturated solutions of nitrogen and carbon dioxide. In their canned forms these beers require additional technology (widgets) to release the bubbles which will form the head of the beer. We extend the mathematical model of bubble nucleation in carbonated liquids to the case of two gases and show that this nucleation mechanism is active in stout beers, though substantially slower than in carbonated beers and confirm this by observation. A rough calculation suggests that despite the slowness of the process, applying a coating of hollow porous fibers to the inside of a can or bottle could be a potential replacement for widgets.

  10. Containerless Liquid to Solid Nucleation Pathways in Two Representative Grades of Commercially Available Zirconium

    NASA Technical Reports Server (NTRS)

    Rulison, A. J.; Rhim, W.-K.; Bayuzick, R.; Hofmeister, W.; Morton, C.

    1997-01-01

    Experimental measurements were conducted to determine the solid metal nucleation pathways of radiatively cooling, molten zirconium spheres of two different commercially available purity grades in a high-vacuum, high-temperature electrostatic levitator. The ensemble distribution of maximum undercooling temperatures was interpreted using Poisson statistics to determine the temperature dependence of the solid metal nucleation rate. For a sample of nominally 99.95% pure zirconium, the results are consistent with heterogeneous solid metal nucleation either on static catalyst particles at least approx. 30 nm diameter or on a surface coating. For a sample of nominally 99% pure zirconium, however, it appears that heterogeneous solid metal nucleation occurred either on a polydispersion of approx. 10 nm (mean diameter) static catalyst particles or on dynamic catalyst particles that precipitated from a solution that became supersaturated as the melt cooled.